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Publication numberUS20030124421 A1
Publication typeApplication
Application numberUS 10/361,945
Publication date3 Jul 2003
Filing date10 Feb 2003
Priority date14 Dec 2001
Also published asCN1320674C, CN1630959A, EP1527488A2, EP1527488B1, EP1527488B2, EP2204869A2, EP2204869A3, EP2204869B1, US7927739, US20030113622, US20050089760, US20080261110, US20120096708, WO2003052845A2, WO2003052845A3
Publication number10361945, 361945, US 2003/0124421 A1, US 2003/124421 A1, US 20030124421 A1, US 20030124421A1, US 2003124421 A1, US 2003124421A1, US-A1-20030124421, US-A1-2003124421, US2003/0124421A1, US2003/124421A1, US20030124421 A1, US20030124421A1, US2003124421 A1, US2003124421A1
InventorsNikolai Issaev, Michael Pozin
Original AssigneeIssaev Nikolai N., Michael Pozin
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Non-aqueous electrochemical cells
US 20030124421 A1
Abstract
An electrochemical secondary cell is disclosed. The cell includes a cathode, an anode, a cathode current collector including stainless steel, and an electrolyte containing a perchlorate salt and a second salt.
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Claims(67)
What is claimed is:
1. An electrochemical cell, comprising:
a cathode;
an anode;
a cathode current collector comprising steel; and
an electrolyte comprising a perchlorate salt and a second salt, wherein the electrochemical cell is a secondary cell.
2. The cell of claim 1, wherein the cathode current collector comprises a stainless steel.
3. The cell of claim 1, wherein the steel is selected from the group consisting of a 200 series stainless steel, a 300 series stainless steel, a 400 series stainless steel, and a cold roll steel.
4. The cell of claim 1, wherein the perchlorate salt comprises LiClO4.
5. The cell of claim 1, wherein the perchlorate salt comprises a material selected from the group consisting of Ca(ClO4)2, Ba(ClO4)2, Al(ClO4)3, Mg(ClO4)2, KClO4, tetrabutylammonium perchlorate, and tetraethylammonium perchlorate.
6. The cell of claim 1, wherein the electrolyte comprises between about 300 ppm and about 50,000 ppm by weight of the perchlorate salt.
7. The cell of claim 1, wherein the electrolyte comprises between about 300 ppm and about 40,000 ppm by weight of the perchlorate salt.
8. The cell of claim 1, wherein the electrolyte comprises between about 300 ppm and about 30,000 ppm by weight of the perchlorate salt.
9. The cell of claim 1, wherein the electrolyte comprises between about 300 ppm and about 20,000 ppm by weight of the perchlorate salt.
10. The cell of claim 1, wherein the electrolyte comprises between about 300 ppm and about 10,000 ppm by weight of the perchlorate salt.
11. The cell of claim 1, wherein the electrolyte comprises between about 300 ppm and about 5,000 ppm by weight of the perchlorate salt.
12. An electrochemical cell, comprising:
a cathode;
an anode;
a cathode current collector including steel; and
an electrolyte containing a perchlorate salt and a second salt, wherein the electrochemical cell is a primary cell.
13. The cell of claim 12, wherein the cathode comprises manganese oxide.
14. The cell of claim 12, wherein the anode comprises lithium.
15. The cell of claim 12, wherein the cathode current collector comprises a stainless steel.
16. The cell of claim 12, wherein the steel is selected from the group consisting of a 200 series stainless steel, a 300 series stainless steel, a 400 series stainless steel, and a cold roll steel.
17. The cell of claim 12, wherein the perchlorate salt comprises LiClO4.
18. The cell of claim 12, wherein the perchlorate salt comprises a material selected from the group consisting of Ca(ClO4)2, Ba(ClO4)2, Al(ClO4)3, Mg(ClO4)2, KClO4, tetrabutylanmonium perchlorate, and tetraethylammonium perchlorate.
19. The cell of claim 12, wherein the electrolyte comprises between about 300 ppm and about 50,000 ppm by weight of the perchlorate salt.
20. The cell of claim 12, wherein the electrolyte comprises between about 300 ppm and about 40,000 ppm by weight of the perchlorate salt.
21. The cell of claim 12, wherein the electrolyte comprises between about 300 ppm and about 30,000 ppm by weight of the perchlorate salt.
22. The cell of claim 12, wherein the electrolyte comprises between about 300 ppm and about 20,000 ppm by weight of the perchlorate salt.
23. The cell of claim 12, wherein the electrolyte comprises between about 300 ppm and about 10,000 ppm by weight of the perchlorate salt.
24. The cell of claim 12, wherein the electrolyte comprises between about 300 ppm and about 5,000 ppm by weight of the perchlorate salt.
25. An electrochemical cell, comprising:
a cathode;
an anode;
an electrolyte comprising a perchlorate salt;
a first portion comprising a steel; and
a second portion in electrical contact with the first portion, wherein the first and second portions are in electrical contact with the cathode.
26. The cell of claim 25, wherein the first portion comprises a stainless steel.
27. The cell of claim 25, wherein the steel is selected from the group consisting of a 200 series stainless steel, a 300 series stainless steel, a 400 series stainless steel, and a cold roll steel.
28. The cell of claim 25, wherein the first portion is defined by a cathode current collector.
29. The cell of claim 25, wherein the first portion is defined by a container of the cell.
30. The cell of claim 25, wherein the first portion is defined by a tab, a rivet, or a contact plate.
31. The cell of claim 25, wherein the first portion has at least one dimension greater than 0.5 mm.
32. The cell of claim 25, wherein the first portion has at least one dimension greater than 1 mm.
33. The cell of claim 25, wherein the first portion has at least one dimension greater than 2 mm.
34. The cell of claim 25, wherein the first and second portion physically contact each other.
35. The cell of claim 25, wherein the second portion comprises a steel.
36. The cell of claim 25, wherein the second portion comprises a stainless steel.
37. The cell of claim 25, wherein the second portion comprises a composition different than a composition of the first portion.
38. The cell of claim 25, wherein the second portion comprises a composition the same as a composition of the first portion.
39. The cell of claim 25, wherein the cathode comprises manganese oxide.
40. The cell of claim 25, wherein the anode comprises lithium.
41. The cell of claim 25, wherein the cell is a primary cell.
42. The cell of claim 25, wherein the cell is a secondary cell.
43. The cell of claim 25, wherein the perchlorate salt comprises LiClO4.
44. The cell of claim 25, wherein the perchlorate salt comprises a material selected from the group consisting of Ca(ClO4)2, Ba(ClO4)2, Al(ClO4)3, Mg(ClO4)2, KClO4, tetrabutylammonium perchlorate, and tetraethylammonium perchlorate.
45. The cell of claim 25, wherein the electrolyte comprises between about 300 ppm and about 50,000 ppm by weight of the perchlorate salt.
46. The cell of claim 25, wherein the electrolyte comprises between about 300 ppm and about 40,000 ppm by weight of the perchlorate salt.
47. The cell of claim 25, wherein the electrolyte comprises between about 300 ppm and about 30,000 ppm by weight of the perchlorate salt.
48. The cell of claim 25, wherein the electrolyte comprises between about 300 ppm and about 20,000 ppm by weight of the perchlorate salt.
49. The cell of claim 25, wherein the electrolyte comprises between about 300 ppm and about 10,000 ppm by weight of the perchlorate salt.
50. The cell of claim 25, wherein the electrolyte comprises between about 300 ppm and about 5,000 ppm by weight of the perchlorate salt.
51. An electrochemical cell, comprising:
a cathode;
an anode;
an electrolyte comprising a perchlorate salt;
a first portion comprising aluminum; and
a second portion in electrical contact with the first portion, wherein the first and second portions are in electrical contact with the cathode.
52. The cell of claim 51, wherein the first portion comprises an aluminum alloy.
53. The cell of claim 51, wherein the first portion is defined by a tab, a rivet, or a contact plate.
54. The cell of claim 51, wherein the second portion comprises a material different than a material of the first portion.
55. The cell of claim 51, wherein the second portion comprises steel or stainless steel.
56. A method of reducing corrosion, comprising:
adding a perchlorate salt to a non-aqueous solution.
57. The method of claim 56, further comprising
placing the solution, a cathode, an anode, and a member comprising steel into an electrochemical cell.
58. The method of claim 57, wherein the member comprises a stainless steel.
59. The method of claim 57, wherein the steel is selected from the group consisting of a 200 series stainless steel, a 300 series stainless steel, a 400 series stainless steel, and a cold roll steel.
60. The method of claim 56, wherein the perchlorate salt comprises LiClO4.
61. The method of claim 56, wherein the perchlorate salt comprises a material selected from the group consisting of Ca(ClO4)2, Ba(ClO4)2, Al(ClO4)3, Mg(ClO4)2, KClO4, tetrabutylammonium perchlorate, and tetraethylammonium perchlorate.
62. The method of claim 56, wherein the electrolyte comprises between about 300 ppm and about 50,000 ppm by weight of the perchlorate salt.
63. The method of claim 56, wherein the electrolyte comprises between about 300 ppm and about 40,000 ppm by weight of the perchlorate salt.
64. The method of claim 56, wherein the electrolyte comprises between about 300 ppm and about 30,000 ppm by weight of the perchlorate salt.
65. The method of claim 56, wherein the electrolyte comprises between about 300 ppm and about 20,000 ppm by weight of the perchlorate salt.
66. The method of claim 56, wherein the electrolyte comprises between about 300 ppm and about 10,000 ppm by weight of the perchlorate salt.
67. The method of claim 56, wherein the electrolyte comprises between about 300 ppm and about 5,000 ppm by weight of the perchlorate salt.
Description
    CROSS-REFERENCE TO RELATED APPLICATIONS
  • [0001]
    This application is a continuation-in-part application of and claims priority to U.S. application Ser. No. 10/022,289, filed on Dec. 14, 2001, hereby incorporated by reference in its entirety.
  • FIELD OF THE INVENTION
  • [0002]
    The invention relates to non-aqueous electrochemical cells.
  • BACKGROUND
  • [0003]
    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.
  • [0004]
    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.
  • [0005]
    In certain embodiments, the battery includes a metal as a construction material. For example, the metal can be used to construct a battery container (or can) or a current collector for the positive electrode. Sometimes, the metal can corrode because the electrode potential of the metal is lower than the normal operating potential of the positive electrode of the battery. When the metal is coupled with different metals in the environment of an electrochemical cell, the metal can also be susceptible to corrosion. Corrosion can increase the internal impedance of a cell, leading to capacity loss and to a decrease in specific energy. Corrosion can also limit the choice of metals available as a construction material.
  • SUMMARY
  • [0006]
    The invention relates to an electrochemical cell that includes parts made from metals, such as steels (e.g., stainless steels), aluminum, or an aluminum-based alloy; these parts contact the electrolyte of the cell. The cell also includes an additive to suppress corrosion of the parts.
  • [0007]
    In one aspect, the invention features an electrochemical cell, including a cathode, an anode, a cathode current collector comprising steel, and an electrolyte comprising a perchlorate salt and a second salt, wherein the electrochemical cell is a secondary cell. The cathode current collector can include a stainless steel.
  • [0008]
    In another aspect, the invention features an electrochemical cell including a cathode, an anode, a cathode current collector including steel, and an electrolyte containing a perchlorate salt and a second salt, wherein the electrochemical cell is a primary cell.
  • [0009]
    In another aspect, the invention features an electrochemical cell including a cathode, an anode, an electrolyte comprising a perchlorate salt, a first portion comprising a steel, and a second portion in electrical contact with the first portion, wherein the first and second portions are in electrical contact with the cathode.
  • [0010]
    The first portion can include a stainless steel, such as a 200 series stainless steel, a 300 series stainless steel, a 400 series stainless steel, or a cold roll steel. The first portion can be defined by a cathode current collector, a container of the cell, a tab, a rivet, or a contact plate. The first portion can have at least one dimension greater than 0.5 mm, e.g., greater than 1 mm, or greater than 2 mm. The first and second portions can physically contact each other.
  • [0011]
    The second portion can include a steel, e.g., a stainless steel. The second portion can include a composition different from or the same as a composition of the first portion.
  • [0012]
    The cell can be a primary cell or a secondary cell. Primary electrochemical cells are meant to be discharged to exhaustion only once, and then discarded. Primary cells are not meant to be recharged. Secondary cells can be recharged for many times, e.g., more than fifty times, more than a hundred times, or more.
  • [0013]
    In another aspect, the invention features a method of reducing corrosion. The method includes adding a perchlorate salt to a non-aqueous solution. The method can further include placing the solution, a cathode, an anode, and a member including steel into an electrochemical cell.
  • [0014]
    The member can include a stainless steel, such as a 200 series stainless steel, a 300 series stainless steel, a 400 series stainless steel, or a cold roll steel.
  • [0015]
    Embodiments of the aspects of the invention can include one or more of the following features.
  • [0016]
    The steel can be a 200 series stainless steel, a 300 series stainless steel, a 400 series stainless steel, and a cold roll steel.
  • [0017]
    The perchlorate salt can include LiClO4. The perchlorate salt can include Ca(ClO4)2, Ba(ClO4)2, Al(ClO4)3, Mg(ClO4)2, KClO4, tetrabutylammonium perchlorate, or tetraethylammonium perchlorate.
  • [0018]
    The electrolyte can include between about 300 ppm and about 50,000 ppm by weight of the perchlorate salt, e.g., about 300 ppm to about 40,000 ppm, about 300 ppm to about 30,000 ppm, about 300 ppm to about 20,000 ppm, about 300 ppm to about 10,000 ppm, or about 300 ppm to about 5,000 ppm.
  • [0019]
    The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other aspects, features, and advantages of the invention will be apparent from the description and drawings, and from the claims.
  • DESCRIPTION OF DRAWINGS
  • [0020]
    [0020]FIG. 1 is a sectional view of a nonaqueous electrochemical cell.
  • [0021]
    [0021]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 LiClO4.
  • [0022]
    [0022]FIG. 3 is a graph showing current density vs. time of the aluminum in an electrode exposed to LiTFS, DME:EC:PC electrolytes containing different amounts of LiClO4.
  • [0023]
    [0023]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 LiClO4.
  • [0024]
    [0024]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 LiClO4.
  • [0025]
    [0025]FIG. 6 is a graph showing current density vs. time of the aluminum in an electrode exposed to LiTFS+LiTFSI, DME:EC:PC electrolytes containing different amounts of LiClO4.
  • [0026]
    [0026]FIG. 7 is a graph showing current density vs. potential of the aluminum in an electrode exposed to LiTFS+LiPF6, DME:EC:PC electrolytes containing different amounts of LiClO4.
  • [0027]
    [0027]FIG. 8 is a graph showing current density vs. time of the aluminum in an electrode exposed to LiTFS+LiPF6, DME:EC:PC electrolytes containing different amounts of LiClO4.
  • [0028]
    [0028]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 LiClO4 and different amounts of Al(ClO4)3.
  • [0029]
    [0029]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 LiClO4 and different amounts of Ba(ClO4)2.
  • [0030]
    [0030]FIG. 11 is a graph showing current density vs. potential of 304 stainless steel in an electrode exposed to LiTFS, DME:EC:PC electrolytes containing no LiClO4 and an amount of LiClO4.
  • [0031]
    [0031]FIG. 12 is a graph showing current density vs. time of 304 stainless steel in an electrode exposed to LiTFS, DME:EC:PC electrolytes containing no LiClO4 and an amount of LiClO4.
  • [0032]
    [0032]FIG. 13 is a graph showing current density vs. potential of 416 stainless steel in an electrode exposed to LiTFS, DME:EC:PC electrolytes containing different amounts of LiClO4.
  • [0033]
    [0033]FIG. 14 is a graph showing current density vs. time of 416 stainless steel in an electrode exposed to LiTFS, DME:EC:PC electrolytes containing different amounts of LiClO4.
  • [0034]
    [0034]FIG. 15 is a graph showing current density vs. time of 416 stainless steel in an electrode exposed to LiTFS, DME:EC:PC electrolytes containing an amount of LiClO4.
  • [0035]
    [0035]FIG. 16 is a graph a graph showing current density vs. time of cold roll steel in an electrode exposed to LiTFS, DME:EC:PC electrolytes containing different amounts of LiClO4.
  • DETAILED DESCRIPTION
  • [0036]
    Referring to FIG. 1, 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.
  • [0037]
    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 cobalt oxides, MnO2, manganese spinels, V2O5, CoF3, molybdenum-based materials such as MoS2 and MoO3, FeS2, SOCl2, 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, or higher. 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. Specific cathode materials are a function of, e.g., the type of cell such as primary or secondary.
  • [0038]
    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 tin-based materials, carbon-based materials, such as 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. Specific anode materials are a function of, e.g., the type of cell such as primary or secondary.
  • [0039]
    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.
  • [0040]
    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), butylene carbonate (BC), dioxolane (DO), tetrahydrofuran (THF), acetonitrile (CH3CN), 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.
  • [0041]
    In preferred embodiments, 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, tetrabutylammonium, and tetraethylammonium perchlorates. Generally, at least 300 ppm by weight of the perchlorate salt is used; this ensures that there is enough salt to suppress corrosion. In addition, less than about 50,000 ppm by weight of the perchlorate salt is generally used. If too much perchlorate salt is used, under certain conditions, the cell can be unsafe. In certain embodiments, greater than or equal to about 300 ppm, 500 ppm, 2,500 ppm, 5,000 ppm, 10,000 ppm, 15,000 ppm, 20,000 ppm, 25,000 ppm, 30,000 ppm, 35,000 ppm, 40,000 ppm, or 45,000 ppm by weight of the perchlorate salt is used. Alternatively or in addition, less than or equal to about 50,000 ppm, 45,000 ppm, 40,000 ppm, 35,000 ppm, 30,000 ppm, 25,000 ppm, 20,000 ppm, 15,000 ppm, 10,000 ppm, 5,000 ppm, 2,500 ppm, or 500 ppm by weight of the perchlorate is used. An effective amount of perchlorate to reduce, e.g., inhibit, corrosion to a desired level in the cell can be determined experimentally, e.g., using cyclic voltammetry.
  • [0042]
    In some embodiments, cell 10 includes an electrolyte formed of a mixture of solvents having DME and PC, and a salt mixture of LiTFS and LiTFSI. The concentration of DME in the mixture of solvents can range from about 30% to about 85% by weight. The concentration of DME in the mixture of solvents can be equal to or greater than 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80% by weight; and/or equal to or less than 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, or 35% by weight. The concentration of PC in the mixture of solvents can be equal to 100% minus the concentration of DME. For example, if the concentration of DME in the mixture of solvents is 75% by weight, then the concentration of PC in the mixture of solvents is 25% by weight. If the concentration of DME in the mixture of solvents is 50%-75% by weight, then the concentration of PC in the mixture of solvents is 25%-50% by weight.
  • [0043]
    For the LiTFS and LiTFSI salt mixture, the total concentration of salt in the mixture of solvents can range from about 0.4 M to about 1.2 M. The total concentration of LiTFS and LiTFSI in the mixture of solvents can be equal to or greater than 0.40 M, 0.45 M, 0.50 M, 0.55 M, 0.60 M, 0.65 M, 0.70 M, 0.75 M, 0.80 M, 0.85 M, 0.90 M, 0.95 M, 1.00 M, 1.05 M, 1.10 M, or 1.15 M; and/or equal to or less than 1.2 M, 1.15 M, 1.10 M, 1.05 M, 1.00 M, 0.95 M, 0.90 M, 0.85 M, 0.80 M, 0.75 M, 0.70 M, 0.65 M, 0.60 M, 0.55 M, 0.50 M, or 0.45 M. Of the total concentration of salt, the concentration of LiTFS in the mixture of solvents can be (in mole fraction) equal to or greater than 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100%; and/or equal to or less than 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or 5%. The concentration of LiTFSI in the mixture of solvents can be equal to 100% minus the concentration of LiTFS in the mixture of solvents. For example, if the total concentration of salt in the mixture of solvents is 0.5 M, and the LiTFS concentration (in mole fraction) in the mixture of solvents is 90% (i.e., 0.45 M), then the LiTFSI concentration in the electrolyte mixture is 10% (i.e., 0.05 M). In embodiments, other types of salts can be added to the electrolyte.
  • [0044]
    Other materials can be added to the electrolyte mixture. For example, in certain embodiments, cell 10 includes an electrolyte formed of a mixture of solvents including EC, DME and PC, and a salt mixture of LiTFS and LiTFSI. The concentration of EC in the mixture of solvents can be between about 5% and 30% by weight. The concentration of EC in the mixture of solvents can be equal to or greater than 5%, 10%, 15%, 20%, or 25% by weight; and/or equal to or less than 30%, 25%, 20%, 15%, or 10% by weight. The concentration of DME in the mixture of solvents can range from about 30% to about 85% by weight. The concentration of DME in the mixture of solvents can be equal to or greater than 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80% by weight; and/or equal to or less than 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, or 35% by weight. The concentration of PC in the mixture of solvents can be equal to 100% minus the concentration of EC and DME. For example, if the concentration of EC in the mixture of solvents is 15% by weight, and the concentration of DME in the mixture of solvents is 60% by weight, then the concentration of PC in the mixture of solvents is 25% by weight. Examples of an EC:DME:PC solvent mixture are 14:62:24 and 10:75:15 percent by weight.
  • [0045]
    The LiTFS and LiTFSI concentrations in the electrolyte, e.g., 0.4-1.2 M, can be generally similar to those described herein. In embodiments, other types of salts can be added to the electrolyte.
  • [0046]
    To assemble the cell, 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, aluminum alloy, 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, nickel, titanium, steel or stainless steel, connects cathode 16 to cap 24. Cap 24 may also be made of aluminum, nickel, titanium, steel or stainless steel. 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.
  • [0047]
    Other configurations of 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.
  • [0048]
    The invention is further described in the following examples, which do not limit the scope of the invention described in the claims.
  • EXAMPLE 1
  • [0049]
    Al Corrosion in Different Electrolytes with Addition of LiClO4
  • [0050]
    Glass Cell Experimentation
  • [0051]
    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 cm2. 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.
  • [0052]
    Cyclic Voltammetry
  • [0053]
    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/cm2 at the first cycle.
  • [0054]
    Chronoamperometry
  • [0055]
    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/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.
  • [0056]
    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 LiClO4 to the electrolyte shifted the potential of aluminum in the positive direction, which indicates corrosion suppression.
  • [0057]
    Curves “a” and “a”′ in FIG. 2 show the corrosion potential of the aluminum in the electrolyte containing no LiClO4. 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.
  • [0058]
    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 LiClO4; 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.
  • [0059]
    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 LiClO4 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.
  • [0060]
    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 LiClO4. 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.
  • [0061]
    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 LiClO4; 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.
  • [0062]
    Referring to FIG. 7, curve “a” shows the corrosion potential of the aluminum subjected to an electrolyte containing a mixture of LiTFS and LiPF6 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.
  • [0063]
    Referring to FIG. 8, curve “a” shows a chronoamperogram of the aluminum electrode exposed to the electrolyte containing LiTFS, LiPF6, 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
  • [0064]
    Al Corrosion in Electrolytes Containing LiTFS DME:EC:PC, with the Addition of Different Perchlorates
  • [0065]
    Electrochemical glass cells were constructed as described in Example 1. Cyclic voltammetry and chromoamperometry were performed as described in Example 1.
  • [0066]
    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 LiClO4, 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.
  • [0067]
    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 LiClO4, 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.
  • [0068]
    The shifts in the corrosion potential that result from the addition of LiClO4, 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
    LiClO4 0 300 600
  • EXAMPLE 3
  • [0069]
    Al Corrosion in Electrolyte Containing LiTFS, DME:EC:PC, (Vial Storage Test)
  • [0070]
    The following test conditions were used:
  • [0071]
    Electrodes: EMD (electrochemically synthesized manganese dioxide) based cathodes applied on the Al current collector
  • [0072]
    Electrolyte (10 mL per sample): LiTFS, DME:EC:PC with and without addition of LiClO4 salt
  • [0073]
    Aging conditions: 60 C. for 20 days
  • [0074]
    Direct determination of Al corrosion was performed in one of two ways:
  • [0075]
    Analytical determination of Al ions in the electrolyte after aging (ICP method)
  • [0076]
    Direct observation of the Al surface (optical microscopy) after aging
  • [0077]
    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.
    TABLE 2
    Al concentration
    Sample Electrolyte after storage (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 +  2.16 0.18
    current collector 2500 ppm LiClO4
  • [0078]
    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.
  • [0079]
    The Al concentration in the electrolyte without LiClO4 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.
  • [0080]
    On the other hand, the samples which were stored in the electrolytes with added LiClO4 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.
  • [0081]
    The analytical data were confirmed by the direct observation of Al surface after aging (under an optical microscope, at a magnification of 60X). The electrodes stored in the electrolyte without LiClO4 exhibited substantial corrosion, as viewed under the optical microscope. The section stored in the electrolyte with added LiClO4 showed virtually no corrosion.
  • EXAMPLE 4
  • [0082]
    Al Current Collector Coupled with Other Metals, (Vial Storage Test)
  • [0083]
    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.
    TABLE 3
    Ni Al Fe
    Sample Electrolyte (ppm) (ppm) (ppm)
    None LiTFS, DME:EC:PC <1.0 <1.0 <1.0
    Cathode (Al cur. LiTFS, DME:EC:PC <1.0 24.4 5.3
    collector with
    welded SS tab)
    Cathode (Al cur. LiTFS, DME:EC:PC 90.9 20.5 <1.0
    collector with
    welded Ni tab)
    Cathode (Al cur. LiTFS, DME:EC:PC + <1.0 <1.0 <1.0
    collector with 2500 ppm LiClO4
    welded SS tab)
    Cathode (Al cur. LiTFS, DME:EC:PC + <1.0 <1.0 <1.0
    collector with 2500 ppm LiClO4
    welded Ni tab)
  • [0084]
    The highest corrosion rate was observed on the sample welded to the SS tab and stored in the electrolyte without added LiClO4 (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).
  • [0085]
    A high concentration of Ni (90.9 ppm) in the resulting electrolyte (Al current collector with welded Ni tab, electrolyte without LiClO4) 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).
  • [0086]
    On the other hand, the samples stored in the electrolytes with added LiClO4 did not show any corrosion (the resulting Al, Ni, Fe concentrations in the electrolyte were at the background level of <1 ppm).
  • EXAMPLE 5
  • [0087]
    Al Corrosion in Electrolyte Containing LiTFS, DME:EC:PC and 2500 ppm of LiClO4, (2/3A Cell Tests)
  • [0088]
    Cells were assembled with investigated parts and electrolytes according to the standard procedure with Al current foil applied as the cathode substrate.
  • [0089]
    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).
  • EXAMPLE 6
  • [0090]
    Corrosion Tests Using Different Aluminum Alloys, (Vial Storage Test)
  • [0091]
    Two cathodes were prepared by coating aluminum foil substrates (1145 Al) with MnO2. 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.
  • [0092]
    Reduction of Corrosion of Steels
  • [0093]
    Addition of a perchlorate salt as described herein can also reduce (e.g., minimize or suppress) corrosion of steel, e.g., stainless steel, in a cell. Examples of steels include 300 series stainless steels (such as 304L or 316L stainless steel), 400 series stainless steels (such as 409, 416, 434, or 444 stainless steel), or cold roll steels (such as 1008 cold roll steel). Other types stainless steels, e.g., 200 series stainless steel, are possible. The steel can be included in one or more components of the cell in relatively pure form or combined with one or more other materials, such as a different stainless steel. Examples of a component of a cell include a cathode current collector, a case, a positive lead, or a cap. Accordingly, adding a perchlorate salt to the cell can reduce corrosion of the component(s). In some cases, the component(s) can include a couple, e.g., two materials in electrical contact with each other. The perchlorate salt can also reduce corrosion of couples of different materials (e.g., 316 and 416 stainless steel) and couples of the same material, because a connection portion (e.g., a weld) can have a different composition or structure than, e.g., two connected portions, due to melting and diffusion. The portions can be, for example, the cathode current collector, a tab, a rivet, the can, and/or a contact plate. As a result, in some embodiments, the cell can be operated more stably at relatively higher operating potentials, e.g., from about 3.6 V up to about 5.0 V.
  • EXAMPLE 7
  • [0094]
    Corrosion of Steel in an Electrolyte Containing LiTFS and DME:EC:PC
  • [0095]
    Glass Cell Experimentation
  • [0096]
    An electrochemical glass cell was constructed as described above but having a steel working electrode, which was fabricated from a rod of a selected steel.
  • [0097]
    Cyclic Voltammetry
  • [0098]
    Corrosion current measurements were performed as described above. The corrosion potential of steel was defined as the potential at which the anodic current density reached 10−5 (or 10−4) A/cm2 at the first cycle of backscan.
  • [0099]
    Chronoamperometry
  • [0100]
    Corrosion current measurements were performed as described above. Corrosion suppression occurred when resulting current density was observed in the range of 10−6 A/cm2 after 30 min. of polarization.
  • [0101]
    304L Stainless Steel: Referring to FIG. 11, cyclic voltammograms taken in an electrolyte containing LiTFS and DME:EC:PC showed significant shifts in corrosion potential of a 304 SS electrode. The addition of LiClO4 to the electrolyte shifted the potential of 304 SS electrode in the positive direction, which indicates corrosion suppression.
  • [0102]
    Curves “a” and “a′” in FIG. 11 show the corrosion potential of the 304 SS electrode (intersection of cyclic voltammogram with 10−4 mA/cm2 current density line) in the electrolyte containing no LiClO4. The corrosion potential of 316L steel electrode is presented on curves “b” and “b′” as a base line. The addition of 2000 ppm of LiClO4 to the electrolyte shifted the potential of the 304L electrode about 200 mV in the positive direction (curves “c” and “c′”). These results demonstrate that the addition of LiClO4 to the electrolyte containing LiTFS salt and mixture of DME:EC:PC results in increasing degrees of corrosion protection of the 304L electrode.
  • [0103]
    Referring to FIG. 12, curve “a” shows a potentiostatic (at 4.2 V vs. Li RE) dependence (chronoamperogram) of the 304L steel electrode exposed to the electrolyte containing LiTFS, DME:EC:PC with no addition of LiClO4. Curve “b” shows the chronoamperogram taken in the same electrolyte with addition of 2000 ppm LiClO4. As shown in FIG. 12, at a LiClO4 concentration of 2000 ppm, the 304 steel corrosion at +4.2 V (vs. Li reference electrode) is effectively suppressed, and the corrosion current is less than 10−6 A/cm2 after 30 min. of measurement. A 304 steel electrode is stable at the potentials more negative than +4.2 V vs. Li RE.
  • [0104]
    416L Stainless Steel: Referring to FIG. 13, curve “a” shows the corrosion potential of 416 steel electrode (intersection of the backscan cyclic voltammogram with 110−4 mA/cm2 current density line) in an electrolyte containing LiTFS, DME:EC:PC, and no LiC104. Adding 0.2% of LiClO4 to the electrolyte shifted the corrosion potential of the 416 steel electrode 250 mV in the positive direction (curves “b”); adding 0.4% of LiClO4 to the electrolyte shifted the potential 440 mV (curves “c”); and adding 0.6% and 0.8% of LiClO4 to the electrolyte shifted the potential 530 and 600 mV, respectively (curves “d” and “e”). These results demonstrate that the addition of increasing amounts of LiClO4 to the electrolyte containing LiTFS, and DME:EC:PC results in increasing degrees of corrosion protection of the a 416 steel electrode.
  • [0105]
    Referring to FIG. 14, curve “a” shows a chronoamperogram of 416 steel electrode (4.0 V vs. Li RE) exposed to an electrolyte containing LiTFS, DME:EC:PC, and no LiClO4. Curves “b”, “c”, “d”, “e” show chronoamperograms of the 416 steel electrode exposed to the same electrolyte containing 0.2, 0.4, 0.6, 0.8% LiClO4, respectively. As shown in FIG. 14, the addition of increasing amounts of LiClO4 to the electrolyte containing LiTFS, and DME:EC:PC results in increasing degrees of corrosion protection of the 416 steel electrode. The resulting current density in the electrolyte with addition of LiClO4 after 30 min. of polarization is in the range of 4*10−5 A/cm2 and decreasing.
  • [0106]
    Referring to FIG. 15, curve “a” shows a chronoamperogram of a 416 steel electrode (4.0 V vs. Li RE) exposed to the electrolyte containing LiTFS, DME:EC:PC, and 0.8% of LiClO4. As shown in FIG. 15, the resulting current density after 50 hours of polarization is in the range of 1.510−5 A/cm2 and decreasing. As shown in FIG. 15, at a LiClO4 concentration of 0.8%, the corrosion of 416 steel at +4.0 V (vs. Li reference electrode) is effectively suppressed. A 416 steel electrode is stable at potentials more negative than +4.0 V vs. Li RE.
  • [0107]
    1008 Cold Roll Steel (CRS): Referring to FIG. 16, curve “a” shows a chronoamperogram of 1008 CRS electrode (3.6 V vs. Li RE) exposed to an electrolyte containing LiTFS, DME:EC:PC, and no LiClO4. Curve “b” shows a chronoamperogram of 1008 CRS electrode exposed to the same electrolyte containing 1.0% LiClO4. As shown in FIG. 16, the addition of 1.0% of LiClO4 to the electrolyte containing LiTFS, and DME:EC:PC results in successful corrosion suppression of the 1008 CRS electrode. The resulting current density in the electrolyte with the addition of 1% of LiClO4 after 16 hours of polarization is in the range of 110−5 A/cm2 and decreasing.
  • EXAMPLE 8
  • [0108]
    Steel Corrosion in Electrolyte Containing LiTFS, DME:EC:PC (Vial Storage Test)
  • [0109]
    The test method was generally as described in Example 6 but using steel current collectors. Direct determination of steel corrosion was performed by analytical determination of Fe ions in the electrolyte after aging (ICP method);
  • [0110]
    Stainless steel current collectors: 304 and 416 steel current collectors did not show any sign of corrosion after 20 days of storage in the electrolyte at 60 C. (background level of Fe ions in liquid phase).
  • [0111]
    CRS current collector: Direct measurements of steel corrosion were performed by determining the level of Fe ions in the electrolyte after aging of EMD based cathodes with steel current collector. The electrodes stored in the electrolyte without LiClO4 exhibited substantial corrosion, as viewed under an optical microscope. A sample stored in the electrolyte with added LiClO4 showed virtually no corrosion. Analytical results (ICP) are summarized in a Table 2.
    TABLE 2
    Fe concentration after
    Sample Electrolyte storage (ppm)
    None LiTFS, DME:EC:PC <1.0
    EMD based cathode on LiTFS, DME:EC:PC 17.5, 16.3
    CRS current collector
    EMD based cathode on LiTFS, DME:EC:PC +  1.1, 1.0
    CRS current collector 1.0% LiClO4
  • [0112]
    The level of Fe ions in the electrolyte indicates the rate of CRS corrosion. The Fe concentration in the electrolyte without LiClO4 addition is relatively high (the range is 16-18 ppm). Thus, part of the CRS current collector has dissolved (corroded) under the potential of the applied active cathode material (3.6V). Samples that were stored in the electrolytes with added LiClO4 did not show any corrosion (the resulting Fe concentration in the electrolyte is at the background level 1.0-1.1 ppm). The data (Table 2) confirm results of the electrochemical measurements in a glass cell: 1.0% of LiClO4 suppresses the corrosion of CRS at the potential of EMD cathode.
  • [0113]
    All publications, patents, and patent applications referred to 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.
  • Other Embodiments
  • [0114]
    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.
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US345124 *6 Jul 1886F OneBriel bailhache
US2993946 *27 Sep 195725 Jul 1961Rca CorpPrimary cells
US3732124 *28 Jun 19718 May 1973Accumulateurs FixesElectrochemical cells comprising current collector member embedded into the protruding edges of the electrodes
US3761314 *22 Jun 197125 Sep 1973Accumulateurs FixesHigh discharge rate electric cells and batteries
US3905851 *22 Mar 197416 Sep 1975Union Carbide CorpMethod of making battery separators
US4129691 *13 Jan 197812 Dec 1978Saft-Societe Des Accumulateurs Fixes Et De TractionOrganic solvent electrolytes for high specific energy primary cells
US4279972 *27 Aug 197921 Jul 1981Duracell International Inc.Non-aqueous electrolyte cell
US4401735 *28 Dec 197930 Aug 1983Duracell International Inc.Non-aqueous Li/MnO2 cell
US4499160 *20 Jun 198312 Feb 1985Matzliach BabaiCathode and electrochemical cell containing same
US4526846 *14 Jun 19822 Jul 1985Duracell Inc.Corrosion prevention additive
US4529675 *21 Nov 198416 Jul 1985General Electric CompanyRechargeable electrochemical cell having improved current collector means
US4555457 *28 Sep 198326 Nov 1985Acr Electronics Inc.Battery cell containing potassium monoperoxysulfate in the cathode mix
US4755440 *2 Feb 19875 Jul 1988Ramot University For Applied Research And Industrial Development Ltd.Electrochemical cell
US4803137 *25 Apr 19887 Feb 1989Bridgestone CorporationNon-aqueous electrolyte secondary cell
US4863817 *13 Oct 19885 Sep 1989Bridgestone CorporationNonaqueous electrolyte cell
US4865932 *12 May 198812 Sep 1989Bridgestone CorporationElectric cells and process for making the same
US4925751 *26 Apr 198915 May 1990Shackle Dale RHigh power solid state electrochemical laminar cell
US4957833 *5 Dec 198918 Sep 1990Bridgestone CorporationNon-aqueous liquid electrolyte cell
US4971686 *26 Dec 198920 Nov 1990Pitney Bowes Inc.Mail handling machine with mis-sealed envelope detector
US5077152 *25 Sep 199031 Dec 1991Ricoh Company, LtdNegative electrode for secondary battery
US5114811 *5 Feb 199019 May 1992W. Greatbatch Ltd.High energy density non-aqueous electrolyte lithium cell operational over a wide temperature range
US5176968 *27 Dec 19905 Jan 1993Duracell Inc.Electrochemical cell
US5204196 *25 Feb 199220 Apr 1993Osaka Gas Company LimitedSolid state and conductive polymer composition
US5225296 *21 Nov 19906 Jul 1993Ricoh Company, Ltd.Electrode and method of producing the same
US5240794 *19 Dec 199131 Aug 1993Technology Finance Corporation (Proprietary) LimitedElectrochemical cell
US5272022 *27 Sep 199121 Dec 1993Kabushiki Kaisha ToshibaNon-aqueous electrolyte secondary battery
US5278005 *6 Apr 199211 Jan 1994Advanced Energy Technologies Inc.Electrochemical cell comprising dispersion alloy anode
US5418084 *23 Nov 199223 May 1995Eveready Battery Company, Inc.Electrochemical cell having a safety vent closure
US5462820 *1 Nov 199431 Oct 1995Fuji Photo Film Co., Ltd.Non-aqueous battery with a block copolymer sealing member
US5523073 *30 Mar 19954 Jun 1996Mitsui Mining & Smelting Co., Ltd.Manganese dioxide for lithium primary battery and method of producing the same
US5541022 *22 Nov 199430 Jul 1996Hitachi, Ltd.Composite anode for nonaqueous secondary battery and method for producing the same
US5554462 *21 Dec 199410 Sep 1996SaftCarbon anode for a lithium rechargeable electrochemical cell and a process for its production
US5567548 *12 Feb 199622 Oct 1996Tracor Applied Sciences, Inc.Lithium ion battery with lithium vanadium pentoxide positive electrode
US5569558 *5 Jun 199529 Oct 1996Wilson Greatbatch Ltd.Reduced voltage delay additive for nonaqueous electrolyte in alkali metal electrochemical cell
US5580683 *16 Nov 19943 Dec 1996Wilson Greatbatch Ltd.high pulse power cell
US5595841 *16 Apr 199621 Jan 1997Fuji Photo Film Co., Ltd.Nonaqueous secondary battery
US5639577 *16 Apr 199617 Jun 1997Wilson Greatbatch Ltd.Nonaqueous electrochemical cell having a mixed cathode and method of preparation
US5691081 *29 May 199625 Nov 1997Minnesota Mining And Manufacturing CompanyBattery containing bis(perfluoroalkylsulfonyl)imide and cyclic perfluoroalkylene disulfonylimide salts
US5750277 *2 Oct 199612 May 1998Texas Instruments IncorporatedCurrent interrupter for electrochemical cells
US5773734 *21 Dec 199530 Jun 1998Dana CorporationNitrided powdered metal piston ring
US5811205 *27 Dec 199522 Sep 1998SaftBifunctional electrode for an electrochemical cell or a supercapacitor and a method of producing it
US5851693 *22 Jan 199722 Dec 1998Matsushita Electric Industrial Co., Ltd.Organic electrolyte batteries
US5958625 *8 Sep 199728 Sep 1999Gnb Technologies, Inc.Positive lead-acid battery grids and cells and batteries using such grids
US6001509 *18 Nov 199714 Dec 1999Samsung Display Devices Co., Ltd.Solid polymer electrolytes
US6017656 *3 Oct 199725 Jan 2000Medtronic, Inc.Electrolyte for electrochemical cells having cathodes containing silver vanadium oxide
US6025096 *29 May 199215 Feb 2000Hope; Stephen F.Solid state polymeric electrolyte for electrochemical devices
US6030422 *28 Jul 199929 Feb 2000Wilson Greatbatch Ltd.Method for modifying the electrochemical surface area of a cell using a perforated film
US6030728 *20 Aug 199729 Feb 2000International Business Machines CorporationHigh performance lithium polymer electrolyte battery
US6045950 *26 Jun 19984 Apr 2000Duracell Inc.Solvent for electrolytic solutions
US6053953 *4 Feb 199825 Apr 2000Fuji Photo Film Co., Ltd.Nonaqueous secondary battery and process for preparation thereof
US6090506 *1 Aug 199718 Jul 2000Fuji Photo Film Co. Ltd.Nonaqueous secondary battery
US6165644 *10 Jan 200026 Dec 2000Polyplus Battery Company, Inc.Methods and reagents for enhancing the cycling efficiency of lithium polymer batteries
US6168889 *10 Dec 19982 Jan 2001Micron Technology, Inc.Battery electrolytes and batteries
US6190803 *11 Jul 199720 Feb 2001Fuji Photo Film Co., Ltd.Nonaqueous secondary battery
US6218055 *29 Jul 199917 Apr 2001Mine Safety Appliances CompanyElectrochemical power cells and method of improving electrochemical power cell performance
US6322928 *23 Sep 199927 Nov 20013M Innovative Properties CompanyModified lithium vanadium oxide electrode materials and products
US6352793 *9 Oct 19985 Mar 2002Ngk Insulators, Ltd.Lithium secondary battery
US6447957 *5 Apr 200010 Sep 2002Toyo Aluminum Kabushiki KaishaMetal foil for collector and method of manufacturing the same, collector for secondary battery and secondary battery
US6506516 *7 Jun 199914 Jan 2003Metallgesellschaft AktiengesellschaftLithium bisoxalatoborate, the production thereof and its use as a conducting salt
US6521374 *1 Sep 199918 Feb 2003Sanyo Electric Co., Ltd.Lithium secondary cell
US6689511 *11 Dec 200010 Feb 2004Sharp Kabushiki KaishaSecondary battery and electronic instrument using it
US6780543 *9 Jan 200224 Aug 2004Sanyo Electric Co., Ltd.Aluminum or aluminum alloy-based lithium secondary battery
US20010028871 *17 Apr 200111 Oct 2001LimtechProcess for the purification of lithium carbonate
US20010033964 *12 Jan 200125 Oct 2001Merck Patent Gesellschaft Mit Beschrankter HaftungAlkylspiroborate salts for use in electrochemical cells
US20020028389 *10 Jul 20017 Mar 2002Matsushita Electric Industrial Co., Ltd.Non-aqueous electrolyte and electrochemical device comprising the same
US20030113622 *14 Dec 200119 Jun 2003Blasi Jane A.Electrolyte additive for non-aqueous electrochemical cells
US20030143112 *24 Oct 200231 Jul 2003Board Of Trustees Of The University Of IllinoisColorimetric artificial nose having an array of dyes and method for artificial olfaction
US20030186110 *9 Jan 20032 Oct 2003Sloop Steven E.System and method for removing an electrolyte from an energy storage and/or conversion device using a supercritical fluid
US20040005267 *25 Mar 20038 Jan 2004Boryta Daniel AlfredProduction of lithium compounds directly from lithium containing brines
US20040053138 *12 Sep 200318 Mar 2004Ralph OtterstedtOvercharge protection of nonaqueous rechargeable lithium batteries by cyano-substituted thiophenes as electrolyte additives
US20040096746 *21 Sep 200120 May 2004Ulrich WietelmannMethod for drying organic liquid electrolytes
US20050019670 *28 May 200427 Jan 2005Khalil AmineLong life lithium batteries with stabilized electrodes
US20050191545 *26 Feb 20041 Sep 2005Qinetiq LimitedElectrode assembly
US20050202320 *15 Mar 200415 Sep 2005Totir Dana A.Non-aqueous electrochemical cells
US20060216597 *14 Mar 200628 Sep 2006The Gillette Company, A Delaware CorporationFlexible cathodes
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US705413821 Mar 200530 May 2006Sanyo Electric Co., Ltd.Electric double layer capacitor and electrolyte battery
US727925024 Nov 20039 Oct 2007The Gillette CompanyBattery including aluminum components
US7285356 *23 Jul 200423 Oct 2007The Gillette CompanyNon-aqueous electrochemical cells
US745923424 Nov 20032 Dec 2008The Gillette CompanyBattery including aluminum components
US74793488 Apr 200520 Jan 2009The Gillette CompanyNon-aqueous electrochemical cells
US752458119 Oct 200728 Apr 2009The Gillette CompanyNon-aqueous electrochemical cells
US754438424 Nov 20039 Jun 2009The Gillette CompanyMethods of making coated battery components
US75663506 Sep 200628 Jul 2009The Gillette CompanyMethod of making non-aqueous electrochemical cell
US774465917 Jun 200929 Jun 2010The Gillette CompanyMethod of making non-aqueous electrochemical cell
US774928818 Jun 20096 Jul 2010The Gillette CompanyMethod of making non-aqueous electrochemical cell
US792773911 Jun 200819 Apr 2011The Gillette CompanyNon-aqueous electrochemical cells
US84356705 Nov 20087 May 2013The Gillette CompanyBattery including aluminum components
US20030113622 *14 Dec 200119 Jun 2003Blasi Jane A.Electrolyte additive for non-aqueous electrochemical cells
US20040191624 *21 Apr 200330 Sep 2004Mitsuo ShinodaElectrolyte for alkaline battery and alkaline battery employing electrolyte
US20050089760 *17 Nov 200428 Apr 2005The Gillette Company, A Delaware CorporationElectrolyte additive for non-aqueous electrochemical cells
US20050112274 *24 Nov 200326 May 2005Issaev Nikolai N.Battery including aluminum components
US20050112467 *24 Nov 200326 May 2005Berkowitz Fred J.Battery including aluminum components
US20050112468 *24 Nov 200326 May 2005Berkowitz Fred J.Battery including aluminum components
US20060019161 *23 Jul 200426 Jan 2006Issaev Nikolai NNon-aqueous electrochemical cells
US20060228624 *8 Apr 200512 Oct 2006Issaev Nikolai NNon-aqueous electrochemical cells
US20070000121 *6 Sep 20064 Jan 2007The Gillette Company, A Delaware CorporationMethod of making non-aqueous electrochemical cell
US20080088278 *19 Oct 200717 Apr 2008The Gillette Company, A Delaware CorporationNon-aqueous electrochemical cells
US20080261110 *11 Jun 200823 Oct 2008The Gillette CompanyNon-Aqueous Electrochemical Cells
US20090061308 *5 Nov 20085 Mar 2009The Gillette CompanyBattery Including Aluminum Components
EP1580778A1 *22 Mar 200528 Sep 2005Furukawa Precision Engineering Co., Ltd.Electric double layer capacitor and electrolyte battery
EP1771913B1 *14 Jul 20051 Nov 2017Duracell U.S. Operations, Inc.Non-aqueous electrochemical cells
Classifications
U.S. Classification429/199, 429/245, 429/224, 429/231.95
International ClassificationH01M4/66, H01M2/02, H01M6/16, H01M10/36, H01M4/50
Cooperative ClassificationY10T29/49108, H01M4/661, H01M2/26, H01M4/502, H01M6/166, H01M2/0285
European ClassificationH01M2/02E16, H01M6/16E3, H01M4/66A, H01M2/26
Legal Events
DateCodeEventDescription
10 Feb 2003ASAssignment
Owner name: GILLETTE COMPANY, THE, MASSACHUSETTS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ISSAEV, NIKOLAI N.;POZIN, MICHAEL;REEL/FRAME:013770/0662
Effective date: 20030130