RU2692753C2 - Zinc-dioxide lead alkaline-acid membrane battery - Google Patents

Zinc-dioxide lead alkaline-acid membrane battery Download PDF

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RU2692753C2
RU2692753C2 RU2017139214A RU2017139214A RU2692753C2 RU 2692753 C2 RU2692753 C2 RU 2692753C2 RU 2017139214 A RU2017139214 A RU 2017139214A RU 2017139214 A RU2017139214 A RU 2017139214A RU 2692753 C2 RU2692753 C2 RU 2692753C2
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solution
zinc
ion
concentration
sodium hydroxide
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RU2017139214A
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RU2017139214A3 (en
RU2017139214A (en
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Дмитрий Юрьевич Тураев
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Дмитрий Юрьевич Тураев
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/18Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04Diaphragms; Spacing elements
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/36Accumulators not provided for in groups H01M10/05-H01M10/34
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/24Cells comprising two different electrolytes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

FIELD: chemistry.SUBSTANCE: invention relates to a method of producing a zinc-dioxide lead alkaline-acid membrane battery. Zinc-dioxide lead alkaline-acid membrane battery represents two semi-elements: first semi-element - a lead electrode coated with a lead dioxide layer, immersed in a solution of sulphuric acid, second half-element is zinc electrode coated with zinc oxide layer immersed in sodium hydroxide solution containing zinc oxide, wherein first half-element is separated by ion-exchange membrane 1 from auxiliary electrolyte, in its turn, auxiliary electrolyte is separated by ion-exchange membrane 2 from second half-element. Auxiliary electrolyte - solution of sodium sulphate or sulphuric acid, or sodium hydroxide, or sodium sulphate and sulphuric acid, or sodium sulphate and sodium hydroxide is completely removed from space between ion-exchange membranes 1 and 2 at the end of charge.EFFECT: invention provides physical breakdown of electrochemical circuit and termination of process of mutual neutralization of electrolytes of semi-elements.4 cl

Description

Use: as a chemical source of current.

The invention relates to the production of a chemical current source using two different half-cells separated from each other by two ion-exchange membranes and an auxiliary electrolyte located between these membranes, and contains a method of preserving the active masses, electrolytes and high potential differences during storage in the long absence of external electrical load.

The purpose of the invention: to develop a new type of membrane battery containing a method for increasing the time of preservation of used active masses and electrolytes.

Chemical sources of current are known in the prior art using aqueous solutions of electrolytes and one ion exchange (cation-exchange or anion-exchange) membrane [1-4], the main difference of which from non-membrane chemical current sources with one water electrolyte is a large selection of combinations of semi-elements of different chemical composition ( electrode-electrolyte) and the possibility of obtaining for some specially selected electrochemical systems values of emf greater than 3.0 V [1], which is impossible to obtain in membraneless chemical current sources (HIT), using aqueous solutions of electrolytes.

The high value of EMF of membrane HITs using one ion-exchange membrane is caused by obtaining the highest absolute value of the electrode potential of each of the selected electrodes of the corresponding half-cell due to an adequate selection of the composition of the electrolyte solution in contact with this electrode. Separating from each other electrolytes that are heterogeneous in composition and chemical properties with a single ion-exchange membrane only in some cases inhibits the process of their mutual reaction (neutralization, etc.) observed during storage without connecting an external electrical load. Mutual neutralization of electrolytes leads to a change in the composition of the electrolyte in the half cell, which leads to a corresponding change (decrease) in the absolute value of the electrode potential and to a decrease in the emf of the HIT as a whole. The mutual neutralization of electrolytes over time even without connecting an external electrical load is very characteristic of the system described in [1], and in [5] for the same electrochemical system (Pb | PbO 2 | H 2 SO 4 || NaOH, ZnO | Zn ) a calculation showing the decrease in emf by about 2 times (from 3.17 to 1.69) after the complete mutual neutralization of electrolytes. The process of charge and discharge of the Pb | PbO 2 | H 2 SO 4 || NaOH, ZnO | Zn electrochemical system is described in detail in [1] and in [5].

This invention is directed to the improvement of the electrochemical system described in [1], which is the closest prototype.

The literature [6] provides information on storage, activation, operation and service life of backup chemical current sources of the ampoule or bulk type, using aqueous solutions of electrolytes.

In the literature [6-7], information is given that chemical current sources and batteries containing half cells of Pb | PbO 2 | H 2 SO 4 or NaOH, ZnO | Zn, have a shelf life in the charged state equal to several months.

The essence of the invention: since the half-elements Pb | Pb0 2 | H 2 S0 4 or NaOH, ZnO | Zn separately have good preservation during long-term storage, it is necessary to create conditions under which in the electrochemical system Pb | PbO 2 | H 2 SO 4 || NaOH, ZnO | Zn will break the physical contact (separation) of the half cell Pb | PbO 2 | H 2 SO 4 from the half element NaOH, ZnO | Zn. This is achieved by placing two ion-exchange membranes and an auxiliary electrolyte (located between these two ion-exchange membranes) between two half-elements:

Figure 00000001

Where:

Pb | Pb0 2 | H 2 S0 4 half cell contains a solution of sulfuric acid with a concentration of 10-70% by weight;

NaOH, ZnO | Zn half element contains sodium hydroxide solution with a concentration of 10-50% by weight, in which zinc oxide is dissolved to saturation;

12

||, || - accordingly, the ion-exchange membrane 1 and the ion-exchange membrane 2. The ion-exchange membrane 1, as well as the ion-exchange 2, can be cation-exchange of various brands, for example, MF4SK, MK-40, MK-40L or anion-exchange brands of various brands, for example, MA-40 , MA-40L. The choice of the brand of ion-exchange membrane is determined, first of all, by its ion-exchange properties, chemical resistance, type and chemical composition of the electrochemical system under consideration, as well as the location of the ion-exchange membrane relative to the selected active mass of the cell and electrolyte;

auxiliary electrolyte is a solution of sulfuric acid with a concentration of 1-70% by weight, or sodium hydroxide solution with a concentration of 1-50% by weight, or a solution of sodium sulfate with a concentration of 1-400 g / l or a solution of sulfuric acid with a concentration of 1-70% by weight . + sodium sulfate solution with a concentration of 1-400 g / l or sodium hydroxide solution with a concentration of 1-50% by weight. + sodium sulfate solution with a concentration of 1-400 g / l. If necessary, when charging or discharging a membrane chemical current source, the used volume of the auxiliary electrolyte can be periodically or continuously replaced by the same volume of fresh auxiliary electrolyte by arranging an appropriate fluid flow in a forced or gravity mode. The thickness of the auxiliary electrolyte is determined by the distance between the ion-exchange membrane 1 and the ion-exchange membrane 2 and is from 1 to 100 mm and is maintained using a special shaped separator made of chemically resistant material and located in the auxiliary electrolyte between the ion-exchange membrane 1 and 2. The separator prevents the ion-exchange contact membranes 1 and 2 with each other, which may occur, for example, due to deformation (swelling) of ion-exchange membranes when they are in contact with aqueous solutions electrolytes.

When translating the described membrane chemical current source into storage mode (for example, after carrying out the charge process), the auxiliary electrolyte is completely removed from the space between the two ion-exchange membranes, which provides a physical break in the electrochemical circuit and the termination of the process of mutual neutralization of electrolytes of the half-cells.

Structurally described membrane chemical current source of the electrochemical system:

(+) Pb | PbO 2 | H 2 SO 4 || auxiliary electrolyte || NaOH, ZnO | Zn (-) is located in a three-chamber membrane electrolyzer with two ion exchange membranes, in which each of the selected half-cells is an electrode solution chamber, and in the middle (central) chamber is an auxiliary aqueous electrolyte solution. The three-chamber membrane electrolyzer is provided with a cover in which there are openings for the installation of electrodes and the pouring of electrolyte solutions.

To charge (or discharge) the electrochemical system (1), the auxiliary electrolyte is poured into the middle (central) chamber of a three-chamber membrane electrolyzer and is charged (or discharged). When translating the membrane chemical current source into the long-term storage mode, the auxiliary electrolyte solution is completely removed (poured) from the middle chamber into a separate container, and all openings for filling electrolytes are closed with stoppers.

Example 1

In a three-chamber membrane electrolyzer with two cation-exchange membranes of the MF4SK brand, a lead electrode covered with a layer of lead dioxide and 40% by weight, a solution of sulfuric acid, is placed in one extreme chamber. In the other (opposite) extreme chamber of the same electrolyzer, a zinc electrode and 40% by mass, a sodium hydroxide solution, in which zinc oxide is dissolved to saturation, are placed. A 40% solution of sulfuric acid is poured into the middle chamber of the same membrane electrolyzer. The zinc-dioxid-lead alkaline-acid membrane battery thus obtained is ready for use. Carry out the discharge of the membrane battery on the active ohmic load. After discharging the membrane battery, it is charged from an external DC source. After the charge is over, the solution from the middle space is completely removed in a separate container, all openings for filling electrolytes are closed with stoppers, and the zinc-lead-acid alkaline-acid membrane battery is ready for long-term storage.

Example 2

In a three-chamber membrane electrolyzer with two cation-exchange membranes of the MF4SK brand, a lead electrode covered with a layer of lead dioxide and 50% by weight, a solution of sulfuric acid, is placed in one extreme chamber. In another (opposite) extreme chamber of the same electrolyzer, a zinc electrode and a 30% mass, sodium hydroxide solution, in which zinc oxide is dissolved to saturation, are placed. A 40% sodium hydroxide solution is poured into the middle chamber of the same membrane electrolyzer. The zinc-dioxid-lead alkaline-acid membrane battery thus obtained is ready for use. Carry out the discharge of the membrane battery on the active ohmic load. After discharging the membrane battery, it is charged from an external DC source. After the charge is over, the solution from the middle space is completely removed in a separate container, all openings for filling electrolytes are closed with stoppers, and the zinc-lead-acid alkaline-acid membrane battery is ready for long-term storage.

Information sources

1. Turaev D.Yu. Combined acid-base membrane battery. Patent RU 2131633 C1 Russia. Stated 11/05/97. Published 10.06.99 Bull. №16.

2. Turaev D.Yu. Alkaline salt membrane battery. Patent RU 2239260 C1 Russia. Stated 1/28/03. Published 10/27/04 Bull. №30.

3. Turaev D.Yu. Acidic combined membrane battery. Patent RU 2 282 918 C1 Russia. Stated 09.11.04. Published 08.27.06 Bull. №24.

4. Turaev D.Yu. Salt combined membrane battery. Patent RU 2 279 161 C1 Russia. Stated 09.11.04. Published 06/27/06 Bull. №18.

5. D.Yu. Turaev. The use of ion-exchange membranes in chemical current sources. Journal of Applied Chemistry. 2005, T. 78. Vol. 10., p. 1643-1647.

6. Handbook of electrochemistry. Ed. A.M. Sukhotina. - L. Chemistry, 1981.-488 p.

7. Applied electrochemistry. Ed. A.P. Tomilina, M. 1984, 520 p.

Claims (4)

1. A zinc-dioxide-lead alkaline-acid membrane battery consists of two half cells: the first half cell is a lead electrode coated with a layer of lead dioxide immersed in a solution of sulfuric acid, the second half cell is a zinc electrode coated with a layer of zinc oxide immersed in a solution of sodium hydroxide, containing zinc oxide, with the first half cell separated by an ion-exchange membrane 1 from the auxiliary electrolyte, in turn, the auxiliary electrolyte is separated by an ion-exchange membrane 2 from the second half-gel nta, characterized in that the auxiliary electrolyte - a solution of sodium sulfate or sulfuric acid or sodium hydroxide or sodium sulfate and sulfuric acid or sodium sulfate and sodium hydroxide is completely removed from the space between the ion-exchange membranes 1 and 2 at the end of the charge, which provides a physical break in the electrochemical circuit and the termination of the process of mutual neutralization of the electrolytes of the half elements.
2. Zinc-dioxide-lead alkaline-acid membrane battery according to claim 1, characterized in that a sulfuric acid solution with a concentration of 1-70% by weight is used as an auxiliary electrolyte. or sodium hydroxide solution with a concentration of 1-50% of the mass. or a solution of sodium sulfate with a concentration of 1-400 g / l or a solution of sulfuric acid with a concentration of 1-70% of the mass. + sodium sulfate solution with a concentration of 1-400 g / l or sodium hydroxide solution with a concentration of 1-50% by weight. + sodium sulfate solution with a concentration of 1-400 g / l.
3. Zinc-dioxide-lead alkaline-acid membrane battery according to claim 1, characterized in that the type of ion-exchange membrane 1 and 2 is taken from a number - MF4SK, MK-40, MK-40L, MA-40, MA-40L.
4. Zinc-dioxide-lead alkaline-acid membrane battery according to claim 1, characterized in that to improve the electrical characteristics of a chemical current source, the concentration of alkali in the zinc-zincate half cell is 41-50% of the mass.
RU2017139214A 2017-11-13 2017-11-13 Zinc-dioxide lead alkaline-acid membrane battery RU2692753C2 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU872601A1 (en) * 1980-01-02 1981-10-15 Предприятие П/Я А-7155 Method of copper electrolyte processing by electrolysis
RU2131633C1 (en) * 1997-11-05 1999-06-10 Тураев Дмитрий Юрьевич Combined acid-base-salt membrane storage battery
WO2013188636A1 (en) * 2012-06-15 2013-12-19 University Of Delaware Multiple-membrane multiple-electrolyte redox flow battery design

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU872601A1 (en) * 1980-01-02 1981-10-15 Предприятие П/Я А-7155 Method of copper electrolyte processing by electrolysis
RU2131633C1 (en) * 1997-11-05 1999-06-10 Тураев Дмитрий Юрьевич Combined acid-base-salt membrane storage battery
WO2013188636A1 (en) * 2012-06-15 2013-12-19 University Of Delaware Multiple-membrane multiple-electrolyte redox flow battery design

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