USRE40727E1 - Alkaline cells having low toxicity rechargeable zinc electrodes - Google Patents
Alkaline cells having low toxicity rechargeable zinc electrodes Download PDFInfo
- Publication number
- USRE40727E1 USRE40727E1 US11/598,153 US59815306A USRE40727E US RE40727 E1 USRE40727 E1 US RE40727E1 US 59815306 A US59815306 A US 59815306A US RE40727 E USRE40727 E US RE40727E
- Authority
- US
- United States
- Prior art keywords
- weight
- nickel
- fluoride
- zinc
- alkaline cell
- 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, expires
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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/244—Zinc electrodes
-
- 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
- H01M10/24—Alkaline accumulators
- H01M10/26—Selection of materials as electrolytes
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/32—Nickel oxide or hydroxide electrodes
-
- 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
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
-
- 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
Definitions
- This invention relates to alkaline cells, and particularly to alkaline galvanic cells having zinc electrodes and alkaline electrolyte, together with a nickel positive electrode.
- the invention provides low toxicity rechargeable zinc electrodes for such cells.
- buffered electrolytes are also contemplated, for improvement of rechargeable zinc cells.
- CARLSON U.S. Pat. No. 4,273,841 issued Jun. 16, 1981, which teaches an aqueous alkaline solution having potassium hydroxide, potassium fluoride, and potassium phosphate.
- CHARKEY U.S. Pat. No. 5,556,720, issued Sep. 17 1996 teaches the use of a zinc negative electrode that has zinc active material, barium hydroxide, and strontium hydroxide, in a conductive matrix which includes a metallic oxide that is more electropositive than zinc.
- the zinc negative electrode is split into electrode assemblies which are separated by a hydrophobic element.
- HIMY et al U.S. Pat. No. 4,084,047 teaches a zinc electrode that has a minor amount of one or more of a number of oxides including tantalum oxide, lead oxide, cadmium oxide, tin oxide, gallium oxide, and indium hydroxide. All of these are intended to reduce shape change, and to inhibit hydrogen gassing.
- pasted nickel hydroxide electrodes can have their performance improved by the addition of conductive diluents to improve active material utilization, and such as to establish a conductive insoluble CoOOH network in situ within a pasted nickel hydroxide electrode.
- the Jones Patent appears to be somewhat effective in extending cycle life of the cell by the addition of calcium hydroxide to the zinc electrode.
- buffered electrolytes with or without fluoride additions may also result in increased zinc electrode lifespan. They are particularly described in the Adler et al patent, noted above, where a mixture of alkaline electrolyte having a strength of 2M to 12M is combined with a carbonate of 0.5M to 4M, and a fluoride of 0.5M to 4M.
- the Carlson Patent noted above, describes a mixture that employs 5% to 10% of hydroxide, 10% to 20% of phosphate, and 5% to 15% of fluoride.
- a purpose of the present invention is to provide a formulation for a negative electrode that avoids issues of toxicity—thereby avoiding use of such elements as mercury.
- nickel is one of the most expensive components of a nickel zinc cell, it is intended to provide the highest utilization of the nickel electrode as may be possible.
- the present invention provides a nickel zinc alkaline cell having a zinc oxide electrode supported on a conductive substrate, an alkaline electrolyte, and a positive electrode having nickel hydroxide paste supported on a conductive substrate.
- the negative zinc oxide electrode comprises 85% to 95% zinc oxide powder, 1% to 10% bismuth oxide, 1% to 2% of a binder, and 0.05% to 5% by weight of a fluoride salt.
- the fluoride salt is a salt of a metal which is chosen from the group consisting of: sodium, potassium, rubidium, caesium, lithium, and mixtures thereof.
- the fluoride salt is potassium fluoride, which may be present in the amount of 0.05% to 4.5% by weight of the zinc oxide. 0.5% has been found to be quite successful.
- the bismuth oxide is present in the amount of 3% to 9% by weight of the zinc oxide.
- the alkaline electrolyte comprises a mixture of sodium hydroxide, potassium hydroxide, lithium hydroxide, and an acid chosen from the group consisting of: boric acid, phosphoric acid, and mixtures thereof.
- boric acid When boric acid is present, it has a concentration of 0.6 to 1.3 moles per liter.
- the stoichiometric excess of alkali hydroxide is between 2.5 moles and 5.0 moles.
- lithium hydroxide is present in the amount of about 0.05 to 3.0 moles.
- the inventor herein has unexpectedly discovered that the beneficial high solution alkalinity can be employed with the defined formulations of electrolyte and electrodes, and in particular the present inventor has unexpectedly discovered a surprising increase in nickel electrode efficiency as a result of practising the present invention.
- the present inventor has provided a zinc electrode in a nickel zinc cell that contains bismuth oxide, a binder, and a small amount of alkali metal fluoride.
- This zinc electrode may be used in conjunction with a borate electrolyte which contains a mixture of alkali hydroxides; and when used in a nickel zinc cell having a nickel oxide counter electrode, unexpected cell efficiency values are derived.
- the positive electrode is a nickel hydroxide electrode
- the cost of that electrode must be kept in mind.
- a high fluoride concentration may result in the premature passivation of the zinc electrode, particularly at high discharge rates, and this results in a sudden disproportionate loss in cell capacity as the discharge rate is increased.
- Typical nickel zinc cells were constructed for purposes of experimentation with respect to the present invention, and the cells were constructed in keeping with the present invention having the addition of fluoride to the zinc oxide electrode.
- a typical cell comprises a pasted nickel hydroxide positive electrode and a slurry coated zinc oxide negative electrode, with at least 100% coulombic excess of zinc oxide over the nickel hydroxide content.
- the conducting substrate for the nickel hydroxide positive electrode is a nickel foam; and typically, the conductive substrate for the zinc oxide negative electrode is copper expanded metal.
- Conductive enhancement additives were included in the positive electrode paste formulation, and comprised up to 2% to 3% by weight of each of nickel metal powder and cobalt metal powder.
- the zinc electrode contained approximately 85% to 95% of zinc oxide powder, from 1% to 10% by weight of bismuth oxide—preferably, from 3% to 9%—1% to 2% of a binder as is well known to those skilled in the art, and from 0.05% up to 5% by weight of a fluoride salt of a metal chosen from the group of metals consisting of sodium, potassium, rubidium, caesium, lithium, and combinations thereof. Typically, 0.5% potassium fluoride was employed.
- the type 1 cell was constructed in the manner described above, with the zinc oxide negative electrode having 0.5% by weight of potassium fluoride.
- the type 2 cell was constructed as described above, but with no potassium fluoride additive to the negative electrode.
- the type 3 cell was a standard cell, having no fluoride additive in the negative electrode, but having 0.1 mole fluoride buffering in the electrolyte.
- the type 4 cell was constructed as the type 3 cell, except that it had 0.02 mole fluoride buffering in the electrolyte.
- the electrolyte had a stoichiometric excess of alkaline hydroxide in the range of 2.5 moles to 5 moles. Also, the alkaline mixture contained between 0.05 moles and 3 moles of lithium hydroxide.
- the other cells having fluoride doping in the electrolyte, showed no significant advantage over the standard cell.
Abstract
Description
TABLE 1 | |||||
% Utilization of | |||||
Nickel Electrode | |||||
Cell Type | Zinc Electrode | Electrolyte | at 1 Amp. | ||
1 | 0.5% Fl | Fl Free | 91 | ||
2 | Standard | Fl Free | 76 | ||
3 | Standard | 0.1M Fl | 77 | ||
4 | Standard | 0.02M Fl | 75 | ||
Claims (23)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/598,153 USRE40727E1 (en) | 2001-03-15 | 2006-11-09 | Alkaline cells having low toxicity rechargeable zinc electrodes |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US27637201P | 2001-03-15 | 2001-03-15 | |
US10/098,195 US6818350B2 (en) | 2001-03-15 | 2002-03-15 | Alkaline cells having low toxicity rechargeable zinc electrodes |
US11/598,153 USRE40727E1 (en) | 2001-03-15 | 2006-11-09 | Alkaline cells having low toxicity rechargeable zinc electrodes |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/098,195 Reissue US6818350B2 (en) | 2001-03-15 | 2002-03-15 | Alkaline cells having low toxicity rechargeable zinc electrodes |
Publications (1)
Publication Number | Publication Date |
---|---|
USRE40727E1 true USRE40727E1 (en) | 2009-06-09 |
Family
ID=23056396
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/098,195 Ceased US6818350B2 (en) | 2001-03-15 | 2002-03-15 | Alkaline cells having low toxicity rechargeable zinc electrodes |
US10/980,423 Abandoned US20050112464A1 (en) | 2001-03-15 | 2004-11-02 | Alkaline cells having low toxicity rechargeable zinc electrodes |
US11/598,153 Expired - Lifetime USRE40727E1 (en) | 2001-03-15 | 2006-11-09 | Alkaline cells having low toxicity rechargeable zinc electrodes |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/098,195 Ceased US6818350B2 (en) | 2001-03-15 | 2002-03-15 | Alkaline cells having low toxicity rechargeable zinc electrodes |
US10/980,423 Abandoned US20050112464A1 (en) | 2001-03-15 | 2004-11-02 | Alkaline cells having low toxicity rechargeable zinc electrodes |
Country Status (2)
Country | Link |
---|---|
US (3) | US6818350B2 (en) |
CA (1) | CA2377065A1 (en) |
Families Citing this family (20)
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 |
US6818350B2 (en) | 2001-03-15 | 2004-11-16 | 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 |
US20080163478A1 (en) * | 2003-08-18 | 2008-07-10 | Powergenix Systems, Inc. | Method for manufacturing nickel zinc batteries |
EP1661195B1 (en) * | 2003-08-18 | 2016-01-13 | PowerGenix Systems, Inc. | Method of manufacturing nickel zinc batteries |
US20060207084A1 (en) * | 2004-08-17 | 2006-09-21 | Powergenix, Inc. | Method of manufacturing nickel zinc batteries |
WO2006094110A2 (en) * | 2005-03-01 | 2006-09-08 | Powergenix Systems, Inc. | Method of manufacturing nickel zinc batteries |
US8703330B2 (en) * | 2005-04-26 | 2014-04-22 | Powergenix Systems, Inc. | Nickel zinc battery design |
CN101026234A (en) * | 2007-02-12 | 2007-08-29 | 范正刚 | Zinc-nickel battery negative plate |
US7931988B2 (en) | 2007-10-05 | 2011-04-26 | Powergenix Systems, Inc. | Tin and tin-zinc plated substrates to improve Ni-Zn cell performance |
WO2009123888A1 (en) * | 2008-04-02 | 2009-10-08 | Powergenix Systems, Inc. | Cylindrical nickel-zinc cell with negative can |
US8501351B2 (en) * | 2009-05-18 | 2013-08-06 | Powergenix Systems, Inc. | Pasted zinc electrode for rechargeable nickel-zinc batteries |
KR101822666B1 (en) | 2009-08-07 | 2018-03-08 | 파워지닉스 시스템즈, 인코포레이티드 | Carbon Fiber Zinc Negative Electrode |
CN102484279B (en) | 2009-09-08 | 2015-06-17 | 鲍尔热尼系统公司 | Heat Sealing Separators For Nickel Zinc Cells |
US20110086252A1 (en) | 2009-10-13 | 2011-04-14 | Powergenix Systems, Inc. | Cylindrical nickel-zinc cell with positive can |
CN104205430A (en) | 2012-02-07 | 2014-12-10 | 鲍尔热尼系统公司 | Nickel-zinc rechargeable pencil battery |
CN103022472B (en) * | 2012-12-17 | 2015-03-11 | 湖南丰日电源电气股份有限公司 | Large-power zinc-nickel mixed battery cathode slurry and preparation method thereof |
JP6647866B2 (en) | 2012-12-20 | 2020-02-14 | ジンクファイブ・パワー・インコーポレーテッドZincFive Power,Inc. | Controlling the state of charge of a battery in a system with an independent power supply |
US9337683B2 (en) | 2012-12-20 | 2016-05-10 | Powergenix Systems, Inc. | Controlling battery states of charge in systems having separate power sources |
CN109075314B (en) * | 2016-10-03 | 2021-04-27 | 松下知识产权经营株式会社 | Alkaline dry cell |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3558356A (en) | 1967-02-28 | 1971-01-26 | Texas Instruments Inc | Nickel-zinc battery system which is negative limited during charging thereof |
US4017665A (en) | 1974-05-21 | 1977-04-12 | Prazska Akumulatorka, Narodni Podnik | Composition for a zinc electrode |
US4037033A (en) | 1975-01-20 | 1977-07-19 | Tokyo Shibaura Electric Co. Ltd. | Rechargeable nickel-zinc battery |
US4084047A (en) | 1976-11-29 | 1978-04-11 | The United States Of America As Represented By The Secretary Of The Navy | Stable alkaline zinc electrode |
US4224391A (en) | 1979-09-14 | 1980-09-23 | Electrochimica Corporation | Electrolyte for zinc anode batteries and method of making same |
US4273841A (en) | 1980-08-14 | 1981-06-16 | General Electric Company | Ternary electrolyte for secondary electrochemical cells |
US4304828A (en) | 1980-06-27 | 1981-12-08 | Energy Research Corporation | Zinc electrode |
US4358517A (en) | 1979-10-30 | 1982-11-09 | General Motors Corporation | Nickel-zinc cell |
US5215836A (en) | 1991-07-18 | 1993-06-01 | Electrochimica Corporation | Alkaline galvanic cells |
US5453336A (en) | 1991-11-12 | 1995-09-26 | Regents Of The University Of California | Rechargeable zinc cell with alkaline electrolyte which inhibits shape change in zinc electrode |
US5556720A (en) | 1994-08-18 | 1996-09-17 | Energy Research Corporation | Sealed zinc secondary battery and zinc electrode therefor |
US20030186127A1 (en) | 2000-11-10 | 2003-10-02 | Jeffrey Phillips | Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials positive to zinc potential |
US6790559B2 (en) | 2001-03-15 | 2004-09-14 | Powergenix Systems, Inc. | Alkaline cells having positive nickel hydroxide electrodes with fluoride salt additives |
US6797433B2 (en) | 2000-11-10 | 2004-09-28 | Powergenix Systems, Inc. | Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials negative to zinc potential |
US6818350B2 (en) | 2001-03-15 | 2004-11-16 | Powergenix Systems, Inc. | Alkaline cells having low toxicity rechargeable zinc electrodes |
-
2002
- 2002-03-15 US US10/098,195 patent/US6818350B2/en not_active Ceased
- 2002-03-15 CA CA002377065A patent/CA2377065A1/en not_active Abandoned
-
2004
- 2004-11-02 US US10/980,423 patent/US20050112464A1/en not_active Abandoned
-
2006
- 2006-11-09 US US11/598,153 patent/USRE40727E1/en not_active Expired - Lifetime
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3558356A (en) | 1967-02-28 | 1971-01-26 | Texas Instruments Inc | Nickel-zinc battery system which is negative limited during charging thereof |
US4017665A (en) | 1974-05-21 | 1977-04-12 | Prazska Akumulatorka, Narodni Podnik | Composition for a zinc electrode |
US4037033A (en) | 1975-01-20 | 1977-07-19 | Tokyo Shibaura Electric Co. Ltd. | Rechargeable nickel-zinc battery |
US4084047A (en) | 1976-11-29 | 1978-04-11 | The United States Of America As Represented By The Secretary Of The Navy | Stable alkaline zinc electrode |
US4224391A (en) | 1979-09-14 | 1980-09-23 | Electrochimica Corporation | Electrolyte for zinc anode batteries and method of making same |
US4358517A (en) | 1979-10-30 | 1982-11-09 | General Motors Corporation | Nickel-zinc cell |
US4304828A (en) | 1980-06-27 | 1981-12-08 | Energy Research Corporation | Zinc electrode |
US4273841A (en) | 1980-08-14 | 1981-06-16 | General Electric Company | Ternary electrolyte for secondary electrochemical cells |
US5215836A (en) | 1991-07-18 | 1993-06-01 | Electrochimica Corporation | Alkaline galvanic cells |
US5453336A (en) | 1991-11-12 | 1995-09-26 | Regents Of The University Of California | Rechargeable zinc cell with alkaline electrolyte which inhibits shape change in zinc electrode |
US5556720A (en) | 1994-08-18 | 1996-09-17 | Energy Research Corporation | Sealed zinc secondary battery and zinc electrode therefor |
US20030186127A1 (en) | 2000-11-10 | 2003-10-02 | Jeffrey Phillips | Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials positive to zinc potential |
US6797433B2 (en) | 2000-11-10 | 2004-09-28 | Powergenix Systems, Inc. | Negative electrode formulation for a low toxicity zinc electrode having additives with redox potentials negative to zinc potential |
US6790559B2 (en) | 2001-03-15 | 2004-09-14 | Powergenix Systems, Inc. | Alkaline cells having positive nickel hydroxide electrodes with fluoride salt additives |
US6818350B2 (en) | 2001-03-15 | 2004-11-16 | Powergenix Systems, Inc. | Alkaline cells having low toxicity rechargeable zinc electrodes |
Also Published As
Publication number | Publication date |
---|---|
US20020182501A1 (en) | 2002-12-05 |
US6818350B2 (en) | 2004-11-16 |
CA2377065A1 (en) | 2002-09-15 |
US20050112464A1 (en) | 2005-05-26 |
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