CA2189341A1 - Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture - Google Patents

Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture

Info

Publication number
CA2189341A1
CA2189341A1 CA002189341A CA2189341A CA2189341A1 CA 2189341 A1 CA2189341 A1 CA 2189341A1 CA 002189341 A CA002189341 A CA 002189341A CA 2189341 A CA2189341 A CA 2189341A CA 2189341 A1 CA2189341 A1 CA 2189341A1
Authority
CA
Canada
Prior art keywords
zinc
cell
cathode
powder
anode
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.)
Granted
Application number
CA002189341A
Other languages
French (fr)
Other versions
CA2189341C (en
Inventor
Josef Daniel-Ivad
Klaus Tomantschger
James R. Book
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.)
2216345 ONTARIO Inc
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of CA2189341A1 publication Critical patent/CA2189341A1/en
Application granted granted Critical
Publication of CA2189341C publication Critical patent/CA2189341C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride accumulators
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
    • 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
    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Secondary Cells (AREA)

Abstract

The zinc active powder for a mercury-free rechargeable electrochemical cell is coated with a surfactant, and separately with an aqueous solution of indium sulphate. Without any subsequent filtering, washing or drying, the powder is assembled into an electrochemical cell. The cell can include a hydrogen recombination catalyst in contact with the electrochemically active material of the cathode.

Claims (38)

1. A method of manufacturing a mercury-free zinc anode for use in a rechargeable electrochemical cell capable of at least twenty charge and recharge cycles without shorting by zinc dendrite growth, the method comprising the steps of:
(a) coating mercury-free zinc active powder with a film of an organic surfactant and with an aqueous solution of indium sulphate, the amounts of the surfactant and indium sulphate solution being such as to leave the zinc powder free flowing, wherein the indium sulphate solution is acidic; and (b) subsequently processing the coated zinc active powder into an anode, without treatment to remove sulphate ions.
2. A method as claimed in claim 1, wherein the zinc active powder is placed in a liquid to solid blender, the surfactant and the acidic indium sulphate solution are sprayed onto the zinc powder, while the powder is tumbled in the blender to achieve a uniform coating of the zinc powder particles by the film of the surfactant and the indium sulphate solution.
3. A method as claimed in claim 1 or 2, wherein the zinc active powder is selected from the group consisting of (1) metallic zinc powder of 99.98% purity (2) a zinc alloy powder containing at least 99% metallic zinc, and (3) a zinc active powder comprising in the range of up to 20% zinc oxide powder with the balance comprising of at least one of metallic zinc powder and zinc alloy powder.
4. A method as claimed in any preceding claim, wherein the aqueous solution of indium sulphate has a pH between 1 and 2.
5. A method as claimed in any preceding claim, wherein the surfactant is provided as an aqueous solution.
6. A method as claimed in any preceding claim, wherein the surfactant is added to the zinc active powder, and the indium sulphate solution is subsequently added to the zinc active powder.
7. A method as claimed in any preceding claim, which includes the following additional step after the coating is completed:
(c) adding a gelling agent and an aqueous solution of potassium hydroxide to form a gelled anode mixture.
8. A method as claimed in claim 7, when carried out in a solid to liquid blender, wherein the zinc active powder is left in the solid to liquid blender after carrying out steps (a) and (b), and step (c) is carried out in thesolid to liquid blender, with blending and tumbling of the zinc active powder being carried out continuously through steps (a), (b) and (c).
9. A method as claimed in claim 7, wherein the aqueous solution of potassium hydroxide contains dissolved in it zinc oxide up to saturation.
10. A method as claimed in any preceding claim, which comprises a part of a method of assembling an electrochemical cell, which method comprises the following additional steps of:
(1) providing an external metallic can and cathode active materials within and in contact with the can, the cathode active materials defining a hollow interior space;
(2) providing a separator on the interior of the cathode bounding the hollow interior space;
(3) filling the hollow interior space within the separator with the coated zinc active powder, a gelling agent, and an electrolyte as the gelled anode mixture;
(4) closing the container and providing a collector nail extending into the anode.
11. A method as claimed in claim 10, wherein the cathode active material comprises at least one of manganese dioxide, manganese oxyhydroxide and bismuth modified manganese oxide, and the cathode active materials are provided in the form of hollow cylindrical pellets.
12. A method as claimed in claim 11, wherein a hydrogen recombination catalyst is provided in the cell by a method selected from the following group:
(1) mixing the hydrogen recombination catalyst with the cathode active materials;
(2) providing the hydrogen recombination catalyst on the interior of the container; and (3) by providing the hydrogen recombination catalyst at the interface between the cathode active materials and the separator.
13. A mercury-free rechargeable cell capable of at least twenty charge and recharge cycles without shorting by zinc dendrite growth comprising: a cathode, an electrolyte; an anode; and a separator between the anode and the cathode, wherein the anode comprises a zinc active powder that has been coated with a film of a surfactant and a film of an aqueous, acidic solution of indium sulphate and subsequently processed into a zinc anode and then assembled into the electrochcmical cell, without treatment to remove sulphate ions.
14. A cell as claimed in claim 13, wherein the zinc active powder is selected from the group consisting of (1) metallic zinc of 99.98% purity (2) a zinc alloy powder containing at least 99% metallic zinc, and (3) a zinc active powder comprising in the range of up to 20% zinc oxide powder with the balance comprising of at least one of metallic zinc powder and zinc alloy powder.
15. A cell as claimed in claim 14, wherein the zinc powder comprises a zinc alloy powder including at least one of 0.02% to 0.08%, lead and up to 1.0% indium, with the balance being zinc.
16. A cell as claimed in claim 14 or 15, wherein the amount of the surfactant is in the range 0.001% - 0.25% by weight of the anode, and the amount of the indium sulphate is in the range of 0.01% - 0.25% by weight of the anode, and wherein the surfactant has a molecular weight in the range 300 to 1500.
17. A cell as claimed in claim 16, wherein the surfactant has a molecular weight in the range 300 to 1500 and is selected from the group consisting of compounds having polyoxypropylene chains and compounds with polyoxyethylene chains and of copolymers thereof.
18. A cell as claimed in claim 16, wherein the surfactant is polypropylene glycol having a molecular weight in the range of 400-800.
19. A cell as claimed in claim 13, wherein the electrolyte comprises an aqueous solution of at least one of (i) potassium hydroxide having a concentration in the range of about 25% to 45% and optionally including potassium zincate having a concentration in the range of 0% to 12%; and (ii) a mixture of potassium hydroxide having a concentration in the range of 4 to 6 molar and potassium fluoride having a concentration in the range 1.0 to 2.5 molar.
20. A cell as claimed in claim 19, wherein the anode includes a gelling agent, to form a gelled anode.
21. A cell as claimed in claim 19, wherein the separator includes at least one absorbent layer and at least one semipermeable membrane layer.
22. A cell as claimed in claim 19, wherein the separator consists of at least one layer of microporous polypropylene.
23. A cell as claimed in claim 19, wherein the anode comprises a pasted anode and includes 4-10% PTFE colloidal suspension and a current collector screen, and wherein the zinc active powder is kneaded with the PTFE
colloidal suspension and then rolled on to at least one side of the current collector screen.
24. A cell as claimed in claim 23, wherein the zinc active powder contains zinc oxide powder in the range of 0 to 90%; with the balance comprised of at least one of metallic zinc powder powder of 99.98% purity and a zinc alloy powder containing at least 99% zinc.
25. A cell as claimed in claim 19 or 23, wherein the electrochemically active material of the cathode comprises at least one of manganese dioxide and a bismuth modified oxide of manganese.
26. A rechargeable cell as claimed in claim 13, wherein the electrochemically active cathode materials of said cathode are mixed with graphite; and at least one of potassium hydroxide and potassium fluoride electrolyte; and which includes a finely divided hydrogen recombination catalyst comprising at least one of a hydrogen storage alloy, silver, and a silver oxide which are electronically and ionically connected to the electrochemically active components of said cathode.
27. A cell as claimed in claim 26, wherein the cathode contains barium sulphate in the range of 3-15% by weight of the cathode active material.
28. A cell as claimed in claim 27, wherein the cathode contains a hydrophobic additive in the range of .1 to 10% by weight of the active material of the cathode, which hydrophobic additive comprises at least one of polytetrafluoroethylene, polyethylene, polypropylene and metal stearate.
29. A cell as claimed in claim 26, wherein the catalyst comprises a hydrogen storage alloy, which comprises an intermetallic alloy capable of absorbing hydrogen gas and maintaining a hydrogen gas pressure below 30 atmospheres.
30. A cell as claimed in claim 26, wherein the catalyst comprises 0.1-5%
by weight of the electrochemically active material of the cathode.
31. A cell as claimed in claim 30, wherein at least a portion of the catalyst is provided in an electrically conductive coating on an external surface of the cathode.
32. A cell as claimed in claim 31, which includes an external metallic can, forming a container holding the cathode, anode and electrolyte, wherein the cathode is in contact with an inner surface of the can, and wherein the portion of the catalyst provided in a coating is located on the inner surface of the can, in contact with the cathode.
33. A cell as claimed in claim 26 or 32, wherein the electrochemically active material of the cathode comprises at least one of manganese dioxide and bismuth modified manganese oxide.
34. A mercury-free rechargeable cell, capable of at least twenty charge and discharge cycles, the cell comprising: a cathode; an electrolyte; an anode including zinc as an electrochemically active material; and a coating, including a hydrogen recombination catalyst, provided on an external surface of the cathode.
35. A cell as claimed in claim 34, wherein the hydrogen recombination catalyst is selected from the group comprising a hydrogen storage alloy, silver and silver oxide, present as a finely divided powder.
36. A cell as claimed in claim 34, which includes an external metallic can, forming a container for the cell, where the cathode is in contact with a surface of the can, and wherein the coating is provided on an inner surface of the can, and in contact with the cathode.
37. A cell as claimed in claim 36, wherein the catalyst comprises a hydrogen storage alloy, which comprises an intermetallic alloy capable of absorbing hydrogen gas and maintaining hydrogen gas pressure below 30 atmospheres.
38. A cell as claimed in claim 37, wherein the cathode includes oxides of manganese as the active material, and the cathode contains at least one of:
barium sulphate in the range of 3-15% by weight of the cathode; and a hydrophobic additive in the range of 0.1 to 10% by weight of the cathode active material, which hydrophobic additive comprises at least one of polytetrafluoroethylene, polyethylene, polypropylene, and metal stearate.
CA2189341A 1994-05-06 1994-10-17 Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture Expired - Fee Related CA2189341C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US08/239,059 1994-05-06
US08/239,059 US5626988A (en) 1994-05-06 1994-05-06 Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture
PCT/CA1994/000573 WO1995031011A1 (en) 1994-05-06 1994-10-17 Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture

Publications (2)

Publication Number Publication Date
CA2189341A1 true CA2189341A1 (en) 1995-11-16
CA2189341C CA2189341C (en) 2010-03-30

Family

ID=22900412

Family Applications (1)

Application Number Title Priority Date Filing Date
CA2189341A Expired - Fee Related CA2189341C (en) 1994-05-06 1994-10-17 Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture

Country Status (12)

Country Link
US (1) US5626988A (en)
EP (2) EP0817299A2 (en)
CN (1) CN1073292C (en)
AT (1) ATE180104T1 (en)
AU (1) AU682541B2 (en)
BR (1) BR9408576A (en)
CA (1) CA2189341C (en)
DE (1) DE69418492T2 (en)
GB (1) GB9422988D0 (en)
MY (1) MY112134A (en)
PH (1) PH31191A (en)
WO (1) WO1995031011A1 (en)

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EP0758491B1 (en) 1999-05-12
ATE180104T1 (en) 1999-05-15
AU7850894A (en) 1995-11-29
MY112134A (en) 2001-04-30
CN1116778A (en) 1996-02-14
DE69418492T2 (en) 1999-11-25
GB9422988D0 (en) 1995-01-04
EP0758491A1 (en) 1997-02-19
WO1995031011A1 (en) 1995-11-16
AU682541B2 (en) 1997-10-09
DE69418492D1 (en) 1999-06-17
US5626988A (en) 1997-05-06
PH31191A (en) 1998-04-24
CA2189341C (en) 2010-03-30
BR9408576A (en) 1997-08-19
CN1073292C (en) 2001-10-17
EP0817299A2 (en) 1998-01-07

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