WO2005015665A2 - High capacity alkaline cells - Google Patents
High capacity alkaline cells Download PDFInfo
- Publication number
- WO2005015665A2 WO2005015665A2 PCT/US2004/025895 US2004025895W WO2005015665A2 WO 2005015665 A2 WO2005015665 A2 WO 2005015665A2 US 2004025895 W US2004025895 W US 2004025895W WO 2005015665 A2 WO2005015665 A2 WO 2005015665A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- recited
- electrochemical cell
- anode
- cathode
- separator
- Prior art date
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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- Cathode 24 further presents an inner surface 27 that define a centrally shaped void 28 in a cylindrical cell within which anode 26 is disposed.
- a separator 32 is disposed between the anode 26 and cathode 24.
- a cell of the invention includes a cathode that comprises an oxide of copper as a cathode active material.
- the present inventors also recognize that j et-milling of commercially available CuO to reduce particle size and increase surface area results in a higher operating voltage.
- the surface area plays an important role in the reaction kinetics and hence the operating voltage of the battery.
- the present invention recognizes that an applied current to a cathode creates a stress that is distributed among the entire surface area of the cathode. Accordingly, cathodes having a greater surface area perform better than those having smaller surface areas as illustrated in Fig. 7.
- the surface area of the CuO can also be increased by modifying the process conditions during synthesis of the CuO, particularly if using a solution process.
- the particle size is within a range whose lower end is between, and includes, .1 microns and 10 microns, and whose upper end is between, and includes, 50 microns and 150 microns.
- Fig. 8 shows the effect of CuS particle size on the rate capability of a jet- milled CuO/ CuS cathode in a flooded half-cell where the current is progressively stepped between 5 mA and 35 mA.
- the electrode comprising CuS of particle size smaller than 25 micrometers shows a significantly lower polarization (higher voltage) than a cathode comprising CuS particles > 25 micrometers in diameter. Since a smaller particle size contributes a higher surface area than larger particles of the same mass, this result indicates that a higher surface area CuS provides superior current carrying capability (rate capability) in a cathode comprising CuO/CuS.
- Each layer or pellet comprises either a distinct cathode active material or a physical mixture of the materials suitable for use in combination with the invention. It is specifically contemplated that where separate cathode layers or pellets are provided, at least one layer or pellet can comprise a physical mixture of copper oxide with another additive (e.g., a metal oxide or sulfide) while another layer or pellet can comprise a mixed compound.
- another additive e.g., a metal oxide or sulfide
- anode-fouling species examples include various Cu, Ag, S, Fe, Ni, and Sb species.
- a high capacity anode-formulation is also provided for use in alkaline cells.
- cathodes of conventional alkaline cells for example cathodes whose cathode active ingredient is MnO 2 , consume more water by the cathodic reaction than is produced by the anodic reaction (i.e., the reaction of zinc anode and electrolyte).
- the total cell reaction as represented, consumes water as shown below and are thus said to be "water consuming” :
- the separator can be a film and is optionally formed on the cathode or inserted into the cell during cell manufacture.
- a particularly suitable film has as small a cross-sectional thickness as is practical while retaining manufacturing processibility (e.g., flexibility, mechanical stability, integrity at processing temperatures, integrity within the cell, and the like), adequate electrolyte absorption, as well as the advantageous properties noted herein.
- Suitable dry film thicknesses typically range from about 10 to about 250 microns. The present inventors have recognized that depending on the difference between the pH value of the bulk electrolyte and the pH value of the electrolyte retained in the separator, the thickness of a film separator may be selectively optimized to effectively limit the migration of anode- fouling soluble species.
- the separator is also compatible with known variations and improvements in cathode, anode and electrolyte structure and chemistry, but finds particular advantage for cells having a cathode that contains one or more cathode active materials comprising at least one of a primary oxide or sulfide of a metal, a binary oxide or sulfide of a metal, a ternary oxide or sulfide of a metal or a quaternary oxide or sulfide of a metal, where the metal is selected from manganese, copper, nickel, iron and silver, that can dissolve to form one or more anode-fouling soluble species, including but not limited to ionic metallic species and sulfur species, that can disadvantageously migrate from the cathode to the anode in the bulk electroly
- a second general method of producing a sealed separator is physical, using a heat-sealable polymeric material, such as PVA, polyethylene, polypropylene, nylon, and the like.
- the seal is formed by providing a layer of the polymeric material, in the form of a continuous film, or porous fibrous film, and inserting the layer into the area to be sealed (e.g., the outer periphery of a separator to be installed into a size AA cell).
- the separator then can form a seal under controlled heating with or without application of pressure.
- Cylindrical cells typically include an annular grommet disposed proximal the negative cell terminal end that is compressed either axially or radially against the cathode and separator to prevent anode spillover.
- the negative end of the separator can abut and be sealed against the grommet by dispensing a polymer to the periphery of the separator at the negative end, and sealing the polymer against the grommet under controlled heating conditions.
- a chemical bond including cross-linking may also be used to create a seal.
- Example 2 This is an example that illustrates the ability of various separators to effectively limit the migration of anode-fouling species.
- Side A of the glass tube fixture was filled with 34% KOH having a known concentration of copper ions and electrolyte free of copper ions was added to compartment B.
- the concentration of complex copper ions on side B was measured after 1 week at room temperature.
- FIG. 23 shows that with a cathode comprising a CuO/CuS mixture, 2 layers of hybrid separator are effective in limiting migration of anode- fouling soluble copper and sulfur species even after 5 days, thereby allowing the cell to discharge to full capacity. Furthermore, adding 0.2wt% PVA to the cathode is shown to extend cell discharge capacity by enabling better utilization of the cathode capacity.
- the film was then digested in 25 mL of deionized water at 70°C until dissolved.
- the pH was recorded along with the temperature of the solution during measurement.
- the pH at 23°C of retained electrolyte within each film was calculated using solution pH and temperature data using standard chemical calculation methods. Control samples were run using duplicates of the materials being tested but exposing them to only pH 7 de-ionized water solution. Variation from pH 7 was compensated (added or subtracted) from the conesponding sample to yield the normalized pH of the electrolyte retained within the sample separator. Table 6 shows that in separators that demonstrate adequate Exclusion Values, the pH values of the retained electrolyte in these separators are lower than the pH values in the bulk electrolyte.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2004264244A AU2004264244A1 (en) | 2003-08-08 | 2004-08-09 | High capacity alkaline cells |
JP2006523305A JP2007502008A (en) | 2003-08-08 | 2004-08-09 | High capacity alkaline battery |
EP04780688A EP1665419B1 (en) | 2003-08-08 | 2004-08-09 | High capacity alkaline cells |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US49369503P | 2003-08-08 | 2003-08-08 | |
US60/493,695 | 2003-08-08 | ||
US52841403P | 2003-12-10 | 2003-12-10 | |
US60/528,414 | 2003-12-10 | ||
US57729204P | 2004-06-04 | 2004-06-04 | |
US60/577,292 | 2004-06-04 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2005015665A2 true WO2005015665A2 (en) | 2005-02-17 |
WO2005015665A3 WO2005015665A3 (en) | 2006-06-29 |
Family
ID=34139613
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/025894 WO2005015662A2 (en) | 2003-08-08 | 2004-08-09 | Separators for alkaline electrochemical cells |
PCT/US2004/025895 WO2005015665A2 (en) | 2003-08-08 | 2004-08-09 | High capacity alkaline cells |
PCT/US2004/025809 WO2005015664A2 (en) | 2003-08-08 | 2004-08-09 | Alkaline cells having high capacity |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/025894 WO2005015662A2 (en) | 2003-08-08 | 2004-08-09 | Separators for alkaline electrochemical cells |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/025809 WO2005015664A2 (en) | 2003-08-08 | 2004-08-09 | Alkaline cells having high capacity |
Country Status (8)
Country | Link |
---|---|
US (4) | US20050084755A1 (en) |
EP (3) | EP1661196B1 (en) |
JP (3) | JP2007502006A (en) |
AR (1) | AR045347A1 (en) |
AU (3) | AU2004264243A1 (en) |
DE (1) | DE602004029587D1 (en) |
TW (1) | TW200520292A (en) |
WO (3) | WO2005015662A2 (en) |
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AU2004264244A1 (en) | 2005-02-17 |
WO2005015664A3 (en) | 2006-06-01 |
US20050074674A1 (en) | 2005-04-07 |
JP2007502007A (en) | 2007-02-01 |
EP1661196B1 (en) | 2010-10-13 |
JP2007502006A (en) | 2007-02-01 |
TW200520292A (en) | 2005-06-16 |
WO2005015662A2 (en) | 2005-02-17 |
EP1665419A2 (en) | 2006-06-07 |
US7931981B2 (en) | 2011-04-26 |
AU2004264243A1 (en) | 2005-02-17 |
AR045347A1 (en) | 2005-10-26 |
WO2005015662A3 (en) | 2006-04-13 |
WO2005015664A2 (en) | 2005-02-17 |
US20050084755A1 (en) | 2005-04-21 |
EP1665418A2 (en) | 2006-06-07 |
AU2004264238A1 (en) | 2005-02-17 |
DE602004029587D1 (en) | 2010-11-25 |
EP1661196A2 (en) | 2006-05-31 |
WO2005015665A3 (en) | 2006-06-29 |
EP1665419B1 (en) | 2011-11-16 |
US7645540B2 (en) | 2010-01-12 |
US20050079415A1 (en) | 2005-04-14 |
US7763384B2 (en) | 2010-07-27 |
US20100112431A1 (en) | 2010-05-06 |
JP2007502008A (en) | 2007-02-01 |
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