US20030113622A1 - Electrolyte additive for non-aqueous electrochemical cells - Google Patents

Electrolyte additive for non-aqueous electrochemical cells Download PDF

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Publication number
US20030113622A1
US20030113622A1 US10/022,289 US2228901A US2003113622A1 US 20030113622 A1 US20030113622 A1 US 20030113622A1 US 2228901 A US2228901 A US 2228901A US 2003113622 A1 US2003113622 A1 US 2003113622A1
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Prior art keywords
cell
electrolyte
aluminum
perchlorate salt
ppm
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US10/022,289
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Jane Blasi
Nikolai Issaev
Michael Pozin
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Gillette Co LLC
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Gillette Co LLC
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=21808824&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20030113622(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Gillette Co LLC filed Critical Gillette Co LLC
Priority to US10/022,289 priority Critical patent/US20030113622A1/en
Assigned to GILLETTE COMPANY, THE reassignment GILLETTE COMPANY, THE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BLASI, JANE A., ISSAEV, NIKOLAI N., POZIN, MICHAEL
Priority to CNB028249887A priority patent/CN1320674C/en
Priority to BRPI0214896-0A priority patent/BR0214896A/en
Priority to EP02795827.1A priority patent/EP1527488B2/en
Priority to AU2002360562A priority patent/AU2002360562A1/en
Priority to JP2003553641A priority patent/JP4623965B2/en
Priority to PCT/US2002/039652 priority patent/WO2003052845A2/en
Priority to EP10003463A priority patent/EP2204869B1/en
Priority to ARP020104824A priority patent/AR038015A1/en
Priority to US10/361,945 priority patent/US20030124421A1/en
Publication of US20030113622A1 publication Critical patent/US20030113622A1/en
Priority to US10/990,379 priority patent/US20050089760A1/en
Priority to US12/137,100 priority patent/US7927739B2/en
Priority to US13/342,338 priority patent/US20120096708A1/en
Abandoned legal-status Critical Current

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    • 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
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/14—Primary casings, jackets or wrappings of a single cell or a single battery for protecting against damage caused by external factors
    • H01M50/145—Primary casings, jackets or wrappings of a single cell or a single battery for protecting against damage caused by external factors for protecting against corrosion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • 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
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Definitions

  • This invention relates to non-aqueous electrochemical cells for batteries.
  • a battery contains a negative electrode, typically called the anode, and a positive electrode, typically called the cathode.
  • the anode contains an active material that can be oxidized; the cathode contains or consumes an active material that can be reduced.
  • the anode active material is capable of reducing the cathode active material.
  • Aluminum can be used as a construction material in a battery. However, aluminum can corrode because the electrode potential of aluminum is lower than the normal operating potential of the positive electrode of the battery. This corrosion increases the internal impedance of a cell, leading to capacity loss and to a decrease in specific energy. When aluminum is coupled with metals of a different nature in the environment of an electrochemical cell, the aluminum can also be susceptible to corrosion degradation.
  • the invention relates to an electrochemical cell that includes parts made from aluminum or an aluminum-based alloy; these parts contact the electrolyte of the cell.
  • the cell also includes an additive to suppress aluminum corrosion.
  • the invention features a secondary electrochemical cell including a cathode, an anode, a current collector including aluminum, and an electrolyte containing a perchlorate salt and a second salt that is different from the perchlorate salt.
  • the second salt is not a perchlorate salt.
  • the electrolyte is essentially free of LiPF 6 .
  • the electrolyte can contain at least 5000 ppm by weight of the perchlorate salt or at least 10,000 ppm by weight of the perchlorate salt.
  • An example of the second salt is LiTFS.
  • the invention features an electrochemical cell including a cathode containing MnO 2 , an anode containing lithium, and an electrolyte containing a perchlorate salt.
  • the cell includes an aluminum surface in electrical contact with a second metal surface.
  • the surface is a portion of an object having at least one dimension greater than 0.5 mm, 1 mm, or 2 mm.
  • An “aluminum surface” can be the surface of an object made of pure aluminum, or a surface made of an aluminum-based alloy.
  • the second metal surface is different than the aluminum surface.
  • the different metal can be, e.g., steel, stainless steel, or nickel.
  • the different metal can also be a different alloy of aluminum. That is, different alloys of aluminum are considered to be different metals.
  • the cell can include a cathode current collector containing aluminum.
  • the electrolyte can contain about 500 to about 2500 ppm by weight of a perchlorate salt.
  • the perchlorate salt can be, e.g., LiClO 4 , Ca(ClO 4 ) 2 , Al(ClO 4 ) 3 , or Ba(ClO 4 ) 2 .
  • the electrolyte is essentially free of LiPF 6 .
  • the invention features an electrochemical cell including a cathode containing an aluminum current collector, an anode, and an electrolyte containing a lithium salt and a perchlorate salt.
  • the cell is a primary electrochemical cell. Primary electrochemical cells are meant to be discharged to exhaustion only once, and then discarded. Primary cells are not meant to be recharged.
  • the cathode can contain MnO 2 and the anode can contain lithium.
  • the electrolyte can contain at least 500 ppm by weight of the perchlorate salt, or at least 1000, 1500, or 2500 ppm by weight of the perchlorate salt.
  • the electrolyte can also contain less than 20,000 ppm by weight of the perchlorate salt.
  • the perchlorate salt can be, e.g., LiClO 4 , Ca(ClO 4 ) 2 , Al(ClO 4 ) 3 , or Ba(ClO 4 ) 2 .
  • the electrolyte can also include LiPF 6 , e.g., at least 5000 ppm by weight LiPF 6 or at least 10,000 ppm by weight LiPF 6 . In other aspects, the electrolyte is essentially free of LiPF 6 .
  • the case of the cell can be aluminum, either in whole or in part.
  • the invention features an electrochemical cell comprising a cathode containing MnO 2 , an anode containing lithium, and an electrolyte containing about 500 ppm to about 2000 ppm of a perchlorate salt.
  • the perchlorate salt can be, e.g., LiClO 4 , Ca(ClO 4 ) 2 , Al(ClO 4 ) 3 , or Ba(ClO 4 ) 2 .
  • the invention features an electrochemical cell comprising a cathode containing MnO 2 , an anode containing lithium, and an electrolyte containing a perchlorate salt; the cell is a primary electrochemical cell and includes two pieces of aluminum in electrical contact with each other. The two pieces can be made of the same alloy of aluminum.
  • the invention features a method of inhibiting aluminum corrosion in a primary electrochemical cell.
  • the method includes: (a) adding a perchlorate salt to the electrolyte of the cell; and (b) placing the electrolyte, an anode containing Li, and a cathode containing MnO 2 and an aluminum current collector into a cell case.
  • the perchlorate salt can be, e.g., LiClO 4 , Ca(ClO 4 ) 2 , Al(ClO 4 ) 3 , or Ba(ClO 4 ) 2 .
  • FIG. 1 is a sectional view of a nonaqueous electrochemical cell.
  • FIG. 2 is a graph showing current density vs. potential of the aluminum in an electrode exposed to LiTFS, DME:EC:PC electrolytes containing different amounts of LiClO 4 .
  • FIG. 3 is a graph showing current density vs. of the aluminum in an electrode exposed to LiTFS, DME:EC:PC electrolytes containing different amounts of LiClO 4 .
  • FIG. 4 is a graph showing current density vs. time of the aluminum in an electrode exposed to a LiTFS, DME:EC:PC electrolyte containing LiClO 4 .
  • FIG. 5 is a graph showing current density vs. potential of the aluminum in an electrode exposed to LiTFS+LiTFSI, DME:EC:PC electrolytes containing different amounts of LiClO 4 .
  • FIG. 6 is a graph showing current density vs. time of the aluminum in an electrode exposed to LiTFS+LiTFSTM, DME:EC:PC electrolytes containing different amounts of LiClO 4 .
  • FIG. 7 is a graph showing current density vs. potential of the aluminum in an electrode exposed to LiTFS+LiPF 6 , DME:EC:PC electrolytes containing different amounts of LiClO 4 .
  • FIG. 8 is a graph showing current density vs. time of the aluminum in an electrode exposed to LiTFS+LiPF 6 , DME:EC:PC electrolytes containing different amounts of LiClO 4 .
  • FIG. 9 is a graph showing current density vs. potential of the aluminum in an electrode exposed to a LiTFS, DME:EC:PC electrolyte containing different amounts of LiClO 4 and different amounts of Al(ClO 4 ) 3 .
  • FIG. 10 is a graph showing current density vs. potential of the aluminum in an electrode exposed to a LiTFS, DME:EC:PC electrolyte containing different amounts of LiClO 4 and different amounts of Ba(ClO 4 ) 2 .
  • an electrochemical cell 10 includes an anode 12 in electrical contact with a negative lead 14 , a cathode 16 in electrical contact with a positive lead 18 , a separator 20 and an electrolytic solution.
  • Anode 12 , cathode 16 , separator 20 and the electrolytic solution are contained within a case 22 .
  • the electrolytic solution includes a solvent system and a salt that is at least partially dissolved in the solvent system.
  • Cathode 16 includes an active cathode material, which is generally coated on the cathode current collector.
  • the current collector is generally titanium, stainless steel, nickel, aluminum, or an aluminum alloy, e.g., aluminum foil.
  • the active material can be, e.g., a metal oxide, halide, or chalcogenide; alternatively, the active material can be sulfur, an organosulfur polymer, or a conducting polymer. Specific examples include MnO 2 , V 2 O 5 , CoF 3 , MoS 2 , FeS 2 , SOCl 2 , MoO 3 , S, (C 6 H 5 N) n , (S 3 N 2 ) n , where n is at least 2.
  • the active material can also be a carbon monofluoride.
  • An example is a compound having the formula CF x , where x is 0.5 to 1.0.
  • the active material can be mixed with a conductive material such as carbon and a binder such as polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • An example of a cathode is one that includes aluminum foil coated with MnO 2 . The cathode can be prepared as described in U.S. Pat. No. 4,279,972.
  • Anode 12 can consist of an active anode material, usually in the form of an alkali metal, e.g., Li, Na, K, or an alkaline earth metal, e.g., Ca, Mg.
  • the anode can also consist of alloys of alkali metals and alkaline earth metals or alloys of alkali metals and Al.
  • the anode can be used with or without a substrate.
  • the anode also can consist of an active anode material and a binder.
  • an active anode material can include carbon, graphite, an acetylenic mesophase carbon, coke, a metal oxide and/or a lithiated metal oxide.
  • the binder can be, for example, PTFE.
  • the active anode material and binder can be mixed to form a paste which can be applied to the substrate of anode 12 .
  • Separator 20 can be formed of any of the standard separator materials used in nonaqueous electrochemical cells.
  • separator 20 can be formed of polypropylene, (e.g., nonwoven polypropylene or microporous polypropylene), polyethylene, and/or a polysulfone.
  • the electrolyte can be in liquid, solid or gel (polymer) form.
  • the electrolyte can contain an organic solvent such as propylene carbonate (PC), ethylene carbonate (EC), dimethoxyethane (DME), dioxolane (DO), tetrahydrofuran (THF), acetonitrile (CH 3 CN), gamma-butyrolactone, diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) dimethylsulfoxide (DMSO) methyl acetate (MA), methyl formiate (MF), sulfolane or combinations thereof.
  • PC propylene carbonate
  • EC ethylene carbonate
  • DME dimethoxyethane
  • DO dioxolane
  • THF tetrahydrofuran
  • CH 3 CN acetonitrile
  • EMC ethyl methyl carbonate
  • DMSO dimethylsulfoxide
  • the electrolyte can alternatively contain an inorganic solvent such as SO 2 or SOCl 2 .
  • the electrolyte also contains a lithium salt such as lithium trifluoromethanesulfonate (LiTFS) or lithium trifluoromethanesulfonimide (LiTFSI), or a combination thereof. Additional lithium salts that can be included are listed in U.S. Pat. No. 5,595,841, which is hereby incorporated by reference in its entirety.
  • the electrolyte may contain LiPF 6 ; in other embodiments, the electrolyte is essentially free of LiPF 6 .
  • the electrolyte also contains a perchlorate salt, which inhibits corrosion in the cell.
  • Suitable salts include lithium, barium, calcium, aluminum, sodium, potassium, magnesium, copper, zinc, ammonium, and tetrabutylammonium perchlorates. Generally, at least 500 ppm by weight of the perchlorate salt is used; this ensures that there is enough salt to suppress corrosion. In addition, less than about 20,000 by weight of the perchlorate salt is generally used. If too much perchlorate salt is used, the cell can be internally shorted under certain conditions during use.
  • separator 20 can be cut into pieces of a similar size as anode 12 and cathode 16 and placed therebetween as shown in FIG. 1.
  • Anode 12 , cathode 16 , and separator 20 are then placed within case 22 , which can be made of a metal such as nickel, nickel plated steel, stainless steel, or aluminum, or a plastic such as polyvinyl chloride, polypropylene, polysulfone, ABS or a polyamide.
  • Case 22 is then filled with the electrolytic solution and sealed.
  • One end of case 22 is closed with a cap 24 and an annular insulating gasket 26 that can provide a gas-tight and fluid-tight seal.
  • Positive lead 18 which can be made of aluminum, connects cathode 16 to cap 24 .
  • Cap 24 may also be made of aluminum.
  • a safety valve 28 is disposed in the inner side of cap 24 and is configured to decrease the pressure within battery 10 when the pressure exceeds some predetermined value. Additional methods for assembling the cell are described in U.S. Pat. Nos. 4,279,972; 4,401,735; and 4,526,846.
  • battery 10 can also be used, including, e.g., the coin cell configuration.
  • the batteries can be of different voltages, e.g., 1.5V, 3.0V, or 4.0V.
  • An electrochemical glass cell was constructed having an Al working electrode, a Li reference electrode, and two Li auxiliary electrodes.
  • the working electrode was fabricated from a 99.999% Al rod inserted into a Teflon sleeve to provide a planar electrode area of 0.33 cm.
  • the native oxide layer was removed by first polishing the planar working surface with 3 ⁇ m aluminum oxide paper under an argon atmosphere, followed by thorough rinsing of the Al electrode in electrolyte. All experiments were performed under an Ar atmosphere.
  • Corrosion current measurements were made according to a modified procedure generally described in X. Wang et al., Electrochemica Acta, vol. 45, pp. 2677-2684 (2000).
  • the corrosion potential of Al was determined by continuous cyclic voltammetry. In each cycle, the potential was initially set to an open circuit potential, then anodically scanned to +4.5 V and reversed to an open circuit potential. A scan rate of 50 mV/s was selected, at which good reproducibility of the corrosion potential of aluminum was obtained.
  • the corrosion potential of aluminum was defined as the potential at which the anodic current density reached 10 ⁇ 5 A/cm 2 at the first cycle.
  • Corrosion current measurements were made according to the procedure described in EP 0 852 072.
  • the aluminum electrode was polarized at various potentials vs. a Li reference electrode while the current was recorded vs. time.
  • Current vs. time measurements were taken during a 30-minute period.
  • the area under current vs. time curve was used as a measure of the amount of aluminum corrosion occurring.
  • the experiment also could be terminated in case the current density reached 3 mA/cm 2 before the 30 minute time period elapsed and no corrosion suppression occurred. Corrosion suppression occurred when the resulting current density was observed in the range of 10 ⁇ 6 A/cm 2 .
  • Curves “a” and “a′” in FIG. 2 show the corrosion potential of the aluminum in the electrolyte containing no LiClO 4 .
  • the addition of 500 ppm of LiClO 4 to the electrolyte shifted the potential of the aluminum 150 mV in the positive direction (curves “b” and “b′”); the addition of 1000 ppm of LiClO 4 to the electrolyte shifted the potential 300 mV (curves “c” and “c′”); and the addition of 2500 ppm of LiClO 4 to the electrolyte shifted the potential 600 mV (curves “d” and “d′”).
  • curve “a” shows a potentiostatic dependence (chronoamperogram) of the aluminum electrode exposed to the electrolyte containing LiTFS, DME:EC:PC with the addition of 500 ppm LiClO 4 ;
  • curve “b” shows the chronoamperogram taken in the same electrolyte with addition of 1000 ppm LiClO 4 ;
  • curve “c” shows the chronoamperogram taken in the electrolyte containing LiTFS, DME:EC:PC, and 2500 ppm LiClO 4 .
  • the aluminum corrosion at +3.6 V vs. a Li reference electrode
  • the corrosion current is less than 10 ⁇ 6 A/cm 2 after 30 minutes of measurement.
  • the electrochemical window of Al stability can be extended as high as +4.2 V (vs. a Li reference electrode) by increasing the concentration of LiClO 4 to 1% (10,000 ppm).
  • LiClO 4 concentration of 1% aluminum corrosion is effectively suppressed at 4.2 V.
  • the corrosion current after 30 minutes is 8-10 ⁇ A/cm 2 , and the current continues to fall over time.
  • the falling current indicates passivation of the Al surface.
  • the increased level of the resulting current (10 ⁇ A/cm 2 vs. 1 ⁇ A/cm 2 after 30 minutes of experiment) is due to the increased background current at these potentials.
  • curves “a”, “a′”, and “a′′” show the corrosion potential of an aluminum electrode subjected to an electrolyte containing a mixture of LiTFS and LiTFSI salts, DME:EC:PC, and no LiClO 4 .
  • curve “a” shows the chronoamperogram of the aluminum electrode exposed to the electrolyte containing a mixture of LiTFS and LiTFSI salts, DME:EC:PC, and 1000 ppm LiClO 4
  • curve “b” shows the chronoamperogram of the aluminum electrode exposed to the same electrolyte containing 2500 ppm LiClO 4 .
  • the aluminum corrosion at +3.6 V is effectively suppressed, and resulting corrosion current of the Al electrode is about 10 ⁇ 6 A/cm 2 after 30 minutes.
  • curve “a” shows the corrosion potential of the aluminum subjected to an electrolyte containing a mixture of LiTFS and LiPF 6 salts, DME:EC:PC, and no LiClO 4 .
  • the addition of 500 ppm of LiClO 4 to this electrolyte shifted the corrosion potential of the aluminum 125 mV in the positive direction (curve “b”); the addition of 2500 ppm of LiClO 4 to the electrolyte shifted the potential 425 mV (curve “c”); and the addition of 5000 ppm of LiClO 4 to the electrolyte shifted the potential 635 mV (curve “d”).
  • curve “a” shows a chronoamperogram of the aluminum electrode exposed to the electrolyte containing LiTFS, LiPF 6 , DME:EC:PC with no LiClO 4 ;
  • curve “b” shows a chronoamperogram taken in the same electrolyte with 2500 ppm LiClO 4 added;
  • curve “c” shows a chronoamperogram taken in the electrolyte containing LiTFS, LiPF 6 , DME:EC:PC, and 5000 ppm LiClO 4 .
  • the aluminum corrosion at +3.6 V vs. a Li reference electrode
  • the corrosion current is less than 10 ⁇ 6 A/cm 2 after 30 minutes of measurement.
  • Electrochemical glass cells were constructed as described in Example 1. Cyclic voltammetry and chromoamperometry were performed as described in Example 1.
  • curves “a”, “b”, and “c” show the corrosion potential of an aluminum electrode exposed to the electrolyte LiTFS, DME:EC:PC containing 0, 1000 and 2500 ppm of LiClO 4, respectively.
  • Curves “a′”, “b′,” and “c′” show the corrosion potential of an aluminum electrode exposed to the electrolyte LiTFS, DME:EC:PC containing 0, 1000 and 2500 ppm of Al(ClO 4 ) 3 , respectively.
  • curves “a”, “b”, and “c” show the corrosion potential of an aluminum electrode exposed to the electrolyte LiTFS, DME:EC:PC containing 0, 1000 and 2500 ppm of LiClO 4 , respectively.
  • Curves “a′”, “b′” and “c′” show the corrosion potential of an aluminum electrode exposed to the electrolyte LiTFS, DME:EC:PC containing 0, 1000 and 2500 ppm of Ba(ClO 4 ) 2 , respectively.
  • Electrodes EMD (electrochemically synthesized manganese dioxide) based cathodes applied on the Al current collector
  • the level of Al ions in the electrolyte indicates the rate of Al corrosion.
  • the background level of Al ions in solution is about 2 ppm.
  • the corrosion of a metal is said to be suppressed when, after the test described above is performed, the concentration of metal ions in the electrolyte is less than about 3 ppm, which is just above the background level.
  • the Al concentration in the electrolyte without LiClO 4 addition is high (the range is 19.4-23 ppm). Thus, part of the Al substrate has dissolved (corroded) under the potential of the applied active cathode material.
  • a high concentration of Ni (90.9 ppm) in the resulting electrolyte indicates the severe corrosion of the Ni tab coupled with Al (the Al corroded as well, as indicated by the presence of 20.5 ppm Al).
  • the assembled cells (2/3A size) were stored 20 days at 60° C. Electrolyte removed from the cells after storage was submitted for ICP analysis. The electrolyte did not show any traces of Al, Fe, or Ni (the concentrations were at the background level).
  • Two cathodes were prepared by coating aluminum foil substrates (1145 Al) with MnO 2 . Pieces of aluminum foil (3003 Al) were welded to the aluminum foil of each of the cathodes.
  • One cathode was stored for 20 days at 60° C. over LiTFS, DME:EC:PC electrolyte containing 2500 ppm of LiClO 4 .
  • the second cathode was stored for 20 days at 60° C. over LiTFS, DME:EC:PC electrolyte containing no LiClO 4 . After the 20-day period, the electrolytes were analyzed by ICP.
  • the first electrolyte (2500 ppm LiClO 4 in the electrolyte) contained less than 1 ppm Al, while the second electrolyte (no LiClO 4 in the electrolyte) contained 18 ppm Al.

Abstract

An electrochemical secondary cell is disclosed. The cell includes a cathode, an anode, a current collector including aluminum, and an electrolyte containing a perchlorate salt and a second salt. The electrolyte is essentially free of LiPF6.

Description

    BACKGROUND
  • This invention relates to non-aqueous electrochemical cells for batteries. [0001]
  • Batteries are commonly used electrical energy sources. A battery contains a negative electrode, typically called the anode, and a positive electrode, typically called the cathode. The anode contains an active material that can be oxidized; the cathode contains or consumes an active material that can be reduced. The anode active material is capable of reducing the cathode active material. [0002]
  • When a battery is used as an electrical energy source in a device, electrical contact is made to the anode and the cathode, allowing electrons to flow through the device and permitting the respective oxidation and reduction reactions to occur to provide electrical power. An electrolyte in contact with the anode and the cathode contains ions that flow through the separator between the electrodes to maintain charge balance throughout the battery during discharge. [0003]
  • Aluminum can be used as a construction material in a battery. However, aluminum can corrode because the electrode potential of aluminum is lower than the normal operating potential of the positive electrode of the battery. This corrosion increases the internal impedance of a cell, leading to capacity loss and to a decrease in specific energy. When aluminum is coupled with metals of a different nature in the environment of an electrochemical cell, the aluminum can also be susceptible to corrosion degradation. [0004]
    • SUMMARY
  • The invention relates to an electrochemical cell that includes parts made from aluminum or an aluminum-based alloy; these parts contact the electrolyte of the cell. The cell also includes an additive to suppress aluminum corrosion. [0005]
  • In one aspect, the invention features a secondary electrochemical cell including a cathode, an anode, a current collector including aluminum, and an electrolyte containing a perchlorate salt and a second salt that is different from the perchlorate salt. Preferably, the second salt is not a perchlorate salt. The electrolyte is essentially free of LiPF[0006] 6. The electrolyte can contain at least 5000 ppm by weight of the perchlorate salt or at least 10,000 ppm by weight of the perchlorate salt. An example of the second salt is LiTFS.
  • In another aspect, the invention features an electrochemical cell including a cathode containing MnO[0007] 2, an anode containing lithium, and an electrolyte containing a perchlorate salt. The cell includes an aluminum surface in electrical contact with a second metal surface. Preferably, the surface is a portion of an object having at least one dimension greater than 0.5 mm, 1 mm, or 2 mm. An “aluminum surface” can be the surface of an object made of pure aluminum, or a surface made of an aluminum-based alloy. The second metal surface is different than the aluminum surface. The different metal can be, e.g., steel, stainless steel, or nickel. The different metal can also be a different alloy of aluminum. That is, different alloys of aluminum are considered to be different metals.
  • Because aluminum weighs less than other metals, such as stainless steel, that are used in electrochemical cells, the cell is relatively light. The cell also has low ohmic resistance under polarization, because aluminum is very conductive. Furthermore, aluminum is less expensive than stainless steel. The aluminum is protected from corrosion by the addition of a perchlorate salt. [0008]
  • The cell can include a cathode current collector containing aluminum. The electrolyte can contain about 500 to about 2500 ppm by weight of a perchlorate salt. The perchlorate salt can be, e.g., LiClO[0009] 4, Ca(ClO4)2, Al(ClO4)3, or Ba(ClO4)2. In some embodiments, the electrolyte is essentially free of LiPF6.
  • In another aspect, the invention features an electrochemical cell including a cathode containing an aluminum current collector, an anode, and an electrolyte containing a lithium salt and a perchlorate salt. The cell is a primary electrochemical cell. Primary electrochemical cells are meant to be discharged to exhaustion only once, and then discarded. Primary cells are not meant to be recharged. The cathode can contain MnO[0010] 2 and the anode can contain lithium. The electrolyte can contain at least 500 ppm by weight of the perchlorate salt, or at least 1000, 1500, or 2500 ppm by weight of the perchlorate salt. The electrolyte can also contain less than 20,000 ppm by weight of the perchlorate salt. The perchlorate salt can be, e.g., LiClO4, Ca(ClO4)2, Al(ClO4)3, or Ba(ClO4)2. The electrolyte can also include LiPF6, e.g., at least 5000 ppm by weight LiPF6 or at least 10,000 ppm by weight LiPF6. In other aspects, the electrolyte is essentially free of LiPF6. The case of the cell can be aluminum, either in whole or in part.
  • In another aspect, the invention features an electrochemical cell comprising a cathode containing MnO[0011] 2, an anode containing lithium, and an electrolyte containing about 500 ppm to about 2000 ppm of a perchlorate salt. The perchlorate salt can be, e.g., LiClO4, Ca(ClO4)2, Al(ClO4)3, or Ba(ClO4)2.
  • In another aspect, the invention features an electrochemical cell comprising a cathode containing MnO[0012] 2, an anode containing lithium, and an electrolyte containing a perchlorate salt; the cell is a primary electrochemical cell and includes two pieces of aluminum in electrical contact with each other. The two pieces can be made of the same alloy of aluminum.
  • In yet another aspect, the invention features a method of inhibiting aluminum corrosion in a primary electrochemical cell. The method includes: (a) adding a perchlorate salt to the electrolyte of the cell; and (b) placing the electrolyte, an anode containing Li, and a cathode containing MnO[0013] 2 and an aluminum current collector into a cell case. The perchlorate salt can be, e.g., LiClO4, Ca(ClO4)2, Al(ClO4)3, or Ba(ClO4)2.
  • The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.[0014]
    • DESCRIPTION OF DRAWINGS
  • FIG. 1 is a sectional view of a nonaqueous electrochemical cell. [0015]
  • FIG. 2 is a graph showing current density vs. potential of the aluminum in an electrode exposed to LiTFS, DME:EC:PC electrolytes containing different amounts of LiClO[0016] 4.
  • FIG. 3 is a graph showing current density vs. of the aluminum in an electrode exposed to LiTFS, DME:EC:PC electrolytes containing different amounts of LiClO[0017] 4.
  • FIG. 4 is a graph showing current density vs. time of the aluminum in an electrode exposed to a LiTFS, DME:EC:PC electrolyte containing LiClO[0018] 4.
  • FIG. 5 is a graph showing current density vs. potential of the aluminum in an electrode exposed to LiTFS+LiTFSI, DME:EC:PC electrolytes containing different amounts of LiClO[0019] 4.
  • FIG. 6 is a graph showing current density vs. time of the aluminum in an electrode exposed to LiTFS+LiTFS™, DME:EC:PC electrolytes containing different amounts of LiClO[0020] 4.
  • FIG. 7 is a graph showing current density vs. potential of the aluminum in an electrode exposed to LiTFS+LiPF[0021] 6, DME:EC:PC electrolytes containing different amounts of LiClO4.
  • FIG. 8 is a graph showing current density vs. time of the aluminum in an electrode exposed to LiTFS+LiPF[0022] 6, DME:EC:PC electrolytes containing different amounts of LiClO4.
  • FIG. 9 is a graph showing current density vs. potential of the aluminum in an electrode exposed to a LiTFS, DME:EC:PC electrolyte containing different amounts of LiClO[0023] 4 and different amounts of Al(ClO4)3.
  • FIG. 10 is a graph showing current density vs. potential of the aluminum in an electrode exposed to a LiTFS, DME:EC:PC electrolyte containing different amounts of LiClO[0024] 4 and different amounts of Ba(ClO4)2.
    • DETAILED DESCRIPTION
  • Referring to FIG. 1, an [0025] electrochemical cell 10 includes an anode 12 in electrical contact with a negative lead 14, a cathode 16 in electrical contact with a positive lead 18, a separator 20 and an electrolytic solution. Anode 12, cathode 16, separator 20 and the electrolytic solution are contained within a case 22. The electrolytic solution includes a solvent system and a salt that is at least partially dissolved in the solvent system.
  • [0026] Cathode 16 includes an active cathode material, which is generally coated on the cathode current collector. The current collector is generally titanium, stainless steel, nickel, aluminum, or an aluminum alloy, e.g., aluminum foil. The active material can be, e.g., a metal oxide, halide, or chalcogenide; alternatively, the active material can be sulfur, an organosulfur polymer, or a conducting polymer. Specific examples include MnO2, V2O5, CoF3, MoS2, FeS2, SOCl2, MoO3, S, (C6H5N)n, (S3N2)n, where n is at least 2. The active material can also be a carbon monofluoride. An example is a compound having the formula CFx, where x is 0.5 to 1.0. The active material can be mixed with a conductive material such as carbon and a binder such as polytetrafluoroethylene (PTFE). An example of a cathode is one that includes aluminum foil coated with MnO2. The cathode can be prepared as described in U.S. Pat. No. 4,279,972.
  • [0027] Anode 12 can consist of an active anode material, usually in the form of an alkali metal, e.g., Li, Na, K, or an alkaline earth metal, e.g., Ca, Mg. The anode can also consist of alloys of alkali metals and alkaline earth metals or alloys of alkali metals and Al. The anode can be used with or without a substrate. The anode also can consist of an active anode material and a binder. In this case an active anode material can include carbon, graphite, an acetylenic mesophase carbon, coke, a metal oxide and/or a lithiated metal oxide. The binder can be, for example, PTFE. The active anode material and binder can be mixed to form a paste which can be applied to the substrate of anode 12.
  • [0028] Separator 20 can be formed of any of the standard separator materials used in nonaqueous electrochemical cells. For example, separator 20 can be formed of polypropylene, (e.g., nonwoven polypropylene or microporous polypropylene), polyethylene, and/or a polysulfone.
  • The electrolyte can be in liquid, solid or gel (polymer) form. The electrolyte can contain an organic solvent such as propylene carbonate (PC), ethylene carbonate (EC), dimethoxyethane (DME), dioxolane (DO), tetrahydrofuran (THF), acetonitrile (CH[0029] 3CN), gamma-butyrolactone, diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) dimethylsulfoxide (DMSO) methyl acetate (MA), methyl formiate (MF), sulfolane or combinations thereof. The electrolyte can alternatively contain an inorganic solvent such as SO2 or SOCl2. The electrolyte also contains a lithium salt such as lithium trifluoromethanesulfonate (LiTFS) or lithium trifluoromethanesulfonimide (LiTFSI), or a combination thereof. Additional lithium salts that can be included are listed in U.S. Pat. No. 5,595,841, which is hereby incorporated by reference in its entirety. In some embodiments, the electrolyte may contain LiPF6; in other embodiments, the electrolyte is essentially free of LiPF6. The electrolyte also contains a perchlorate salt, which inhibits corrosion in the cell. Examples of suitable salts include lithium, barium, calcium, aluminum, sodium, potassium, magnesium, copper, zinc, ammonium, and tetrabutylammonium perchlorates. Generally, at least 500 ppm by weight of the perchlorate salt is used; this ensures that there is enough salt to suppress corrosion. In addition, less than about 20,000 by weight of the perchlorate salt is generally used. If too much perchlorate salt is used, the cell can be internally shorted under certain conditions during use.
  • To assemble the cell, [0030] separator 20 can be cut into pieces of a similar size as anode 12 and cathode 16 and placed therebetween as shown in FIG. 1. Anode 12, cathode 16, and separator 20 are then placed within case 22, which can be made of a metal such as nickel, nickel plated steel, stainless steel, or aluminum, or a plastic such as polyvinyl chloride, polypropylene, polysulfone, ABS or a polyamide. Case 22 is then filled with the electrolytic solution and sealed. One end of case 22 is closed with a cap 24 and an annular insulating gasket 26 that can provide a gas-tight and fluid-tight seal. Positive lead 18, which can be made of aluminum, connects cathode 16 to cap 24. Cap 24 may also be made of aluminum. A safety valve 28 is disposed in the inner side of cap 24 and is configured to decrease the pressure within battery 10 when the pressure exceeds some predetermined value. Additional methods for assembling the cell are described in U.S. Pat. Nos. 4,279,972; 4,401,735; and 4,526,846.
  • Other configurations of [0031] battery 10 can also be used, including, e.g., the coin cell configuration. The batteries can be of different voltages, e.g., 1.5V, 3.0V, or 4.0V.
  • The invention is further described in the following examples, which do not limit the scope of the invention described in the claims. [0032]
    • EXAMPLE 1 Al Corrosion in Different Electrolytes with Addition of LiClO4
  • Glass Cell Experimentation [0033]
  • An electrochemical glass cell was constructed having an Al working electrode, a Li reference electrode, and two Li auxiliary electrodes. The working electrode was fabricated from a 99.999% Al rod inserted into a Teflon sleeve to provide a planar electrode area of 0.33 cm. The native oxide layer was removed by first polishing the planar working surface with 3 μm aluminum oxide paper under an argon atmosphere, followed by thorough rinsing of the Al electrode in electrolyte. All experiments were performed under an Ar atmosphere. [0034]
  • Cyclic Voltammetry [0035]
  • Corrosion current measurements were made according to a modified procedure generally described in X. Wang et al., [0036] Electrochemica Acta, vol. 45, pp. 2677-2684 (2000). The corrosion potential of Al was determined by continuous cyclic voltammetry. In each cycle, the potential was initially set to an open circuit potential, then anodically scanned to +4.5 V and reversed to an open circuit potential. A scan rate of 50 mV/s was selected, at which good reproducibility of the corrosion potential of aluminum was obtained. The corrosion potential of aluminum was defined as the potential at which the anodic current density reached 10−5 A/cm2 at the first cycle.
  • Chronoamperometry [0037]
  • Corrosion current measurements were made according to the procedure described in [0038] EP 0 852 072. The aluminum electrode was polarized at various potentials vs. a Li reference electrode while the current was recorded vs. time. Current vs. time measurements were taken during a 30-minute period. The area under current vs. time curve was used as a measure of the amount of aluminum corrosion occurring. The experiment also could be terminated in case the current density reached 3 mA/cm2 before the 30 minute time period elapsed and no corrosion suppression occurred. Corrosion suppression occurred when the resulting current density was observed in the range of 10−6 A/cm2.
  • Referring to FIG. 2, cyclic voltammograms taken in the electrolyte containing LiTFS and DME:EC:PC showed significant shifts in the corrosion potential of the Al electrode. The addition of LiClO[0039] 4 to the electrolyte shifted the potential of aluminum in the positive direction, which indicates corrosion suppression.
  • Curves “a” and “a′” in FIG. 2 show the corrosion potential of the aluminum in the electrolyte containing no LiClO[0040] 4. The addition of 500 ppm of LiClO4 to the electrolyte shifted the potential of the aluminum 150 mV in the positive direction (curves “b” and “b′”); the addition of 1000 ppm of LiClO4 to the electrolyte shifted the potential 300 mV (curves “c” and “c′”); and the addition of 2500 ppm of LiClO4 to the electrolyte shifted the potential 600 mV (curves “d” and “d′”). These results demonstrate that the addition of increasing amounts of LiClO4 to the electrolyte containing LiTFS salt and mixture of DME:EC:PC results in increasing degrees of corrosion protection of the aluminum electrode.
  • Referring to FIG. 3, curve “a” shows a potentiostatic dependence (chronoamperogram) of the aluminum electrode exposed to the electrolyte containing LiTFS, DME:EC:PC with the addition of 500 ppm LiClO[0041] 4; curve “b” shows the chronoamperogram taken in the same electrolyte with addition of 1000 ppm LiClO4; curve “c” shows the chronoamperogram taken in the electrolyte containing LiTFS, DME:EC:PC, and 2500 ppm LiClO4. As shown in FIG. 3, at a LiClO4 concentration of 2500 ppm, the aluminum corrosion at +3.6 V (vs. a Li reference electrode) is effectively suppressed, and the corrosion current is less than 10−6 A/cm2 after 30 minutes of measurement.
  • Referring to FIG. 4, the electrochemical window of Al stability can be extended as high as +4.2 V (vs. a Li reference electrode) by increasing the concentration of LiClO[0042] 4 to 1% (10,000 ppm). At a LiClO4 concentration of 1%, aluminum corrosion is effectively suppressed at 4.2 V. The corrosion current after 30 minutes is 8-10 μA/cm2, and the current continues to fall over time. The falling current indicates passivation of the Al surface. The increased level of the resulting current (10 μA/cm2 vs. 1 μA/cm2 after 30 minutes of experiment) is due to the increased background current at these potentials.
  • Referring to FIG. 5, curves “a”, “a′”, and “a″” show the corrosion potential of an aluminum electrode subjected to an electrolyte containing a mixture of LiTFS and LiTFSI salts, DME:EC:PC, and no LiClO[0043] 4. The addition of 500 ppm of LiClO4 to this electrolyte shifted the corrosion potential of the aluminum 150 mV in the positive direction (curves “b” and “b′”); the addition of 1000 ppm of LiClO4 to the electrolyte shifted the potential 280 mV (curves “c” and “c′”); and the addition of 2500 ppm of LiClO4 to the electrolyte shifted potential 460 mV (curves “d” and “d′”). These results demonstrate that the addition of increasing amounts of LiClO4 to the electrolyte containing the mixture of LiTFS and LiTFSI salts and DME:EC:PC results in increasing degrees of corrosion protection of the aluminum electrode.
  • Referring to FIG. 6, curve “a” shows the chronoamperogram of the aluminum electrode exposed to the electrolyte containing a mixture of LiTFS and LiTFSI salts, DME:EC:PC, and 1000 ppm LiClO[0044] 4; and curve “b” shows the chronoamperogram of the aluminum electrode exposed to the same electrolyte containing 2500 ppm LiClO4. As shown in FIG. 5, at a LiClO4 concentration of 2500 ppm in LiTFS, LiTFSI, DME:EC:PC electrolyte, the aluminum corrosion at +3.6 V is effectively suppressed, and resulting corrosion current of the Al electrode is about 10−6 A/cm2 after 30 minutes.
  • Referring to FIG. 7, curve “a” shows the corrosion potential of the aluminum subjected to an electrolyte containing a mixture of LiTFS and LiPF[0045] 6 salts, DME:EC:PC, and no LiClO4. The addition of 500 ppm of LiClO4 to this electrolyte shifted the corrosion potential of the aluminum 125 mV in the positive direction (curve “b”); the addition of 2500 ppm of LiClO4 to the electrolyte shifted the potential 425 mV (curve “c”); and the addition of 5000 ppm of LiClO4 to the electrolyte shifted the potential 635 mV (curve “d”). These results demonstrate that the addition of increasing amounts of LiClO4 to the electrolyte containing the mixture of LiTFS, LiPF6 salts, and DME:EC:PC results in increasing degrees of corrosion protection of the aluminum electrode.
  • Referring to FIG. 8, curve “a” shows a chronoamperogram of the aluminum electrode exposed to the electrolyte containing LiTFS, LiPF[0046] 6, DME:EC:PC with no LiClO4; curve “b” shows a chronoamperogram taken in the same electrolyte with 2500 ppm LiClO4 added; curve “c” shows a chronoamperogram taken in the electrolyte containing LiTFS, LiPF6, DME:EC:PC, and 5000 ppm LiClO4. As shown in FIG. 8, at a LiClO4 concentration of 5000 ppm, the aluminum corrosion at +3.6 V (vs. a Li reference electrode) is effectively suppressed, and the corrosion current is less than 10−6 A/cm2 after 30 minutes of measurement.
    • EXAMPLE 2 Al Corrosion in Electrolytes Containing LiTFS, DME:EC:PC, with the Addition of Different Perchlorates
  • Electrochemical glass cells were constructed as described in Example 1. Cyclic voltammetry and chromoamperometry were performed as described in Example 1. [0047]
  • Referring to FIG. 9, curves “a”, “b”, and “c” show the corrosion potential of an aluminum electrode exposed to the electrolyte LiTFS, DME:EC:PC containing 0, 1000 and 2500 ppm of LiClO[0048] 4, respectively. Curves “a′”, “b′,” and “c′” show the corrosion potential of an aluminum electrode exposed to the electrolyte LiTFS, DME:EC:PC containing 0, 1000 and 2500 ppm of Al(ClO4)3, respectively. These results demonstrate that the addition of Al(ClO4)3 salt, like the addition of LiClO4 salt, suppressed the corrosion of Al.
  • Referring to FIG. 10, curves “a”, “b”, and “c” show the corrosion potential of an aluminum electrode exposed to the electrolyte LiTFS, DME:EC:PC containing 0, 1000 and 2500 ppm of LiClO[0049] 4, respectively. Curves “a′”, “b′” and “c′” show the corrosion potential of an aluminum electrode exposed to the electrolyte LiTFS, DME:EC:PC containing 0, 1000 and 2500 ppm of Ba(ClO4)2, respectively. These results demonstrate that the addition of Ba(ClO4)2 salt, like the addition of LiClO4 salt, suppressed the corrosion of Al.
  • The shifts in the corrosion potential that result from the addition of LiClO[0050] 4, Al(ClO4)3, and Ba(ClO4)2 to an electrolyte containing LiTFS and DME:EC:PC are summarized below in Table 1.
    TABLE 1
    Anodic shift of corrosion potential (mV)
    Additive 0 ppm 1000 ppm 2500 ppm
    Al(ClO4)3 0 170 450
    Ba(ClO4)2 0 170 400
    LiClO 4 0 300 600
    • Example 3 Al Corrosion in Electrolyte Containing LiTFS, DME:EC:PC, (Vial Storage Test)
  • The following test conditions were used: [0051]
  • Electrodes: EMD (electrochemically synthesized manganese dioxide) based cathodes applied on the Al current collector [0052]
  • Electrolyte (10 mL per sample): LiTFS, DME:EC:PC with and without addition of LiClO[0053] 4 salt
  • Aging conditions: 60° C. for 20 days [0054]
  • Direct determination of Al corrosion was performed in one of two ways: [0055]
  • Analytical determination of Al ions in the electrolyte after aging (ICP method) [0056]
  • Direct observation of the Al surface (optical microscopy) after aging [0057]
  • Measurements of Al corrosion were performed by measuring the Al ions in the electrolyte after aging of the EMD based cathodes with an Al current collector. Analytical results (ICP) are summarized in Table 2. [0058]
    TABLE 2
    Al concentration after storage
    Sample Electrolyte (ppm)
    None LiTFS, DME:EC:PC  1.94 ± 0.20
    EMD based cathode on Al LiTFS, DME:EC:PC 21.55 ± 1.58
    current collector
    EMD based cathode on Al LiTFS, DME:EC:PC + 2500  2.16 ± 0.18
    current collector ppm LiClO4
  • The level of Al ions in the electrolyte indicates the rate of Al corrosion. As shown above, the background level of Al ions in solution is about 2 ppm. As referred to herein, the corrosion of a metal is said to be suppressed when, after the test described above is performed, the concentration of metal ions in the electrolyte is less than about 3 ppm, which is just above the background level. [0059]
  • The Al concentration in the electrolyte without LiClO[0060] 4 addition is high (the range is 19.4-23 ppm). Thus, part of the Al substrate has dissolved (corroded) under the potential of the applied active cathode material.
  • On the other hand, the samples which were stored in the electrolytes with added LiClO[0061] 4 did not show any corrosion (the resulting Al concentration in the electrolyte is at the background level 1.9-2.3 ppm). These data confirm results of the electrochemical measurements in a glass cell: 2500 ppm of LiClO4 completely suppresses the corrosion of Al at the potential of the EMD cathode.
  • The analytical data were confirmed by the direct observation of Al surface after aging (under an optical microscope, at a magnification of 60×). The electrodes stored in the electrolyte without LiClO[0062] 4 exhibited substantial corrosion, as viewed under the optical microscope. The section stored in the electrolyte with added LiClO4 showed virtually no corrosion.
    • EXAMPLE 4 Al Current Collector Coupled with Other Metals, (Vial Storage Test)
  • The same cathodes on the Al substrate as described above were used in this experiment. In this case, the Al substrates were welded to stainless steel (SS) or nickel (Ni) tabs. A description of the samples and analytical results is presented in Table 3. [0063]
    TABLE 3
    Ni Al Fe
    Sample Electrolyte (ppm) (ppm) (ppm)
    None LiTFS, DME:EC:PC <1.0 <1.0 <1.0
    Cathode (Al cur. collector with LiTES, DME:EC:PC <1.0 <24.4 <5.3
    welded SS tab)
    Cathode (Al cur. collector with LiTES, DME:EC:PC 90.9 20.5 <1.0
    welded Ni tab)
    Cathode (Al cur. collector with LiTFS, DME:EC:PC + 2500 <1.0 <1.0 <1.0
    welded SS tab) ppm LiClO4
    Cathode (Al cur. collector with LiTFS, DME:EC:PC + 2500 <1.0 <1.0 <1.0
    welded Ni tab) ppm LiClO4
  • The highest corrosion rate was observed on the sample welded to the SS tab and stored in the electrolyte without added LiClO[0064] 4 (the resulting solution contains the residue colored as a rust, and the SS tab is separated from the Al substrate). The presence of iron (5.3 ppm of Fe ions in the resulting electrolyte) indicates a high rate of SS corrosion as well as Al corrosion (24.4 ppm of the Al in the resulting electrolyte).
  • A high concentration of Ni (90.9 ppm) in the resulting electrolyte (Al current collector with welded Ni tab, electrolyte without LiClO[0065] 4) indicates the severe corrosion of the Ni tab coupled with Al (the Al corroded as well, as indicated by the presence of 20.5 ppm Al).
  • On the other hand, the samples stored in the electrolytes with added LiClO[0066] 4 did not show any corrosion (the resulting Al, Ni, Fe concentrations in the electrolyte were at the background level of <1 ppm).
    • EXAMPLE 5 Al corrosion in electrolyte containing LiTFS, DME:EC:PC and 2500 ppm of LiClO4, (2/3A cell tests)
  • Cells were assembled with investigated parts and electrolytes according to the standard procedure with Al current foil applied as the cathode substrate. [0067]
  • The assembled cells (2/3A size) were stored 20 days at 60° C. Electrolyte removed from the cells after storage was submitted for ICP analysis. The electrolyte did not show any traces of Al, Fe, or Ni (the concentrations were at the background level). [0068]
    • EXAMPLE 6 Corrosion Tests Using Different Aluminum Alloys, (Vial Storage Test)
  • Two cathodes were prepared by coating aluminum foil substrates (1145 Al) with MnO[0069] 2. Pieces of aluminum foil (3003 Al) were welded to the aluminum foil of each of the cathodes. One cathode was stored for 20 days at 60° C. over LiTFS, DME:EC:PC electrolyte containing 2500 ppm of LiClO4. The second cathode was stored for 20 days at 60° C. over LiTFS, DME:EC:PC electrolyte containing no LiClO4. After the 20-day period, the electrolytes were analyzed by ICP. The first electrolyte (2500 ppm LiClO4 in the electrolyte) contained less than 1 ppm Al, while the second electrolyte (no LiClO4 in the electrolyte) contained 18 ppm Al. These results indicate that the presence of LiClO4 can suppress corrosion when two different alloys of aluminum are in electrical contact in the presence of electrolyte.
  • All publications, patents, and patent applications mentioned in this application are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference. [0070]
    • Other embodiments
  • A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. For example, although the examples described above relate to batteries, the invention can be used to suppress aluminum corrosion in systems other than batteries, in which an aluminum-metal couple occurs. Other embodiments are within the scope of the following claims. [0071]

Claims (47)

What is claimed is:
1. An electrochemical cell comprising a cathode, an anode, a current collector including aluminum, an electrolyte containing a perchlorate salt and a second salt, wherein the electrochemical cell is a secondary cell, and wherein the electrolyte is essentially free of LiPF6.
2. The cell of claim 1, wherein the electrolyte contains at least 5000 ppm by weight of a perchlorate salt.
3. The cell of claim 2, wherein the electrolyte contains at least 10,000 ppm by weight of a perchlorate salt.
4. An electrochemical cell comprising a cathode containing MnO2, an anode containing lithium, and an electrolyte containing a perchlorate salt, wherein the cell includes an aluminum surface in electrical contact with a second metal surface, wherein the second metal surface is different than the aluminum surface.
5. The cell of claim 4, wherein the second metal surface is a steel surface.
6. The cell of claim 4, wherein the second metal surface is a stainless steel surface.
7. The cell of claim 4, wherein the second metal surface is an aluminum or aluminum alloy surface.
8. The cell of claim 4, wherein the second metal surface is a nickel surface.
9. The cell of claim 4, wherein the cell includes a cathode current collector comprising aluminum.
10. The cell of claim 4, wherein the electrolyte contains about 500 to about 2500 ppm by weight of the perchlorate salt.
11. The cell of claim 4, wherein the perchlorate salt is LiClO4.
12. The cell of claim 4, wherein the perchlorate salt is Ca(ClO4)2.
13. The cell of claim 4, wherein the perchlorate salt is Ba(ClO4)2.
14. The cell of claim 4, wherein the perchlorate salt is Al(ClO4)3.
15. The cell of claim 4, wherein the electrolyte is essentially free of LiPF6.
16. The cell of claim 4, wherein the aluminum surface is a portion of an object having at least one dimension greater than 0.5 mm.
17. The cell of claim 4, wherein the aluminum surface is a portion of an object having at least one dimension greater than 1 mm.
18. The cell of claim 4, wherein the aluminum surface is a portion of an object having at least one dimension greater than 2 mm.
19. An electrochemical cell comprising a cathode containing an aluminum current collector, an anode, and an electrolyte containing a lithium salt and a perchlorate salt, wherein the cell is a primary electrochemical cell.
20. The cell of claim 19, wherein the cathode contains MnO2.
21. The cell of claim 19, wherein the anode contains lithium.
22. The cell of claim 19, wherein the electrolyte contains at least 500 ppm by weight of the perchlorate salt.
23. The cell of claim 19, wherein the electrolyte contains at least 1000 ppm by weight of the perchlorate salt.
24. The cell of claim 19, wherein the electrolyte contains at least 1500 ppm by weight of the perchlorate salt.
25. The cell of claim 19, wherein the electrolyte contains at least 2500 ppm by weight of the perchlorate salt.
26. The cell of claim 19, wherein the electrolyte contains less than 20,000 ppm by weight of the perchlorate salt.
27. The cell of claim 19, wherein the perchlorate salt is LiClO4.
28. The cell of claim 19, wherein the perchlorate salt is Ca(ClO4)2.
29. The cell of claim 19, wherein the perchlorate salt is Ba(ClO4)2.
30. The cell of claim 19, wherein the perchlorate salt is Al(ClO4)3.
31. The cell of claim 19, wherein the cell includes a case comprising aluminum.
32. The cell of claim 31, wherein the case consists essentially of aluminum.
33. The cell of claim 19, wherein the electrolyte further comprises LiPF6.
34. The cell of claim 33, wherein the electrolyte contains at least 5000 ppm by weight LiPF6.
35. The cell of claim 34, wherein the electrolyte contains at least 10,000 ppm by weight LiPF6.
36. The cell of claim 19, wherein the electrolyte is essentially free of LiPF6.
37. An electrochemical cell comprising a cathode containing MnO2, an anode containing lithium, an aluminum surface, and an electrolyte containing about 500 ppm to about 2000 ppm by weight of a perchlorate salt.
38. The cell of claim 37, wherein the perchlorate salt is LiClO4.
39. The cell of claim 37, wherein the perchlorate salt is Ca(ClO4)2.
40. The cell of claim 37, wherein the perchlorate salt is Ba(ClO4)2.
41. The cell of claim 37, wherein the perchlorate salt is Al(ClO4)3.
42. An electrochemical cell comprising a cathode containing MnO2, an anode containing lithium, and an electrolyte containing a perchlorate salt, wherein the cell is a primary electrochemical cell, and wherein the cell includes two pieces of aluminum in electrical contact with each other.
43. A method of inhibiting aluminum corrosion in an electrochemical cell, the method comprising:
(a) adding a perchlorate salt to an electrolyte; and
(b) placing the electrolyte, an anode containing Li, and a cathode containing MnO2 and an aluminum current collector into a cell case to form the cell, wherein the cell is a primary electrochemical cell.
44. The method of claim 43, wherein the perchlorate salt is LiClO4.
45. The method of claim 43, wherein the perchlorate salt is Ca(ClO4)2.
46. The method of claim 43, wherein the perchlorate salt is Ba(ClO4)2.
47. The method of claim 43, wherein the perchlorate salt is Al(ClO4)3.
US10/022,289 2001-12-14 2001-12-14 Electrolyte additive for non-aqueous electrochemical cells Abandoned US20030113622A1 (en)

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US10/361,945 US20030124421A1 (en) 2001-12-14 2003-02-10 Non-aqueous electrochemical cells
US10/990,379 US20050089760A1 (en) 2001-12-14 2004-11-17 Electrolyte additive for non-aqueous electrochemical cells
US12/137,100 US7927739B2 (en) 2001-12-14 2008-06-11 Non-aqueous electrochemical cells
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US7927739B2 (en) 2011-04-19
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EP1527488B2 (en) 2017-07-19
EP2204869A3 (en) 2010-09-01
JP2005538498A (en) 2005-12-15
CN1630959A (en) 2005-06-22
BR0214896A (en) 2006-05-30
CN1320674C (en) 2007-06-06
US20120096708A1 (en) 2012-04-26
EP2204869A2 (en) 2010-07-07
AR038015A1 (en) 2004-12-22
WO2003052845A2 (en) 2003-06-26
AU2002360562A1 (en) 2003-06-30
US20080261110A1 (en) 2008-10-23
US20050089760A1 (en) 2005-04-28
EP1527488B1 (en) 2013-11-20
EP1527488A2 (en) 2005-05-04
JP4623965B2 (en) 2011-02-02
US20030124421A1 (en) 2003-07-03
AU2002360562A8 (en) 2003-06-30

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