EP1218957A1 - Piles a base de nickel-zinc rechargeables - Google Patents

Piles a base de nickel-zinc rechargeables

Info

Publication number
EP1218957A1
EP1218957A1 EP00958057A EP00958057A EP1218957A1 EP 1218957 A1 EP1218957 A1 EP 1218957A1 EP 00958057 A EP00958057 A EP 00958057A EP 00958057 A EP00958057 A EP 00958057A EP 1218957 A1 EP1218957 A1 EP 1218957A1
Authority
EP
European Patent Office
Prior art keywords
cell
nickel
cathode
anode
zinc
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.)
Withdrawn
Application number
EP00958057A
Other languages
German (de)
English (en)
Inventor
W. Technical University Graz TAUCHER-MAUTNER
Karl Technical University Graz KORDESCH
Wayne Hartford
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.)
Energy Ventures Inc
Original Assignee
Energy Ventures 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 Energy Ventures Inc filed Critical Energy Ventures Inc
Publication of EP1218957A1 publication Critical patent/EP1218957A1/fr
Withdrawn legal-status Critical Current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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/806—Nonwoven fibrous fabric containing only fibres
    • 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
    • H01M10/28—Construction or manufacture
    • H01M10/283—Cells or batteries with two cup-shaped or cylindrical collectors
    • 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
    • H01M10/30—Nickel 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/78—Shapes other than plane or cylindrical, e.g. helical
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to rechargeable nickel-zinc alkaline cells.
  • Alkaline nickel-zinc cells in the form of plate cells are commonly known but have not achieved commercial importance to date, mainly due to the limited life of the zinc electrode. Deterioration of the zinc electrode is caused by a change in the shape of the electrode, the growth of zinc dendrites, and corrosion of the electrode.
  • cells In order to reduce the solubility of zinc and, thereby reduce any shape change of the electrode, cells have been formed using electrolytes with low alkalinity and containing KF and K CO 3 and Ca (OH) 2 as anode additives.
  • plate type sealed nickel-zinc cells dendrite formation is mostly eliminated since any dendrite produced is quickly oxidized by the oxygen present in the system.
  • Ni-Zinc Batteries D. Linden (ed.), Handbook of Batteries, Chapter 29, McGraw-Hill, Inc., NY, 1995
  • J. Jindra J. Power Sources, 66, 15 (1997)
  • the contents of these publications are incorporated herein by reference.
  • Ni-Zn cell system follows the following reaction:
  • NiOOH + Zn + 2 H 2 O ⁇ > 2 Ni(OH) 2 + Zn(OH) 2
  • Oxygen evolution has been found to occur at the end of a charge cycle (i.e. at a charge state of approximately 70-80%) and during overcharging of a cell (which is necessary for a better charge acceptance of the nickel electrode).
  • oxygen can be directly recombined at the zinc electrode or an auxiliary electrode can be incorporated to enhance recombination.
  • hydrogen evolution can also occur at the zinc electrode.
  • a sufficient excess of ZnO has to be provided. In general a Zn:Ni ratio between about 2 and 3 should be established.
  • Niobium-zinc cells different types of nickel electrodes are used: sintered, nonsintered and lightweight substrates. A description of such electrodes is provided in "Handbook of Batteries” (David Lindon (ed.), pg. 29.3), the contents of which are incorporated herein by reference.
  • Sintered nickel electrodes are prepared by sintering carbonyl nickel powder into a porous plaque containing a nickel screen and is then filled with active nickel hydroxide. Typically sintered nickel electrodes have a ratio of inactive to active nickel between 1 to 1.4 :1 providing excellent cycle life and stability, but with the disadvantage of being very heavy.
  • Non-sintered nickel electrodes are made by kneading and calendering an electrode strip consisting of nickel hydroxide, graphite and plastic binder laminated on both sides of an appropriate current collector. Applying lightweight substrates based on a fiber structure filled with active electrode mass has the advantage of reducing electrode weight as well as material costs.
  • Cylindrical cells with spirally rolled nickel electrode/separator/zinc electrode assemblies quite similar to Ni-Cd cells, have been tentatively produced by some manufacturers, but they suffered from serious short circuit troubles due to zinc dendrites growing during the charge cycles across the narrow (open) spiral distances between cathodes and anodes.
  • the objectives of this invention are mainly to produce high current, high capacity, cylindrical consumer cells that could be hermetically sealed and showing an acceptable cycle life at deep discharge conditions.
  • the present invention provides a rechargeable electrochemical cell comprising: a generally cylindrical container having an interior surface and an exterior surface; a generally cylindrical cathode contacting the container, the cathode being coaxial with the container; a generally cylindrical anode contained within the cathode and being coaxial therewith; a separator for physically separating the anode and the cathode; and, an electrolyte for electrically contacting the anode and the cathode; wherein the anode comprises a zinc material, the cathode comprises a nickel material.
  • the cathode material comprises a porous nickel material coated a with nickel hydroxide paste.
  • Figure 1 shows a cut through a cylindrical AA-size Ni-Zn cell made according to this invention.
  • Figure 2 shows a nickel electrode with two layers from the top and a three- dimensional view.
  • Figure 3 shows multiple (three) sleeves of a nickel electrode from the top and a three- dimensional view.
  • Figure 4 shows the discharge capacity of cell A75 and A79 with one nickel layer as a function of cycles.
  • Figure 5 shows the discharge capacity of cell A71 and A86 with two-nickel layers as a function of cycles.
  • Figure 6 shows the discharge capacity of cell A121 containing 2 % and cell A79 with 8.6 % Ni powder / T-210 as a function of cycles.
  • Figure 7 shows the discharge capacity of cell A128 containing 2 % and cell A131 with 0 % Co extra- fine powder as a function of cycles.
  • the invention is directed to fabrication of a rechargeable galvanic element with a positive nickel oxide electrode and a negative zinc electrode containing an alkaline electrolyte and a separator.
  • the cathode consists of a nickel foam structure that is filled with a nickel hydroxide rich paste made of a polyvinylalcohol (PVA) slurry.
  • PVA polyvinylalcohol
  • the nickel hydroxide is suitably compressed or compacted into a sheet or tape of defined thickness, rolled up into one or more layers and inserted into a nickel-plated steel can.
  • the nickel electrode is shaped into a very tight cylindrical cathode.
  • the filled foam can be compressed into a multiple of sleeves which are inserted exactly the same, also forming a cylindrical cathode.
  • Such nickel foam based cathodes are exhibiting an exceptionally low resistance and high efficiency leading to a sharp cut-off after the capacity is completely exhausted thereby establishing a cathode limited cell.
  • the anode consists of zinc powder, zinc oxide and a gelling agent, such as for example, Carbopol.
  • a gelling agent such as for example, Carbopol.
  • the anode capacity is chosen as a multiple of the cathode capacity.
  • the separator is preferably of the cellulose type. A brass nail located in the center of the cell builds the negative terminal. Other materials for the negative current collector will be apparent to persons skilled in the art.
  • the cell is characterized by prevention of excessive swelling of the cathode due to the cylindrical design in contrast to plate cells. It is further distinguished by the use of special additives to improve recharging.
  • the cathode is provided with hydrogen recombination catalysts for eliminating any hydrogen gas that may evolve.
  • Such catalysts can comprise those used in mercury- free zinc anodes.
  • a most preferred catalyst is silver (Ag).
  • the silver catalyst may be provided in an amount of between about 0.1% to 0.3% (wt.) of the nickel hydroxide.
  • Such Ag catalyst may be incorporated into the Ni foam in the form of a colloidal deposit by means of a spray coating process as known in the art.
  • the electrolyte is preferably a solution of potassium hydroxide with lithium hydroxide as additive.
  • the rechargeable nickel-zinc cells built according to the invention can be manufactured in all conventional cylindrical sizes (e.g. AAA, AA, C and D) but are not limited to these formats. Further the cells of the invention are hermetically sealed and can be used in all consumer electronic devices.
  • the cathode is provided with nickel foil strips to assist the can of the cell in its capacity as a current collector.
  • FIG. 1 of the drawings shows a cut through a cylindrical AA-size Ni-Zn cell embodying the present invention.
  • the cell comprises a Ni-plated steel can 1 housing a porous nickel oxide cathode 2, a zinc anode 3 and a separator 8 as the main components of a rechargeable galvanic element.
  • the cathode 2 may comprise one or several layers of a porous nickel substrate filled with nickel hydroxide, additives and a binder, and is separated from anode 3, which may comprise zinc powder, zinc oxide and gelling agent, by an electrolyte permeable separator 8.
  • the electrolyte which may consist of aqueous potassium and lithium hydroxide, permeates the nickel cathode 2 and zinc anode 3 through separator 8.
  • a current collector nail 7, that is connected to the negative cap 5 and embedded into the plastic top seal 4, is located in the center of the nickel-zinc cell. For safety reasons the plastic top seal 4 is provided with a safety vent break area 6.
  • Figure 2 illustrates the embodiment of a nickel electrode made of two layers of a nickel foam, pasted with a mixture of nickel hydroxide, nickel powder, cobalt powder and a binder (PVA-solution), that is shaped into a very tight cylindrical arrangement.
  • PVA-solution a binder
  • the embodiment of Figure 3 differs from that of Figure 2 in that, three or multiple sleeves of a nickel foam prepare the nickel electrode filled with nickel hydroxide mixture.
  • Separators according to a preferred embodiment of the invention comprise two overlapping layers of a laminated product comprising one piece of regenerated high purity cellulose bonded to a non-woven polyamide synthetic fiber.
  • separators known in the art may also be used.
  • the process of making the cells of the present invention comprises: 1) forming a sheet of Ni foam;
  • separator bag forming a separator in the form of a cylindrical tube open at one end (referred to herein as "separator bag”); 4) placing the separator bag on a mandrel or other such support;
  • the cathode preferably comprises a nickel foam coated with 8.6%
  • the anode preferably comprises 59% zinc oxide, 10% zinc powder, 0.5% Carbopol, and 30.5%o KOH.
  • the anode is preferably in the form of a gel paste.
  • the preferred electrolyte is KOH/LiOH solution.
  • the electrolyte comprises KOH in a concentration in the range of 6 to 9 M and LiOH dissolved in about 1% to the saturation point.
  • the charging of the nickel-zinc cell made according to the preferred embodiment is done by a voltage limited charging circuit, constant current charging, or an electronically controlled overflow circuit bypassing excess current above 1.95 V.
  • a cylindrical AA-size nickel zinc cell was fabricated which consisted of one positive nickel electrode layer and a negative zinc electrode assembled in an arrangement as shown in Figure 1.
  • the nickel electrode was prepared by blending a mixture of 8.6 % of nickel T-210 powder (from Inco Technical Services Ltd., Missisauga, Ontario), 4.3 % of cobalt extra-fine powder (UNION MINIERE, INC. - Carolmet Cobalt Products, Laurinburg, N.C.), 30.0 % of PVA-solution (1.17 % PVA in water/ethanol) and 57.1 % of nickel hydroxide (from Inco Technical Services Ltd., Missisauga, Ontario). Some water was added to obtain a light suspension.
  • the slurry was pasted into a nickel foam of 38 mm x 36 mm provided with a spotwelded nickel foil current collector (36 mm x 4 mm, 0.125 mm thick, 99.98 %, from Goodfellow Cambridge Ltd.,) at the longitudinal direction.
  • the pasting procedure was carried out a few times on both sides of the nickel foam with a spatula to ensure that the slurry completely penetrates into the foam. Wet surplus material was removed from the foam surface.
  • the nickel electrode was dried at 110°C for one hour.
  • the zinc electrode was prepared by mixing up 59 % of zinc oxide (from Merck), 10 % of zinc / type 004F (from Union Miniere S.A., Overpelt, Belgium), 0.50 % of Carbopol 940 (from Nacan, Toronto) and 30.5 % of 7 M KOH to a gel paste.
  • FIG. 4 shows the discharge capacity of each cycle of cylindrical AA- size nickel zinc cells A75 (Retec 80, 1.6 mm thick) and A79 (Inco, 2.7 mm thick) containing one layer of nickel electrode consisting of the above mentioned nickel foam types and a pasted zinc electrode as a function of cycle life.
  • the results obtained show a stable discharge behavior for at least 100 cycles with a relatively flat discharge profile and a small capacity decline during cycling.
  • the first few cycles are formation cycles that run under the cycling condition described above.
  • Example 2 A cell was assembled as described above with the exception that the positive electrode was made of two nickel layers and the appropriate dimension of the nickel foam was 38 mm x
  • Example 3 A cell, A121, was assembled as described in Example 1 except with a thinner Inco 2.2 mm nickel foam but of the same porosity as the 2.7 mm Inco foam and with 2 % of nickel T- 210 powder and 63.7 % of nickel hydroxide. The other components of nickel hydroxide slurry were the same as in Example 1. In this case, it was not necessary to add water to this light suspension that easy penetrates into the Inco foam, 2.2 mm thick.
  • Example 2 Two cells were built as described in Example 1 but with 2% (A128) and 0 % (A131) of cobalt (Co) extra fine powder and with 59.4 % and 61.4 % of nickel hydroxide.
  • the other components of nickel hydroxide slurry were the same as in Example 1 and Inco foam, 2.2 mm thick was used as the foam material.
  • Figure 7 shows the discharge capacity of each cycle of cylindrical AA-size nickel zinc cell A128 and A131.
  • the discharge capacity of cell A128 with 2 % cobalt is approximately 200 mAh higher than that of cell A131 containing 0 % cobalt since the addition of cobalt increases electronic conductivity of nickel electrode mass.
  • the following table summarizes foam type and nickel cathode mass of both cells:

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)
  • Cell Electrode Carriers And Collectors (AREA)
  • Secondary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

La présente invention concerne une pile électrochimique rechargeable comportant une cathode à base de nickel et une anode à base de zinc. La cathode comprend un matériau à base de nickel poreux, tel que de la mousse de nickel revêtue d'une pâte d'hydroxyde de nickel. L'anode comprend un mélange de zinc gélifié et d'hydroxyde de zinc. De plus, ladite pile comprend un électrolyte contenant KOH et LiOH.
EP00958057A 1999-09-03 2000-09-05 Piles a base de nickel-zinc rechargeables Withdrawn EP1218957A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CA002281371A CA2281371A1 (fr) 1999-09-03 1999-09-03 Cellule au nickel-zinc rechargeable
CA2281371 1999-09-03
PCT/CA2000/001007 WO2001018897A1 (fr) 1999-09-03 2000-09-05 Piles a base de nickel-zinc rechargeables

Publications (1)

Publication Number Publication Date
EP1218957A1 true EP1218957A1 (fr) 2002-07-03

Family

ID=4164080

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00958057A Withdrawn EP1218957A1 (fr) 1999-09-03 2000-09-05 Piles a base de nickel-zinc rechargeables

Country Status (7)

Country Link
EP (1) EP1218957A1 (fr)
JP (1) JP2003526877A (fr)
KR (1) KR20020053807A (fr)
CN (1) CN1372703A (fr)
AU (1) AU6974700A (fr)
CA (1) CA2281371A1 (fr)
WO (1) WO2001018897A1 (fr)

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Publication number Priority date Publication date Assignee Title
CA2380952A1 (fr) * 2002-04-08 2003-10-08 Jeffrey Phillips Batterie bipolaire au nickel-zinc a haut rendement, comprenant une couche mince et ayant la capacite d'effectuer la recombinaison de l'oxygene
US6991875B2 (en) 2002-08-28 2006-01-31 The Gillette Company Alkaline battery including nickel oxyhydroxide cathode and zinc anode
JP5144931B2 (ja) * 2003-08-18 2013-02-13 パワージェニックス システムズ， インコーポレーテッド ニッケル亜鉛電池の製造方法
JP4514588B2 (ja) * 2004-11-30 2010-07-28 ソニー株式会社 単三形アルカリ電池
CN100373680C (zh) * 2005-03-14 2008-03-05 河南环宇集团有限公司 动力型圆柱密封锌镍碱性蓄电池
US8703330B2 (en) * 2005-04-26 2014-04-22 Powergenix Systems, Inc. Nickel zinc battery design
KR101536031B1 (ko) 2008-04-02 2015-07-10 파워지닉스 시스템즈, 인코포레이티드 네거티브 캔을 포함하는 원통형 니켈-아연 전지
US8722226B2 (en) 2008-06-12 2014-05-13 24M Technologies, Inc. High energy density redox flow device
US11909077B2 (en) 2008-06-12 2024-02-20 Massachusetts Institute Of Technology High energy density redox flow device
US9786944B2 (en) 2008-06-12 2017-10-10 Massachusetts Institute Of Technology High energy density redox flow device
WO2011084649A2 (fr) * 2009-12-16 2011-07-14 Massachusetts Institute Of Technology Dispositif à écoulement redox à haute densité d'énergie
AU2012208933A1 (en) * 2011-01-21 2013-05-09 Liu, Hao Cylindrical shaped ion-exchange battery
CN102306848A (zh) * 2011-08-24 2012-01-04 黄小鸿 一种高能电池电解液的配方
US8993159B2 (en) 2012-12-13 2015-03-31 24M Technologies, Inc. Semi-solid electrodes having high rate capability
US9362583B2 (en) 2012-12-13 2016-06-07 24M Technologies, Inc. Semi-solid electrodes having high rate capability
US20160308219A1 (en) * 2015-04-14 2016-10-20 Intel Corporation Randomly shaped three dimensional battery cell with shape conforming conductive covering
CN106848407A (zh) * 2017-02-27 2017-06-13 安徽桑瑞斯环保新材料有限公司 一种用于可再充电碱性电化学电池的碱性电池电解质
CN113437369B (zh) * 2021-05-25 2022-06-03 武汉理工大学 一种基于重构外延相的镍锌微电池及其制备方法

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US4552821A (en) * 1983-06-30 1985-11-12 Duracell Inc. Sealed nickel-zinc battery
WO1989004070A1 (fr) * 1987-10-27 1989-05-05 Klaus Tomantschger Recombinaison catalytique d'oxygene emis dans des cellules galvaniques
US5043234A (en) * 1987-10-27 1991-08-27 Battery Technologies Inc. Recombination of evolved oxygen in galvanic cells using transfer anode material
EP0512565B1 (fr) * 1991-05-10 1997-04-16 Japan Storage Battery Company Limited Accumulateur prismatique alcalin étanche avec une électrode d'hydroxide de nickel
US5626988A (en) * 1994-05-06 1997-05-06 Battery Technologies Inc. Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture
EP0975036A4 (fr) * 1997-01-30 2005-11-23 Sanyo Electric Co Batterie d'accumulateurs aux alcalis blindee
JPH11167933A (ja) * 1997-12-02 1999-06-22 Sanyo Electric Co Ltd 密閉型アルカリ亜鉛蓄電池

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Title
See references of WO0118897A1 *

Also Published As

Publication number Publication date
KR20020053807A (ko) 2002-07-05
CN1372703A (zh) 2002-10-02
AU6974700A (en) 2001-04-10
WO2001018897A1 (fr) 2001-03-15
CA2281371A1 (fr) 2001-03-03
JP2003526877A (ja) 2003-09-09

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