WO2002039520A2 - Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials negative to zinc potential - Google Patents

Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials negative to zinc potential Download PDF

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Publication number
WO2002039520A2
WO2002039520A2 PCT/CA2001/001581 CA0101581W WO0239520A2 WO 2002039520 A2 WO2002039520 A2 WO 2002039520A2 CA 0101581 W CA0101581 W CA 0101581W WO 0239520 A2 WO0239520 A2 WO 0239520A2
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
electrode
electrolyte
negative
low toxicity
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.)
Ceased
Application number
PCT/CA2001/001581
Other languages
English (en)
French (fr)
Other versions
WO2002039520A3 (en
Inventor
Jeffrey Philips
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.)
PowerGenix Systems Inc
Original Assignee
PowerGenix Systems Inc
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 PowerGenix Systems Inc filed Critical PowerGenix Systems Inc
Priority to AU2002218079A priority Critical patent/AU2002218079A1/en
Priority to AT01993951T priority patent/ATE431623T1/de
Priority to JP2002541736A priority patent/JP4605988B2/ja
Priority to EP01993951A priority patent/EP1340273B1/en
Priority to DE60138727T priority patent/DE60138727D1/de
Publication of WO2002039520A2 publication Critical patent/WO2002039520A2/en
Publication of WO2002039520A3 publication Critical patent/WO2002039520A3/en
Priority to US10/429,725 priority patent/US6797433B2/en
Priority to US10/429,693 priority patent/US6811926B2/en
Anticipated expiration legal-status Critical
Ceased 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
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/24Electrodes for alkaline accumulators
    • H01M4/244Zinc electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/24Alkaline accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/24Alkaline accumulators
    • H01M10/26Selection of materials as electrolytes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/24Alkaline accumulators
    • H01M10/30Nickel accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • 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

Definitions

  • This invention relates to alkaline galvanic cells having zinc electrodes and an alkaline electrolyte. More particularly, the present invention relates to high energy density rechargeable cells having a zinc or zinc-based negative electrodes, an alkaline electrolyte, and positive electrodes which may be nickel, silver, air, or iron.
  • the capacity of the rechargeable cell should not diminish significantly over a number of cycles, there should be no significant shape change - particularly of the zinc electrode - and no significant dendrite formation.
  • newly developed high energy density rechargeable zinc cells should be free or substantially free of toxicity, so as to be environmentally benign.
  • a robust, long-lasting, rechargeable battery must be brought to the market which contains no cadmium, no lead, and no mercury.
  • the terms "cell” and "battery” may be used interchangeably.
  • a cell comprises two electrodes, one positive and one negative, and an electrolyte; and a battery may comprise a number of cells which are joined together in series, parallel, or series / parallel.
  • batteries there are a plurality of negative and positive plates and a common electrolyte all contained in a single casing; and in some cases, the plates may be bipolar.
  • cells and batteries may be cylindrical or rectangular, they may comprise flat plates or rolled plates, and they may have a relatively low voltage of one or two volts. Batteries may have a relatively high voltage, in the range of twelve to sixteen volts, sometimes much higher.
  • the present invention applies to any of the above considerations in respect of cells and batteries, as it relates to the structure of the electrodes.
  • Batteries in keeping with the present invention will find particular utility in traction markets, being used on scooters and bicycles, as well as in hybrid automobiles, and in the power tool market. In such markets, there is a very great necessity for sealed batteiy systems, which have high energy density and, therefore, relatively low weight per amp-hour unit capacity, as well as low cost per amp-hour unit capacity. Moreover, batteries in keeping with the present invention will provide high amp-hour capacity per unit volume.
  • a particular feature of the present invention is that long life, rechargeable zinc electrodes may be supplied which can be manufactured using equipment that is presently used for nickel cadmium or nickel metal-hydride production.
  • electrodes which embody the present invention are pasted on a high conductivity, low resistance matrix or carrier, which might conveniently be manufactured from copper and/or suitable alloys thereof.
  • a buffered borate electrolyte which is particularly such as that which is taught in EISENBERG United States patent No.
  • alkaline galvanic cells having an electrolyte composition which comprises a solution of a salt formed by reacting boric acid (or, alternatively, phosphoric acid or arsenic acid) with an alkali or earth alkali hydroxide which is present in a sufficient amount to produce a stoichiometric excess of hydroxide to acid in the range of 2.5 to 11.0 equivalents per litre.
  • a soluble alkali or earth or earth alkali fluoride is present, in an amount corresponding to a concentration range of 0.01 to 1.0 equivalents per litre of total solution.
  • Additions to the zinc oxide electrode of fluorides from the elements of group 2a, group 3a, group 3b, and group 4b with redox potentials which are negative of the zinc potential are expected to significantly improve the performance of the fully formed electrode by complexing the zinc and preventing migration.
  • the specific elements covered by the present invention are beryllium, magnesium, calcium, strontium, barium, titanium and aluminum.
  • a typical electrode composition contains between 0.1 and 10%) of the fluoride additive.
  • the electrode also contains between 2-10% bismuth oxide. These oxide and fluoride materials may contain zinc metal, but in most cases they consist of the additive materials and zinc oxide.
  • the mixture is pasted onto a suitable substrate and combined with separators and positive electrode into an electrochemical cell.
  • the positive electrode is a nickel oxide, to define a nickel zinc cell.
  • this invention can equally well apply to any rechargeable zinc containing battery. After the assembly of the battery the electrolyte is added, and a formation charge is applied to convert the zinc oxide to zinc metal. Normally, over 100%> of the rated capacity is input during the formation process.
  • the electrolyte of preference to work optimally with this electrode is a mixture of sodium, potassium, and lithium hydroxides, and boric or phosphoric acid.
  • the boric acid concentration is required to be 0.6 to 1.3 moles per liter.
  • the stoichiometric excess of alkali hydroxide is between 2.7 and 5M.
  • the alkaline mixture must contain between 0.1 and 3M lithium hydroxide. While this electrolyte is preferred, other mixtures can also be used. However, it has been found that electrolytes with even modest fluoride content are incompatible with lithium hydroxide additions.

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)
  • Secondary Cells (AREA)
  • Primary Cells (AREA)
PCT/CA2001/001581 2000-11-10 2001-11-07 Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials negative to zinc potential Ceased WO2002039520A2 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AU2002218079A AU2002218079A1 (en) 2000-11-10 2001-11-07 Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials negative to zinc potential
AT01993951T ATE431623T1 (de) 2000-11-10 2001-11-07 Negativ-elektrodenformulierung für eine zinkelektrode geringer toxizität mit zusatzstoffen mit zum zink-potential negativen redox-potentialen
JP2002541736A JP4605988B2 (ja) 2000-11-10 2001-11-07 酸化還元電位が亜鉛電位に対して負である添加剤を有する低毒性亜鉛電極のための陰極の配合
EP01993951A EP1340273B1 (en) 2000-11-10 2001-11-07 Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials negative to zinc potential
DE60138727T DE60138727D1 (de) 2000-11-10 2001-11-07 Negativ-elektrodenformulierung für eine zinkelektrode geringer toxizität mit zusatzstoffen mit zum zink-potential negativen redox-potentialen
US10/429,725 US6797433B2 (en) 2000-11-10 2003-05-06 Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials negative to zinc potential
US10/429,693 US6811926B2 (en) 2000-11-10 2003-05-06 Formulation of zinc negative electrode for rechargeable cells having an alkaline electrolyte

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA002325308A CA2325308A1 (en) 2000-11-10 2000-11-10 Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials negative to zinc potential
CA2,325,308 2000-11-10

Related Child Applications (3)

Application Number Title Priority Date Filing Date
US10/429,692 Continuation US6801017B2 (en) 2000-11-10 2003-05-06 Charger for rechargeable nickel-zinc battery
US10/429,725 Continuation US6797433B2 (en) 2000-11-10 2003-05-06 Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials negative to zinc potential
US10/429,693 Continuation US6811926B2 (en) 2000-11-10 2003-05-06 Formulation of zinc negative electrode for rechargeable cells having an alkaline electrolyte

Publications (2)

Publication Number Publication Date
WO2002039520A2 true WO2002039520A2 (en) 2002-05-16
WO2002039520A3 WO2002039520A3 (en) 2002-09-06

Family

ID=4167578

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA2001/001581 Ceased WO2002039520A2 (en) 2000-11-10 2001-11-07 Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials negative to zinc potential

Country Status (8)

Country Link
US (2) US6797433B2 (enExample)
EP (1) EP1340273B1 (enExample)
JP (1) JP4605988B2 (enExample)
AT (1) ATE431623T1 (enExample)
AU (1) AU2002218079A1 (enExample)
CA (1) CA2325308A1 (enExample)
DE (1) DE60138727D1 (enExample)
WO (1) WO2002039520A2 (enExample)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011017655A1 (en) 2009-08-07 2011-02-10 Powergenix Systems, Inc. Carbon fiber zinc negative electrode
WO2011031778A1 (en) 2009-09-08 2011-03-17 Powergenix Systems, Inc. Heat sealing separators for nickel zinc cells
WO2011046952A1 (en) 2009-10-13 2011-04-21 Powergenix Systems, Inc. Cylindrical nickel-zinc cell with positive can
US8048558B2 (en) 2005-04-26 2011-11-01 Powergenix Systems, Inc. Cylindrical nickel-zinc cell with negative can
WO2013119422A1 (en) 2012-02-07 2013-08-15 Powergenix Systems, Inc. Nickel-zinc rechargeable pencil battery
WO2014098875A1 (en) 2012-12-20 2014-06-26 Powergenix Systems, Inc. Controlling battery states of charge in systems having separate power sources
US9337683B2 (en) 2012-12-20 2016-05-10 Powergenix Systems, Inc. Controlling battery states of charge in systems having separate power sources

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2325791A1 (en) * 2000-11-10 2002-05-10 Jeffrey Phillips Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials positive to zinc potential
CA2377065A1 (en) 2001-03-15 2002-09-15 Powergenix Systems Inc. Alkaline cells having low toxicity rechargeable zinc electrodes
US7550230B2 (en) * 2001-03-15 2009-06-23 Powergenix Systems, Inc. Electrolyte composition for nickel-zinc batteries
US6849360B2 (en) 2002-06-05 2005-02-01 Eveready Battery Company, Inc. Nonaqueous electrochemical cell with improved energy density
US20080166632A1 (en) * 2003-08-18 2008-07-10 Powergenix, Inc. Method of manufacturing nickel zinc batteries
CN101577347B (zh) * 2003-08-18 2012-05-30 鲍尔热尼系统公司 制造镍锌电池的方法
US8703330B2 (en) * 2005-04-26 2014-04-22 Powergenix Systems, Inc. Nickel zinc battery design
US7931988B2 (en) 2007-10-05 2011-04-26 Powergenix Systems, Inc. Tin and tin-zinc plated substrates to improve Ni-Zn cell performance
US8501351B2 (en) * 2009-05-18 2013-08-06 Powergenix Systems, Inc. Pasted zinc electrode for rechargeable nickel-zinc batteries
EP2750225A4 (en) 2011-08-23 2015-07-29 Nippon Catalytic Chem Ind NEGATIVE ELECTRODE MIXTURE OR GEL ELECTROLYTE AND BATTERY WITH THIS NEGATIVE ELECTRODE MIXTURE OR THIS GEL ELECTROLYTE
WO2014037851A2 (de) * 2012-09-07 2014-03-13 Basf Se Wiederaufladbare elektrochemische zink-sauerstoff-zellen
WO2014150890A1 (en) 2013-03-15 2014-09-25 Hyperion Catalysis International, Inc. Methods of making nanofiber electrodes for batteries
CN110364660B (zh) * 2018-04-10 2022-07-15 浙江浙能中科储能科技有限公司 一种水系锌离子电池复合隔膜及制备方法
CN111463500B (zh) * 2020-03-18 2021-06-22 山东合泰新能源有限公司 一种用于锌阳极碱性二次电池的电解液的制备方法
CN114267827A (zh) * 2020-09-16 2022-04-01 松山湖材料实验室 一种锌电极及其制备方法、二次电池
JP7600946B2 (ja) * 2021-09-29 2024-12-17 トヨタ自動車株式会社 負極活物質層およびアルカリ蓄電池

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8048558B2 (en) 2005-04-26 2011-11-01 Powergenix Systems, Inc. Cylindrical nickel-zinc cell with negative can
US9947919B2 (en) 2009-08-07 2018-04-17 Zincfive Power, Inc. Carbon fiber zinc negative electrode
WO2011017655A1 (en) 2009-08-07 2011-02-10 Powergenix Systems, Inc. Carbon fiber zinc negative electrode
EP3432389A1 (en) 2009-08-07 2019-01-23 ZincFive Power, Inc. Carbon zinc negative electrode
US10763495B2 (en) 2009-08-07 2020-09-01 Zincfive Power, Inc. Carbon fiber zinc negative electrode
WO2011031778A1 (en) 2009-09-08 2011-03-17 Powergenix Systems, Inc. Heat sealing separators for nickel zinc cells
US8597379B2 (en) 2009-09-08 2013-12-03 Powergenix Systems, Inc. Method of selectively heat sealing separators for nickel zinc cells
WO2011046952A1 (en) 2009-10-13 2011-04-21 Powergenix Systems, Inc. Cylindrical nickel-zinc cell with positive can
WO2013119422A1 (en) 2012-02-07 2013-08-15 Powergenix Systems, Inc. Nickel-zinc rechargeable pencil battery
WO2014098875A1 (en) 2012-12-20 2014-06-26 Powergenix Systems, Inc. Controlling battery states of charge in systems having separate power sources
DE212012000292U1 (de) 2012-12-20 2015-07-23 Powergenix Systems, Inc. Steuerung von Batterieladezuständen bei Systemen mit getrennten Stromquellen
US9337683B2 (en) 2012-12-20 2016-05-10 Powergenix Systems, Inc. Controlling battery states of charge in systems having separate power sources
US10967755B2 (en) 2012-12-20 2021-04-06 Zincfive Power, Inc. Controlling battery states of charge in systems having separate power sources

Also Published As

Publication number Publication date
EP1340273B1 (en) 2009-05-13
EP1340273A2 (en) 2003-09-03
ATE431623T1 (de) 2009-05-15
US20030190525A1 (en) 2003-10-09
JP4605988B2 (ja) 2011-01-05
AU2002218079A1 (en) 2002-05-21
US6811926B2 (en) 2004-11-02
DE60138727D1 (de) 2009-06-25
JP2004520683A (ja) 2004-07-08
US20040033420A1 (en) 2004-02-19
US6797433B2 (en) 2004-09-28
WO2002039520A3 (en) 2002-09-06
CA2325308A1 (en) 2002-05-10

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