CA1290394C - High temperature dischargeable galvanic primary element having alkaline electrolyte - Google Patents

High temperature dischargeable galvanic primary element having alkaline electrolyte

Info

Publication number
CA1290394C
CA1290394C CA000564960A CA564960A CA1290394C CA 1290394 C CA1290394 C CA 1290394C CA 000564960 A CA000564960 A CA 000564960A CA 564960 A CA564960 A CA 564960A CA 1290394 C CA1290394 C CA 1290394C
Authority
CA
Canada
Prior art keywords
accordance
electrode
exchange membrane
ion exchange
layers
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 - Lifetime
Application number
CA000564960A
Other languages
French (fr)
Inventor
Rolf Hennrich
Heinz-Werner Nientiedt
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.)
VARTA Batterie AG
Original Assignee
VARTA Batterie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by VARTA Batterie AG filed Critical VARTA Batterie AG
Application granted granted Critical
Publication of CA1290394C publication Critical patent/CA1290394C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/04Cells with aqueous electrolyte
    • H01M6/06Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • H01M50/414Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417Polyolefins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • H01M50/414Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426Fluorocarbon polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/449Separators, membranes or diaphragms characterised by the material having a layered structure
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0002Aqueous electrolytes
    • H01M2300/0014Alkaline electrolytes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Primary Cells (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)
  • Conductive Materials (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

ABSTRACT

A primary element is provided which is dischargeable at high temperatures comprising an alkaline electrolyte in a metallic annular cylindrical housing which encloses in inwardly directed concentric order: an outer positive silver oxide or manganese dioxide electrode in the form of a pressed powder cylinder and an inner negative electrode comprising a concentrically wound cadmium electrode wherein said negative electrode is separated from said positive electrode by a separator interposed therebetween. In storage and testing it has been shown that cells produced in accordance with the present invention may be kept at temperatures of the order of 200°C for over six weeks without any loss of operability.

Description

9(~ 9~

HIGH TEMPERATURE DISCHARGEABLE GALVANIC PRIMARY
ELEMENT HAVING ALKALINE ELECTROLYTE

FIELD OF THE INVENTION

The inventi.on concerns a primary element which is dischargeable at high temperature comprising an alkaline electrolyte in a metal housing of the annular cylindrical type.

BACKGROUND OF THE INVENTION

An element of the general type subject of the present invention is disclosed in Brenner et al, U.S. Patent No.
4,650,680. Annular cylindrical cells of this type principally, because of the performance qualities of alkaline silver oxide/zinc systems are particularly desirable for probes and assistance systems utilized in the exploration of earth resources. In such explorations successively deeper earth layers must be explored and with increasing depth, the correspondingly increasing temperature becomes the deciding limiting factor in the components in the construction of the battery. I-t .is known for example, that manganese oxide cells supplied with aqueous potassium hydroxide remain fully functional above 100C in place of the Leclanche electrolytes used in conventional primary elements. A further advance having the goal of operating at the higher tempera-tures ~2~303~34 while minimizing -the corrosive attack of the aforesaid electro-lytes on the inner portions of the cell, was directed, in the aforesaid patent to the selection of resistance elements for the separator. The combination of ceramic paper and ion exchange membrane was found to be very useful.
Notwithstanding the provision of highly inert separators, alkaline manganese and silver oxide annular cylindrical cells having negative zinc electrodes, reach their operative limit at around 160C. -The reason lies less in the qualitative inferiority of the electrochemically inactive cell components than -the occurrence of explosions which were already noted in numerous cells on the third day during storage tests at 160C. The reason for these explosions is the substantial generation of gas at the zinc electrode, which occurs because the hydrogen over potential at the zinc drops with increasing tcmperature, which in turn give rise to an exponentially increasing rate of generation of gas.
It would be desirable to provide an alkaline primary element basically constructed in accordance with the known principles of construction of annular cylindrical cells and provided with an externally loca-ted positive electrode, which is modified in such a manner that it may be reliably utilized in the higher temperature ranges mentioned above without the possibility of excess gas generation.

~2~3~a~

SUMMARY OF THE INVENTION

By means of -this invention there is provided a novel primary element which is dischargeable at high temperatures comprising an alkaline electrolyte in a metallic annular cylindrical housing enclosing, in inwardly directed concentric order:
a) an outer positive silver oxide or manganese dio~ide electrode in the form of at least one pressed powder cylinder and b) an inner negative electrode comprising a concentrically wound cadmium electrode, wherein said negative electrode is separated ~rom said positive electrode by a separator interposed therebetween.
It has been ~ound desirable to construct the electrodes in a concentric configuration wherein the outer ring cylinder, which comprises the positive electrode, is made of compacted silver oxide or manganese oxide powders and the inner space, which is separated from the positive electrode by a separator comprises a coiled sheet cadmium electrode. lt has been found desirable to produce the cadmium electrode in accordance with the disclosure of DE-OS 2,822,821 wherein cadmium is deposited by cathodic deposition from a cadmium salt solution upon a metal carrier band which is then designated as an electrodeposited electrode.

~29~)39a~

BRIEF DESCRIPTION OF THE DRAWING

The drawing shows a cross-sectional elevational view of an element of the present invention.

DETAILED DESCRIPTION OF THE DRAWINGS

As shown in Figure 1, the device of the present invention comprises an annular cylindrical metallic housing cup 1.
Within this housing are located cathode rings 2 which serve as the positive electrode, made of compacted silver oxide and/or magnesium oxide powders which, if desired, further comprise a conductive material such as carbon. Internally of this annular cylinder and in contact therewith is provided a separator comprising one or more layers of thin sheets and/or fiber layers suitably comprising an outer lattice of PTFE 3 and an inner, sleeve formed, ion exchange membrane ~. The base of this sleeve is strengthened by an insulating inlay 5 also made of PTFE. As ion exchange membranes there may be utilized membranes such as radiation cross-linked polyethylene/polypropylene sheets such as those sold under the trade r-~me of Permion by RAI Research Corporation, of I,ony Island City, New York. Also suitable are equivalent sheets of Nafion~ (tetrafluorethylene/perfluorosulfonyl ethoxy vinyl ether copolymer made by E.I. duPont de Nemours of Wilminyton, Delaware). Such membranes are merely set forth as `* T, ~Je - rn Ct~` l ~L29V39~

examples. It is possible to use other separators as long as they are not negatively effected by the operating temperatures.
Yet another insulating layer 6 separates all of the internal components of the cell from the metal base of -the outer metallic cup 1. The internal space remaining is substantially occupied by the coiled cadmium electrode 7 said coil comprising a metallic carrier band of nickel, nickel/steel, silver or copper coated as aforesaid by cadmium, suitably by electrodeposition.
The negative conductor is provided by rod 8 preferably a stainless steel rod which is affixed to contact disc 9 with nut 10. I~ desired this connection can also be welded or riveted.
The contact sheet 9 is welded to and substantially encloses the top edges of the coil 7. A lid 11 closes the upper opening of metallic cup 1, the pole rod 8 passes through an opening in the said lid 11 to which it is attached by rivet ring nut 12 to Eorm the negative pole of the cell. To ensure that there is no electrical contact between the pole 8 and nut 12 on the one hand and the lid 11 on the other, there are provided sealing, suitably insulating, means 13 between the upper bottom surface and the vertical side surfaces of pole 8 and lid 11 and insulating disc 14 located between ring 12 and lid 11, both 13 and 12 being sui-tably of PTF~. Any other alkali and high temperature proof synthetic material such as polyether ketones may be utilized.
Electrolyte 15 comprises a highly concentrated solution of a~ueous alkali, suitably a~ueous potassium hydroxide but sodium ~L29~3~4 hydroxide may also be used. In the preferred embodiment the lid ll is hermetically sealed to the outer metallic housing 1 by means of laser welding.
A primary element constructed as above is operable at substantially elevated temperatures suitably 200C and more, since under the given conditions no hydrogen is generated. The internal pressure of the cell is determined by the vapor pressure of the electrolyte for example, 6 bar at 200C.
The advantages of these cells in comparison to~the prior art alkaline cylindrical cells utilizing the silver oxide/zinc or manganese dioxide/zinc systems are readily apparent.
In storage testing it has been shown that cells produced in accordance with the present invention may be kept at temperatures of the order of 200C for over six weeks without any loss of operability. In contrast thereto, commercially available alkaline high temperature cells of the silver oxide/zinc type suffered from explosions after a lapse of only 5 days at 163C
since at this point, the amount of hydrogen generated exceeded the retentive capacity of the cell.

Claims (18)

1. A primary element which is dischargeable at high temperatures comprising an alkaline electrolyte in a metallic annular cylindrical housing enclosing in inwardly directed concentric order:
a) an outer positive silver oxide or manganese dioxide electrode in the form of at least one pressed powder cylinder and b) an inner negative electrode comprising a concentrically wound cadmium electrode, wherein said negative electrode is separated from said positive electrode by a separator interposed therebetween.
2. A primary element in accordance with claim wherein said cadmium electrode comprises an electrodeposited layer of cadmium upon a metallic sheet carrier.
3. An element in accordance with claim 2 wherein the carrier is a nickel, nickel/steel, silver or copper carrier.
4. An element in accordance with claim 2 wherein the carrier is a nickel sheet carrier.
5. An element in accordance with claim 1 wherein said separator comprises at least two layers, the outer layer being a PTFE lattice and the inner layer an ion exchange membrane.
6. An element in accordance with claim 2 wherein said separator comprises at least two layers, the outer layer being a PTFE lattice and the inner layer an ion exchange membrane.
7. An element in accordance with claim 3 wherein said separator comprises at least two layers, the outer layer being a PTFE lattice and the inner layer an exchange membrane.
8. An element in accordance with claim 4 wherein said separator comprises at least two layers, the outer layer being a PTFE lattice and the inner layer an ion exchange membrane.
9. An element in accordance with claim 5 wherein the ion exchange membrane is a sleeve provided with an inner insulating insert of PTFE.
10. An element in accordance with claim 9 wherein the ion exchange membrane is radiation cross-linked polyethylene/poly-propylene copolymer.
11. An element in accordance with claim 9 wherein the ion exchange membrane is radiation cross-linked tetrafluor-ethylene/perfluorosulfonyl ethoxy vinyl ether copolymer.
12. An element in accordance with claim 1 wherein the positive electrode is silver oxide.
13. An element in accordance with claim 1 wherein the positive electrode is manganese dioxide.
14. An element in accordance with claim 1 wherein the electrolyte is concentrated aqueous potassium or sodium hydroxide.
15. An element in accordance with claim 14 wherein the electrolyte is concentrated aqueous potassium hydroxide.
16. An element in accordance with claim 1 wherein the outer housing comprises a sealed lid.
17. An element in accordance with claim 16 wherein the lid is a laser welded sealed lid.
18. An element in accordance with claim 16 wherein the negative conductor comprises a metal rod passing through said lid but electrically isolated therefrom.
CA000564960A 1987-05-02 1988-04-25 High temperature dischargeable galvanic primary element having alkaline electrolyte Expired - Lifetime CA1290394C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873714654 DE3714654A1 (en) 1987-05-02 1987-05-02 HIGH TEMPERATURE DISCHARGABLE GALVANIC PRIME ELEMENT WITH ALKALINE ELECTROLYTE
DEP3714654.8 1987-05-02

Publications (1)

Publication Number Publication Date
CA1290394C true CA1290394C (en) 1991-10-08

Family

ID=6326703

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000564960A Expired - Lifetime CA1290394C (en) 1987-05-02 1988-04-25 High temperature dischargeable galvanic primary element having alkaline electrolyte

Country Status (13)

Country Link
US (1) US4897323A (en)
EP (1) EP0289705B1 (en)
JP (1) JP2683027B2 (en)
BR (1) BR8802079A (en)
CA (1) CA1290394C (en)
DE (2) DE3714654A1 (en)
ES (1) ES2032878T3 (en)
GR (1) GR3005452T3 (en)
HK (1) HK34493A (en)
IL (1) IL85815A (en)
MX (1) MX167570B (en)
NO (1) NO171877C (en)
SG (1) SG126492G (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0354966B1 (en) * 1988-01-22 1996-06-12 Japan Storage Battery Company Limited Alkaline secondary battery and process for its production
US5427872A (en) * 1993-11-17 1995-06-27 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Dendrite preventing separator for secondary lithium batteries
KR100274889B1 (en) * 1998-05-08 2001-02-01 김순택 Cap assembly of square secondary battery
RU2153029C1 (en) * 1999-11-01 2000-07-20 Открытое акционерное общество "Интеграл" Electrolyte for cadmium plating
US7479349B2 (en) 2002-12-31 2009-01-20 Cardiac Pacemakers, Inc. Batteries including a flat plate design
US7926243B2 (en) * 2009-01-06 2011-04-19 Graham Packaging Company, L.P. Method and system for handling containers

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL82738C (en) * 1951-09-15
US2970180A (en) * 1959-06-17 1961-01-31 Union Carbide Corp Alkaline deferred action cell
FR1284552A (en) * 1960-11-23 1962-02-16 Yardney International Corp Waterproof electrochemical generator
US3945847A (en) * 1971-12-28 1976-03-23 Union Carbide Corporation Coherent manganese dioxide electrodes, process for their production, and electrochemical cells utilizing them
FR2392502A1 (en) * 1977-05-24 1978-12-22 Wonder METHOD AND DEVICE FOR MANUFACTURING NEGATIVE ELECTRODES, ESPECIALLY IN CADMIUM OR ZINC, FOR ELECTROCHEMICAL GENERATORS AND NEGATIVE ELECTRODES THUS OBTAINED
CA1128121A (en) * 1978-03-30 1982-07-20 Union Carbide Corporation Cadium compound additive for cells using divalent silver oxide
US4185144A (en) * 1978-09-05 1980-01-22 Polaroid Corporation Electrochemical cell with a cadmium patch electrode
JPS58209067A (en) * 1982-05-28 1983-12-05 Toshiba Corp Battery
DE3337570C2 (en) * 1983-10-15 1986-03-13 Varta Batterie Ag, 3000 Hannover Galvanic primary element that can be discharged at high temperatures

Also Published As

Publication number Publication date
EP0289705A2 (en) 1988-11-09
NO880924D0 (en) 1988-03-02
NO171877B (en) 1993-02-01
JPS63284762A (en) 1988-11-22
HK34493A (en) 1993-04-16
MX167570B (en) 1993-03-30
SG126492G (en) 1993-02-19
EP0289705B1 (en) 1992-06-24
EP0289705A3 (en) 1989-03-22
JP2683027B2 (en) 1997-11-26
IL85815A (en) 1991-06-30
DE3872299D1 (en) 1992-07-30
BR8802079A (en) 1988-11-29
IL85815A0 (en) 1988-09-30
GR3005452T3 (en) 1993-05-24
DE3714654A1 (en) 1988-11-10
NO880924L (en) 1988-11-03
US4897323A (en) 1990-01-30
ES2032878T3 (en) 1993-03-01
NO171877C (en) 1993-05-12

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