EP1577423A2 - Electrolytic cell for the production of gas - Google Patents

Electrolytic cell for the production of gas Download PDF

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Publication number
EP1577423A2
EP1577423A2 EP05003729A EP05003729A EP1577423A2 EP 1577423 A2 EP1577423 A2 EP 1577423A2 EP 05003729 A EP05003729 A EP 05003729A EP 05003729 A EP05003729 A EP 05003729A EP 1577423 A2 EP1577423 A2 EP 1577423A2
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EP
European Patent Office
Prior art keywords
cell according
electrodes
electrolyte liquid
gas
azide
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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.)
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Application number
EP05003729A
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German (de)
French (fr)
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EP1577423B1 (en
EP1577423A3 (en
Inventor
Walter Dipl.-Ing. Graf
Michael Dipl.-Ing. Weigand
Robert Glier
Renate Glier
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perma tec GmbH and Co KG
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perma tec GmbH and Co KG
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    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
    • A44B19/00—Slide fasteners
    • A44B19/24—Details
    • A44B19/26—Sliders
    • A44B19/265—Sliders with means for preventing the accidental intrusion of material into the slider body, e.g. with shield or guard
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45B—WALKING STICKS; UMBRELLAS; LADIES' OR LIKE FANS
    • A45B25/00—Details of umbrellas
    • A45B25/18—Covers; Means for fastening same

Definitions

  • the invention relates to a cell for generating gas, in particular for the operation of a lubricant dispenser, with two electrodes for connection to a current source containing circuit and an aqueous electrolyte liquid containing an azide of the formula XN 3 and located between the two electrodes for the electrochemical generation of a gas containing nitrogen (N 2 ).
  • a lubricant dispenser To meter the amount of lubricant by means of a gas-generating cell, wherein the pressure generated by means of the gas a corresponding exit of Lubricant caused by the dispenser.
  • the generation of hydrogen or oxygen to the Electrodes of a galvanic cell known (DE 35 32 335 C2).
  • the cell can optionally with a zinc anode for the production of hydrogen or with a Manganese dioxide cathode for the production of oxygen itself sufficient provide great voltage to the over an external variable resistor To set between the electrodes flowing electrolysis. additionally can also be provided a battery, which better regulation of Amperage possible.
  • the invention is based on the object, a cell with the above indicate characteristics characterized by a good gas generation rate distinguished.
  • the object is achieved in that the electrolyte liquid a magnesium salt as an additive to the chemical bonding of the containing electrochemical reaction resulting hydroxide ions.
  • the Invention is based on the finding that the magnesium salt and The hydroxide hydroxide formed magnesium hydroxide only a very small Having solubility product and according to the reaction equilibrium in the electrolyte liquid is withdrawn.
  • magnesium is in his Compounds electrochemically indifferent and also the precipitated hydrous Hydroxide gel influences ion migration in the electrolyte fluid not noticeable. With the help of the teaching of the invention, it is possible to pH of the electrolyte liquid also with increasing nitrogen formation in to keep a narrow range constant.
  • the electrolyte liquid can have a pH between 8 and 10 exhibit. Preferably, the pH is 8 - 9.5. While the azide suitably made of sodium azide is used as the magnesium salt preferably magnesium sulfate or magnesium perchlorate used. Around a sufficient withdrawal of the resulting hydroxide ions from the To ensure electrolyte fluid is the magnesium salt in relation to Amide added stoichiometrically or in excess.
  • the electrolyte liquid may be added an antifreeze, which preferably consists of ethylene glycol and / or dimethyl sulfoxide. hereby is a proper operation of the gas cell even at low temperatures guaranteed.
  • an antifreeze which preferably consists of ethylene glycol and / or dimethyl sulfoxide. hereby is a proper operation of the gas cell even at low temperatures guaranteed.
  • the electrolyte liquid nickel sulfate as an additive contain.
  • the direct oxidation of azide not only possible on precious metal electrodes, but equally well on Electrodes of steel, preferably chromium-nickel steel or graphite. alternative The electrodes can also be made of plastic with embedded graphite powder consist.
  • FIG. 1 shows a diagram which represents the evolution of gas from a pure sodium azide solution according to the prior art as a function of the content of free sodium hydroxide solution.
  • the caustic soda produced causes even at low concentrations a significant drop in the gas generation rate, so that as the gas production increases, the effectiveness of the cell decreases very rapidly.
  • Fig. 2 shows schematically the structure of a cell according to the invention for gas generation, which is particularly suitable for the operation of a lubricant dispenser.
  • the cell has two electrodes 1, 1 'for connection to a circuit 3 containing a current source 2.
  • the power source 2 may for example consist of a commercially available battery button cell.
  • a sodium azide (NaN 3 ) -containing Between the two electrodes 1, 1 'there is a sodium azide (NaN 3 ) -containing, aqueous electrolyte liquid 4, which serves for the electrochemical generation of a nitrogen (N 2 ) -containing gas.
  • a suitable receiving body 5 is provided, for receiving the electrolyte liquid 4, for receiving the electrolyte liquid 4, for receiving the electrolyte liquid 4, for receiving the electrolyte liquid 4, for receiving the electrolyte liquid 4, for receiving the electrolyte liquid 4, for receiving the electrolyte liquid 4, a suitable receiving body 5 is provided, for.
  • the applied voltage causes the following reaction at the anode 1: 2N 3 - ⁇ 3 N 2 + 2 e -, while a corresponding reduction of hydrogen ions takes place at the cathode 1 ': 2 H + + 2e - ⁇ H 2
  • the electrolyte liquid 4 is added to a magnesium salt for chemical bonding of the hydroxide ions formed during the electrochemical reaction.
  • Magnesium hydroxide has a very low solubility product, so that the magnesium hydroxide formed from the magnesium salt and the hydroxide ions according to the equation Mg 2+ + 2 OH - ⁇ Mg (OH) 2 , which is formed on the cathode 1 ', from the electrolyte liquid 4 fails.
  • the electrolyte fluid according to the invention allows for the electrodes 1, 1 'conventional materials such.
  • steel preferably chromium-nickel steel, or graphite can be used.
  • the electrodes 1, 1 ' may also be made of plastic with embedded graphite powder.
  • the magnesium perchlorate binds the sodium hydroxide formed in the reaction by formation of sparingly soluble magnesium hydroxide. This falls as Precipitation and is thus removed from the reaction equilibrium.
  • magnesium perchlorate has the advantage that the electrolyte liquid remains fluid to below - 20 ° C, so that an addition of antifreeze is not required and the electrolyte liquid can be easily absorbed in a sponge.
  • a simple separation of gas and electrolyte fluid independent of the position is provided.
  • the disposal of a cell containing the electrolyte liquid can be carried out by combustion.
  • the magnesium perchlorate is readily soluble in the water so that the volume of electrolyte can be kept small. Even at temperatures of - 20 ° C, the liquid has sufficient conductivity.
  • Perchloric acid is also a stable compound that behaves inertly under the given conditions.
  • the formation of elemental nitrogen is carried out according to the following reaction equation: 2 Na N 3 + Mg (ClO 4 ) 2 + 2H 2 O ⁇ 3 N 2 + H 2 + Mg (OH) 2 + 2 Na ClO 4 .
  • the solution is slightly alkaline, hygroscopic, odorless, non-aggressive and undecomposed. Depending on the experimental conditions, 1 ml of this solution can supply 75 to 100 ml of gas (N 2 and H 2 ).
  • FIG. 3 illustrates the effect of adding nickel sulfate according to FIG Example b) on the total cell voltage as a function of the electrolysis current.
  • graphite electrodes 10 ⁇ 10 mm were used. From the Fig. 3 it can be seen that by the addition of nickel sulfate, the hydrogen overvoltage the cathode forming electrode can be reduced and at the same cell current compared to the solution a) a corresponding lower cell voltage sets.
  • FIG. 4 illustrates the course of the cell voltage as a function of the current at + 20 ° C and - 20 ° C. It can be seen that the lowering the temperature at the same cell current requires a higher cell voltage.
  • the in Fig. 4 illustrated diagram has been for the electrolyte liquid according to the Example b) created, which even at -20 ° C still sufficiently large cell currents ensures that allow use of the cell according to the invention.

Abstract

Cells (I) for gas production (preferably for operating a lubricant dispenser), comprise two electrodes (1, 1'), which are connected at one end with a current source (2) containing electric circuit (3); and an azide compound containing aqueous electrolyte liquid (4) for electro-chemical production of a nitrogen (N 2) gas is situated between the two electrodes. Cells (I) for gas production (preferably for operating a lubricant dispenser), comprises two electrodes (1, 1'), which are connected at one end with a current source (2) containing electric circuit (3); and an azide compound of formula (XN 3) containing aqueous electrolyte liquid (4) for electro-chemical production of a nitrogen (N 2) gas is situated between the two electrodes, where the electrolyte liquid contains a magnesium salt as additive for the chemical bond with the electro-chemical reaction resulting hydroxide ions.

Description

Die Erfindung betrifft eine Zelle zur Gaserzeugung, insbesondere für den Betrieb eines Schmierstoffspenders, mit
   zwei Elektroden zum Anschluss an einen eine Stromquelle enthaltenden Stromkreis und
   einer zwischen den beiden Elektroden befindlichen, ein Azid der Formel XN3 enthaltenden, wässrigen Elektrolytflüssigkeit zur elektrochemischen Erzeugung eines Stickstoff (N2) enthaltenden Gases.The invention relates to a cell for generating gas, in particular for the operation of a lubricant dispenser, with
two electrodes for connection to a current source containing circuit and
an aqueous electrolyte liquid containing an azide of the formula XN 3 and located between the two electrodes for the electrochemical generation of a gas containing nitrogen (N 2 ).

In der Praxis ist es bekannt, die von einem Schmierstoffspender abgegebene Schmierstoffmenge mittels einer ein Gas erzeugenden Zelle zu dosieren, wobei der mit Hilfe des Gases erzeugte Druck einen entsprechenden Austritt von Schmierstoff aus dem Spender verursacht. In diesem Zusammenhang ist beispielsweise die Erzeugung von Wasserstoff oder Sauerstoff an den Elektroden einer galvanischen Zelle bekannt (DE 35 32 335 C2). Die Zelle kann ggf. mit einer Zinkanode zur Erzeugung von Wasserstoff oder mit einer Mangandioxidkathode zur Erzeugung von Sauerstoff selbst eine ausreichend große Spannung liefern, um über einen äußeren regelbaren Widerstand den zwischen den Elektroden fließenden Elektrolysestrom einzustellen. Zusätzlich kann auch eine Batterie vorgesehen sein, welche eine bessere Regelung der Stromstärke ermöglicht.In practice, it is known that discharged from a lubricant dispenser To meter the amount of lubricant by means of a gas-generating cell, wherein the pressure generated by means of the gas a corresponding exit of Lubricant caused by the dispenser. In this context is For example, the generation of hydrogen or oxygen to the Electrodes of a galvanic cell known (DE 35 32 335 C2). The cell can optionally with a zinc anode for the production of hydrogen or with a Manganese dioxide cathode for the production of oxygen itself sufficient provide great voltage to the over an external variable resistor To set between the electrodes flowing electrolysis. additionally can also be provided a battery, which better regulation of Amperage possible.

Aus der Druckschrift DE 692 26 770 T2 ist eine Gaszelle bekannt, bei der durch Elektrolyse aus einer Natriumazidlösung Stickstoff gebildet wird. Bei der Elektrolyse einer wässrigen Natriumazidlösung fällt die Gaserzeugungsrate mit zunehmender Stickstoffbildung schnell ab, da die bei der Reaktion entstehenden Hydroxid-lonen zu einem starken Anstieg des pH-Wertes in der Lösung führen, wie die nachfolgende Reaktionsgleichung zeigt: 2 NaN3 + 2 H2O → 3N2 + H2 + 2 NaOH From the document DE 692 26 770 T2 a gas cell is known in which by electrolysis of a Natriumazidlösung nitrogen is formed. In the electrolysis of an aqueous sodium azide solution, the gas generation rate drops rapidly with increasing nitrogen formation, since the hydroxide ions formed in the reaction lead to a sharp increase in the pH in the solution, as the following reaction equation shows: 2 NaN 3 + 2 H 2 O → 3N 2 + H 2 + 2 NaOH

Bei hohen pH-Werten unterbleibt die Bildung von freiem Stickstoff, und es wird lediglich Wasser zersetzt. Übliche Puffersubstanzen, z. B. Phosphate sind zur Lösung dieses Problems ungeeignet, da deren Pufferkapazität zu klein ist.At high pHs, the formation of free nitrogen is avoided and it becomes only decomposes water. Usual buffer substances, eg. B. phosphates are for Solution of this problem unsuitable because its buffer capacity is too small.

Eine Verbesserung ist möglich, durch Zusatz von Kaliumjodid und Kaliumthiocyanat, jedoch handelt es sich hierbei um Substanzen, die sich gegenüber Metallen aggressiv verhalten, so dass entsprechend edle Metalle oder Graphitelektroden eingesetzt werden müssen.An improvement is possible by addition of potassium iodide and potassium thiocyanate, however, these are substances that face each other Metals behave aggressively, so that correspondingly noble metals or graphite electrodes must be used.

Der Erfindung liegt die Aufgabe zu Grunde, eine Zelle mit den eingangs beschriebenen Merkmalen anzugeben, die sich durch eine gute Gaserzeugungsrate auszeichnet.The invention is based on the object, a cell with the above indicate characteristics characterized by a good gas generation rate distinguished.

Erfindungsgemäß wird die Aufgabe dadurch gelöst, dass die Elektrolytflüssigkeit ein Magnesiumsalz als Zusatz zur chemischen Bindung von bei der elektrochemischen Reaktion entstehenden Hydroxid-Ionen enthält. Die Erfindung beruht auf der Erkenntnis, dass das aus dem Magnesiumsalz und den Hydroxid-lonen gebildete Magnesiumhydroxid lediglich ein sehr kleines Löslichkeitsprodukt aufweist und entsprechend dem Reaktionsgleichgewicht in der Elektrolytflüssigkeit entzogen wird. Zudem ist Magnesium in seinen Verbindungen elektrochemisch indifferent und auch das ausgefallene wasserhaltige Hydroxidgel beeinflusst die lonenwanderung in der Elektrolytflüssigkeit nicht merklich. Mit Hilfe der erfindungsgemäßen Lehre ist es möglich, den pH-Wert der Elektrolytflüssigkeit auch mit zunehmender Stickstoffbildung in einem engen Bereich konstant zu halten. Da die aus dem Azid zunächst gebildete Stickstoffwasserstoffsäure eine schwache und gleichzeitig leicht flüchtige Säure darstellt, ist die Lösung von Anfang an schwach alkalisch eingestellt. Die Elektrolytflüssigkeit kann einen pH-Wert zwischen 8 und 10 aufweisen. Vorzugsweise beträgt der pH-Wert 8 - 9,5. Während das Azid zweckmäßigerweise aus Natriumazid besteht, wird als Magnesiumsalz vorzugsweise Magnesiumsulfat oder Magnesiumperchlorat verwendet. Um einen ausreichenden Entzug der entstehenden Hydroxid-lonen aus der Elektrolytflüssigkeit zu gewährleisten, ist das Magnesiumsalz im Verhältnis zur Azidmenge stöchiometrisch oder im Überschuss zugesetzt.According to the invention the object is achieved in that the electrolyte liquid a magnesium salt as an additive to the chemical bonding of the containing electrochemical reaction resulting hydroxide ions. The Invention is based on the finding that the magnesium salt and The hydroxide hydroxide formed magnesium hydroxide only a very small Having solubility product and according to the reaction equilibrium in the electrolyte liquid is withdrawn. In addition, magnesium is in his Compounds electrochemically indifferent and also the precipitated hydrous Hydroxide gel influences ion migration in the electrolyte fluid not noticeable. With the help of the teaching of the invention, it is possible to pH of the electrolyte liquid also with increasing nitrogen formation in to keep a narrow range constant. Since the first from the azide Hydrazoic acid formed a weak and light at the same time is volatile acid, the solution is slightly alkaline from the beginning set. The electrolyte liquid can have a pH between 8 and 10 exhibit. Preferably, the pH is 8 - 9.5. While the azide suitably made of sodium azide is used as the magnesium salt preferably magnesium sulfate or magnesium perchlorate used. Around a sufficient withdrawal of the resulting hydroxide ions from the To ensure electrolyte fluid is the magnesium salt in relation to Amide added stoichiometrically or in excess.

Der Elektrolytflüssigkeit kann ein Frostschutzmittel zugesetzt sein, welches vorzugsweise aus Ethylenglykol und/oder Dimethylsulfoxid besteht. Hierdurch ist auch bei tiefen Temperaturen ein ordnungsgemäßer Betrieb der Gaszelle gewährleistet. Zur Vermeidung einer Wasserstoffüberspannung der die Kathode bildenden Elektrode kann die Elektrolytflüssigkeit Nickelsulfat als Zusatz enthalten. Bei der erfindungsgemäßen Lehre ist die direkte Oxidation von Azid nicht nur an Edelmetallelektroden möglich, sondern ebenso gut auch an Elektroden aus Stahl, vorzugsweise Chrom-Nickel-Stahl oder Graphit. Alternativ können die Elektroden auch aus Kunststoff mit eingebettetem Graphitpulver bestehen.The electrolyte liquid may be added an antifreeze, which preferably consists of ethylene glycol and / or dimethyl sulfoxide. hereby is a proper operation of the gas cell even at low temperatures guaranteed. To avoid a hydrogen overvoltage of the cathode forming electrode, the electrolyte liquid nickel sulfate as an additive contain. In the teaching of the invention is the direct oxidation of azide not only possible on precious metal electrodes, but equally well on Electrodes of steel, preferably chromium-nickel steel or graphite. alternative The electrodes can also be made of plastic with embedded graphite powder consist.

Im Folgenden wird die Erfindung anhand einer lediglich ein Ausführungsbeispiel darstellenden Zeichnung ausführlich erläutert. Es zeigen schematisch:

Fig. 1
die Gasentwicklung aus einer reinen Natriumazid-Lösung in Abhängigkeit vom Gehalt an freier Natronlauge,
Fig. 2
den Aufbau einer erfindungsgemäßen Zelle zur Gaserzeugung,
Fig. 3
den Einfluss von Nickel auf die Zellspannung und
Fig. 4
die Zellspannung in Abhängigkeit vom Zellstrom bei unterschiedlichen Temperaturen.
In the following the invention will be explained in detail with reference to a drawing showing only one embodiment. They show schematically:
Fig. 1
the evolution of gas from a pure sodium azide solution as a function of the content of free sodium hydroxide solution,
Fig. 2
the construction of a gas generating cell according to the invention,
Fig. 3
the influence of nickel on the cell voltage and
Fig. 4
the cell voltage as a function of the cell current at different temperatures.

In der Fig. 1 ist ein Diagramm dargestellt, welches die Gasentwicklung aus einer reinen Natriumazid-Lösung gemäß dem Stand der Technik in Abhängigkeit vom Gehalt an freier Natronlauge darstellt. Die bei dem Zerfall des Azids gemäß der Gleichung 2 NaN3 + 2 H2O → 3N2 + H2 + 2 NaOH entstehende Natronlauge verursacht bereits in geringen Konzentrationen einen deutlichen Abfall der Gaserzeugungsrate, so dass mit zunehmender Gasproduktion die Wirksamkeit der Zelle sehr schnell nachlässt.FIG. 1 shows a diagram which represents the evolution of gas from a pure sodium azide solution according to the prior art as a function of the content of free sodium hydroxide solution. The case of the decay of the azide according to the equation 2 NaN 3 + 2 H 2 O → 3N 2 + H 2 + 2 NaOH The caustic soda produced causes even at low concentrations a significant drop in the gas generation rate, so that as the gas production increases, the effectiveness of the cell decreases very rapidly.

Die Fig. 2 zeigt schematisch den Aufbau einer erfindungsgemäßen Zelle zur Gaserzeugung, die insbesondere für den Betrieb eines Schmierstoffspenders geeignet ist. Die Zelle weist zwei Elektroden 1, 1' zum Anschluss an einen eine Stromquelle 2 enthaltenden Stromkreis 3 auf. Die Stromquelle 2 kann beispielsweise aus einer handelsüblichen Batterieknopfzelle bestehen. Zwischen den beiden Elektroden 1, 1' befindet sich eine Natriumazid (NaN3) enthaltende, wässrige Elektrolytflüssigkeit 4, die zur elektrochemischen Erzeugung eines Stickstoff (N2) enthaltenden Gases dient. Zur Aufnahme der Elektrolytflüssigkeit 4 ist ein geeigneter Aufnahmekörper 5 vorgesehen, z. B. in Form eines porösen Körpers oder eines mit Bohrungen versehenen Behälters, wobei in dem Behälter auch ein Schwamm, Vlies oder ähnliches Speichermedium angeordnet sein kann. Durch die angelegte Spannung wird an der Anode 1 die folgende Reaktion hervorgerufen: 2N3 - → 3 N2 + 2 e-, während an der Kathode 1' eine entsprechende Reduktion von Wasserstoffionen erfolgt: 2 H+ + 2e- → H2 Fig. 2 shows schematically the structure of a cell according to the invention for gas generation, which is particularly suitable for the operation of a lubricant dispenser. The cell has two electrodes 1, 1 'for connection to a circuit 3 containing a current source 2. The power source 2 may for example consist of a commercially available battery button cell. Between the two electrodes 1, 1 'there is a sodium azide (NaN 3 ) -containing, aqueous electrolyte liquid 4, which serves for the electrochemical generation of a nitrogen (N 2 ) -containing gas. For receiving the electrolyte liquid 4, a suitable receiving body 5 is provided, for. Example in the form of a porous body or a container provided with holes, wherein in the container and a sponge, nonwoven or similar storage medium can be arranged. The applied voltage causes the following reaction at the anode 1: 2N 3 - → 3 N 2 + 2 e -, while a corresponding reduction of hydrogen ions takes place at the cathode 1 ': 2 H + + 2e - → H 2

Da bei der Reaktion gemäß der für die Kathode 1' geltenden Reaktionsgleichung Wasserstoffionen verbraucht werden, steigt die Konzentration der Hydroxid-lonen während der Stickstofferzeugung deutlich an. Um einen damit einhergehenden Anstieg des pH-Wertes in der Elektrolytflüssigkeit 4 zu vermeiden, ist der Elektrolytflüssigkeit 4 ein Magnesiumsalz zur chemischen Bindung der bei der elektrochemischen Reaktion entstehenden Hydroxid-lonen zugesetzt. Magnesiumhydroxid besitzt ein sehr geringes Löslichkeitsprodukt, so dass das aus dem Magnesiumsalz und den Hydroxid-lonen gebildete Magnesiumhydroxid entsprechend der Gleichung Mg2+ + 2 OH- → Mg (OH)2, welches an der Kathode 1' gebildet wird, aus der Elektrolytflüssigkeit 4 ausfällt. Die erfindungsgemäße Elektrolytflüssigkeit erlaubt es, dass für die Elektroden 1, 1' herkömmliche Materialien, wie z. B. Stahl, vorzugsweise Chrom-Nickel-Stahl, oder Graphit verwendet werden können. Alternativ können die Elektroden 1, 1' auch aus Kunststoff mit eingebettetem Graphitpulver bestehen.Since hydrogen ions are consumed in the reaction according to the reaction equation applicable to the cathode 1 ', the concentration of the hydroxide ions during nitrogen production increases significantly. In order to avoid a concomitant increase in the pH in the electrolyte liquid 4, the electrolyte liquid 4 is added to a magnesium salt for chemical bonding of the hydroxide ions formed during the electrochemical reaction. Magnesium hydroxide has a very low solubility product, so that the magnesium hydroxide formed from the magnesium salt and the hydroxide ions according to the equation Mg 2+ + 2 OH - → Mg (OH) 2 , which is formed on the cathode 1 ', from the electrolyte liquid 4 fails. The electrolyte fluid according to the invention allows for the electrodes 1, 1 'conventional materials such. As steel, preferably chromium-nickel steel, or graphite can be used. Alternatively, the electrodes 1, 1 'may also be made of plastic with embedded graphite powder.

Beispiel:Example:

Es wurden die folgenden Elektrolytflüssigkeiten hergestellt:

  • a) 15,0 g Natriumazid
       31,0 g Magnesiumperchlorat, Gehalt 83 Gew.-%, wasserhaltig 100 ml Wasser.
  • b) Zusammensetzung wie unter a), jedoch mit Zusatz von 0,25 g Nickelsulfat * 6 H2O.
    • The following electrolyte fluids were prepared:
  • a) 15.0 g of sodium azide
    31.0 g of magnesium perchlorate, content 83% by weight, water-containing 100 ml of water.
  • b) Composition as under a), but with the addition of 0.25 g of nickel sulfate * 6 H 2 O.

    • Das Magnesiumperchlorat bindet die bei der Reaktion entstehende Natronlauge durch Bildung von schwer löslichem Magnesiumhydroxid. Dieses fällt als Niederschlag aus und wird dadurch dem Reaktionsgleichgewicht entzogen.The magnesium perchlorate binds the sodium hydroxide formed in the reaction by formation of sparingly soluble magnesium hydroxide. This falls as Precipitation and is thus removed from the reaction equilibrium.

    Die Verwendung von Magnesiumperchlorat besitzt den Vorteil, dass die Elektrolytflüssigkeit bis unter - 20 °C dünnflüssig bleibt, so dass ein Zusatz von Frostschutzmitteln nicht erforderlich ist und die Elektrolytflüssigkeit leicht in einem Schwamm aufgenommen werden kann. Hierdurch ist im praktischen Betrieb eine einfache von der Lage unabhängige Trennung von Gas und Elektrolytflüssigkeit gegeben. Die Entsorgung einer die Elektrolytflüssigkeit enthaltenen Zelle (s. Fig. 2) kann durch Verbrennung erfolgen. Das Magnesiumperchlorat ist im Wasser leicht löslich, so dass das Elektrolytvolumen klein gehalten werden kann. Auch bei Temperaturen von - 20 °C weist die Flüssigkeit eine ausreichende Leitfähigkeit auf. Perchlorsäure ist ferner eine stabile Verbindung, die sich unter den gegebenen Bedingungen inert verhält. Die Bildung von elementarem Stickstoff erfolgt gemäß der folgenden Reaktionsgleichung: 2 Na N3 + Mg (ClO4)2 + 2H2O → 3 N2 + H2 + Mg (OH)2 + 2 Na ClO4. The use of magnesium perchlorate has the advantage that the electrolyte liquid remains fluid to below - 20 ° C, so that an addition of antifreeze is not required and the electrolyte liquid can be easily absorbed in a sponge. As a result, in practice a simple separation of gas and electrolyte fluid independent of the position is provided. The disposal of a cell containing the electrolyte liquid (see Fig. 2) can be carried out by combustion. The magnesium perchlorate is readily soluble in the water so that the volume of electrolyte can be kept small. Even at temperatures of - 20 ° C, the liquid has sufficient conductivity. Perchloric acid is also a stable compound that behaves inertly under the given conditions. The formation of elemental nitrogen is carried out according to the following reaction equation: 2 Na N 3 + Mg (ClO 4 ) 2 + 2H 2 O → 3 N 2 + H 2 + Mg (OH) 2 + 2 Na ClO 4 .

    Die Lösung ist schwach alkalisch, hygroskopisch, geruchlos, nicht aggressiv und unzersetzt haltbar. 1 ml dieser Lösung kann je nach Versuchsbedingungen 75 bis 100 ml Gas (N2 und H2) liefern. The solution is slightly alkaline, hygroscopic, odorless, non-aggressive and undecomposed. Depending on the experimental conditions, 1 ml of this solution can supply 75 to 100 ml of gas (N 2 and H 2 ).

    Die Fig. 3 veranschaulicht die Wirkung eines Zusatzes von Nickelsulfat gemäß Beispiel b) auf die gesamte Zellspannung in Abhängigkeit von der Elektrolysestromstärke. Hierbei wurden Graphitelektroden 10 x 10 mm verwendet. Aus der Fig. 3 ist ersichtlich, dass durch den Zusatz von Nickelsulfat die Wasserstoffüberspannung der die Kathode bildenden Elektrode reduziert werden kann und sich bei gleichem Zellstrom im Vergleich zur Lösung a) eine entsprechend niedrigere Zellspannung einstellt.FIG. 3 illustrates the effect of adding nickel sulfate according to FIG Example b) on the total cell voltage as a function of the electrolysis current. In this case, graphite electrodes 10 × 10 mm were used. From the Fig. 3 it can be seen that by the addition of nickel sulfate, the hydrogen overvoltage the cathode forming electrode can be reduced and at the same cell current compared to the solution a) a corresponding lower cell voltage sets.

    Die Fig. 4 veranschaulicht den Verlauf der Zellspannung in Abhängigkeit von der Stromstärke bei + 20 °C und - 20 °C. Es ist erkennbar, dass die Absenkung der Temperatur bei gleichem Zellstrom eine höhere Zellspannung erfordert. Das in Fig. 4 dargestellte Diagramm wurde für die Elektrolytflüssigkeit gemäß dem Beispiel b) erstellt, welche auch bei -20 °C noch ausreichend große Zellströme gewährleistet, die einen Einsatz der erfindungsgemäßen Zelle ermöglichen.FIG. 4 illustrates the course of the cell voltage as a function of the current at + 20 ° C and - 20 ° C. It can be seen that the lowering the temperature at the same cell current requires a higher cell voltage. The in Fig. 4 illustrated diagram has been for the electrolyte liquid according to the Example b) created, which even at -20 ° C still sufficiently large cell currents ensures that allow use of the cell according to the invention.

    Claims (9)

    Zelle zur Gaserzeugung, insbesondere für den Betrieb eines Schmierstoffspenders, mit
       zwei Elektroden (1,1') zum Anschluss an einen eine Stromquelle (2) enthaltenden Stromkreis (3) und
       einer zwischen den beiden Elektroden (1, 1') befindlichen, ein Azid der Formel XN3 enthaltenden, wässrigen Elektrolytflüssigkeit (4) zur elektrochemischen Erzeugung eines Stickstoff (N2) enthaltenden Gases,
    dadurch gekennzeichnet, dass die Elektrolytflüssigkeit (4) ein Magnesiumsalz als Zusatz zur chemischen Bindung von bei der elektrochemischen Reaktion entstehenden Hydroxid-lonen enthält.    Cell for generating gas, in particular for the operation of a lubricant dispenser, with
    two electrodes (1,1 ') for connection to a current source (2) containing circuit (3) and
    an aqueous electrolyte liquid (4) containing an azide of the formula XN 3 between the two electrodes (1, 1 ') for the electrochemical generation of a gas containing nitrogen (N 2 ),
    characterized in that the electrolyte liquid (4) contains a magnesium salt as an additive for the chemical bonding of hydroxide ions formed in the electrochemical reaction.         Zelle nach Anspruch 1, dadurch gekennzeichnet, dass das Azid aus Natriumazid besteht.Cell according to claim 1, characterized in that the azide consists of sodium azide. Zelle nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Magnesiumsalz aus Magnesiumsulfat besteht.Cell according to claim 1 or 2, characterized in that the magnesium salt consists of magnesium sulphate. Zelle nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Magnesiumsalz aus Magnesiumperchlorat besteht.Cell according to claim 1 or 2, characterized in that the magnesium salt consists of magnesium perchlorate. Zelle nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Magnesiumsalz im Verhältnis zur Azidmenge stöchiometrisch oder im Überschuss zugesetzt ist. Cell according to one of claims 1 to 4, characterized in that the magnesium salt is added stoichiometrically or in excess in relation to the amount of azide. Zelle nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Elektrolytflüssigkeit (4) ein Frostschutzmittel zugesetzt ist.Cell according to one of claims 1 to 5, characterized in that the electrolyte liquid (4) is added to an antifreeze. Zelle nach Anspruch 6, dadurch gekennzeichnet, dass das Frostschutzmittel aus Ethylenglykol und/oder Dimethylsulfoxid besteht.Cell according to claim 6, characterized in that the antifreeze consists of ethylene glycol and / or dimethyl sulfoxide. Zelle nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Elektrolytflüssigkeit (4) Nickelsulfat als Zusatz zur Vermeidung einer Wasserstoffüberspannung der die Kathode bildenden Elektrode (1') enthält.Cell according to one of claims 1 to 7, characterized in that the electrolyte liquid (4) contains nickel sulfate as an additive for preventing a hydrogen overvoltage of the electrode forming the cathode (1 '). Zelle nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Elektroden (1, 1') aus Stahl, vorzugsweise Chrom-Nickel-Stahl, Graphit oder aus Kunststoff mit eingebettetem Graphitpulver bestehen.Cell according to one of claims 1 to 8, characterized in that the electrodes (1, 1 ') made of steel, preferably chromium-nickel steel, graphite or plastic with embedded graphite powder.
    EP05003729A 2004-03-19 2005-02-22 Electrolytic cell for the production of gas Active EP1577423B1 (en)

    Applications Claiming Priority (4)

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    DE102004013593 2004-03-19
    DE102004013593 2004-03-19
    DE102004032260A DE102004032260B4 (en) 2004-03-19 2004-07-03 Cell for gas production
    DE102004032260 2004-07-03

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    EP1577423A2 true EP1577423A2 (en) 2005-09-21
    EP1577423A3 EP1577423A3 (en) 2008-02-13
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    EP (1) EP1577423B1 (en)
    JP (1) JP4210664B2 (en)
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    AT (1) ATE417143T1 (en)
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    Cited By (1)

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    DE102011004799A1 (en) * 2011-02-25 2012-08-30 Varta Microbattery Gmbh Status indicator for temperature-sensitive goods

    Families Citing this family (2)

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    DE102007010518B4 (en) * 2007-03-05 2009-03-19 Perma-Tec Gmbh & Co. Kg Method for dispensing lubricants and gas generating element for carrying out the method
    DE102007037422A1 (en) 2007-08-08 2009-02-19 Perma-Tec Gmbh & Co. Kg lubricant dispenser

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    US20040031695A1 (en) * 1998-07-14 2004-02-19 Colin Oloman Electrolytic generation of nitrogen
    US20030146104A1 (en) * 2002-02-01 2003-08-07 Colin Oloman Electrolytic generation of nitrogen using azole derivatives

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    DE102011004799B4 (en) * 2011-02-25 2012-09-27 Varta Microbattery Gmbh Status indicator for temperature-sensitive goods

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    AU2005201076B2 (en) 2009-09-17
    ATE417143T1 (en) 2008-12-15
    DE102004032260B4 (en) 2006-04-27
    DE102004032260A1 (en) 2006-02-23
    KR20060043761A (en) 2006-05-15
    AU2005201076A1 (en) 2005-10-06
    US20080226953A1 (en) 2008-09-18
    ES2318373T3 (en) 2009-05-01
    EP1577423B1 (en) 2008-12-10
    JP2005264333A (en) 2005-09-29
    US20050205418A1 (en) 2005-09-22
    EP1577423A3 (en) 2008-02-13
    JP4210664B2 (en) 2009-01-21
    US7563355B2 (en) 2009-07-21

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