CA2406410A1 - Lithium ion battery capable of being discharged to zero volts - Google Patents
Lithium ion battery capable of being discharged to zero volts Download PDFInfo
- Publication number
- CA2406410A1 CA2406410A1 CA002406410A CA2406410A CA2406410A1 CA 2406410 A1 CA2406410 A1 CA 2406410A1 CA 002406410 A CA002406410 A CA 002406410A CA 2406410 A CA2406410 A CA 2406410A CA 2406410 A1 CA2406410 A1 CA 2406410A1
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- Prior art keywords
- battery
- negative electrode
- positive
- substrate
- potential
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 238000004090 dissolution Methods 0.000 claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 4
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000007784 solid electrolyte Substances 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- -1 polyethylene Polymers 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 229910032387 LiCoO2 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- DJZIBVUGARDLOC-UHFFFAOYSA-N [Ni]=O.[Co]=O.[Li] Chemical compound [Ni]=O.[Co]=O.[Li] DJZIBVUGARDLOC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000560 biocompatible material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000008035 Back Pain Diseases 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910011259 LiCoOz Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/18—Applying electric currents by contact electrodes
- A61N1/32—Applying electric currents by contact electrodes alternating or intermittent currents
- A61N1/36—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation
- A61N1/372—Arrangements in connection with the implantation of stimulators
- A61N1/378—Electrical supply
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- 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
- H01M4/662—Alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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
- 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
-
- 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
- Y10T29/4911—Electric battery cell making including sealing
Abstract
A lithium ion battery particularly configured to be able to discharge to a very low voltage, e.g. zero volts, without causing permanent damage to the battery. More particularly, the battery is configured to define a Zero Volt Crossing Potential (ZCP) which is lower than a Substrate Dissolution Potential (SDP) to thus avoid low voltage substrate damage.
Description
TITLE . LITHIUM ION BATTERY CAPABLE OF BEING
DISCHARGED TO ZERO VOLTS
RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application 60/199895 filed April 26, 2000.
FIELD OF THE INVENTION
This invention relates generally to rechargeable batteries and more particularly to a rechargeable lithium battery capable of discharging to zero volts without causing damage to the battery.
BACKGROUND OF THE INVENTION
Rechargeable lithium batteries are widely discussed in the literature and are readily commercially available. They typically consist of a positive electrode and a negative electrode spaced by a separator, an electrolyte, a case, and feedthrough pins respectively connected to the electrodes and extending externally of the case. Each electrode is typically formed of a metal substrate that is coated with a mixture of an active material, a binder, and a solvent.
In a typical battery design, the electrodes comprise sheets which are rolled together, separated by separator sheets, and then placed in a prismatic case. Positive and/or negative feed through pins (i.e., terminals) are then connected to the respective electrodes and the case is sealed.
The negative electrode is typically formed of a copper substrate carrying graphite as the active material. The positive electrode is typically formed of an aluminum substrate carrying lithium cobalt dioxide as the active material. The electrolyte is most commonly a 1.1 mixture of EC:DEC in a 1.0 M salt of LiPFs.
The separator is frequently a micro porous membrane made of a polyolephine, such as a combination of polyethylene and/or polypropylene which can, for example, be approximately 25pm thick.
It is typical to use protection circuitry with lithium ion batteries to avoid potential deleterious effects. Thus, protection circuitry is frequently employed to terminate charging if the voltage or temperature of the battery(or any cell) exceeds a certain level. Moreover, it is common to incorporate a low voltage cutoff to disconnect the battery from its load if the voltage of the battery (or any cell) falls below a certain lower level. This latter precaution is taken to prevent permanent damage to the battery which can occur if a voltage greater than a Damage Potential Threshold (DPT) is applied to one of the electrodes. For example, corrosion or decomposition of the negative electrode substrate can occur if a voltage greater than a Substrate Dissolution Potential (SDP) is applied to the negative electrode..
SUMMARY OF THE INVENTION
The present invention is directed to a rechargeable lithium ion battery particularly configured to be able to discharge to a very low voltage, e.g.
zero volts, without causing permanent damage to the battery. More particularly, a battery in accordance with the invention is configured to define a Zero Volt Crossing Potential (ZCP) which is lower than the battery's Damage Potential Threshold (DPT) and more specifically its Substrate Dissolution Potential (SDP), to thus avoid low voltage substrate damage.
The ZCP refers to the voltage of each of the electrodes relative to a lithium reference (Li/Li+) when the battery potential, i.e., the potential between the electrodes, is zero. The SDP refers to the dissolution potential of the negative electrode substrate relative to the lithium reference (Li/Li+). A
conventional lithium ion battery typically exhibits a ZCP of about 3.6 volts which can slightly exceed the battery's SDP.
In accordance with the present invention, the material selected for the negative electrode substrate has a dissolution potential greater than the ZCP.
Commercially pure titanium and titanium alloys are preferred. Nickel, nickel alloys, and stainless steel can also be used.
In the normal operation of a lithium ion battery, a solid electrolyte interface (SEI) layer, i.e., a passivation layer, is formed on the negative electrode, attributable to a reaction between the negative electrode and the electrolyte. The SEI layer comprises an insulating membrane that tends to inhibit the continuing reaction of the negative electrode and electrolyte. It has been recognized that this SEI layer can dissolve at a voltage above a certain level, i.e., Film Dissolution Potential (FDP), which can lead to permanent damage to the negative electrode. In accordance with a preferred embodiment of the invention, the battery is configured to assure a ZCP lower than said FDP.
A battery's ZCP level relative to the lithium reference is dependent in part on the materials used for the positive and/or negative electrodes. In accordance with a preferred embodiment of the invention, a positive electrode active material, e.g., LiNiXCo,_xOZ (0<x<_ 1 ), is selected which exhibits a discharge curve appropriate to achieve a relatively low ZCP level. This feature of the preferred embodiment facilitates the implementation of a battery in accordance with the invention characterized by a Zero Crossing Potential (ZCP) less than its Substrate Dissolution Potential (SDP) and/or its Film Dissolution Potential (FDP).
Batteries in accordance with the present invention are particularly suited for use in critical applications where physical access to the battery may be difficult. For example, batteries in accordance with the invention find application in medical devices configured to be implanted under the skin in a patient's body.
Such a medical device is typically comprised of a hermetically sealed housing formed of biocompatible material and dimensioned sufficiently small as to be able to be implanted without interfering with normal bodily function. A
battery in accordance with the invention includes a case configured for mounting in the device housing. The battery case can be of a variety of shapes, e.g., prismatic or cylindrical, and typically defines a volume of between .05 cc and 30 cc.
Batteries within this range exhibit capacities between 1.0 milliamp hours and amp hours. An exemplary battery for use in such a device includes a prismatic hermetically sealed battery casing having dimensions of 35 mm x l7mm x_5.5 mm. The device is intended to be implanted in the lower back region to help alleviate back pain using neurostimulation techniques.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other features and uniqueness of the invention will be better visualized from the following drawings and schematics.
Figure 1 A schematically depicts positive and negative battery electrodes rolled around a mandrel for placement in a battery case and Figure 1 B depicts in cross-section a complete battery;
Figure 2 shows a typical deep discharge curve for a conventional lithium ion battery using copper as the negative electrode substrate and lithium cobalt dioxide LiCo02 as the positive electrode active material;
Figure 3 shows a typical deep discharge curve for a zero volt battery in accordance with the present invention using titanium as the negative electrode substrate;
Figure 4 shows a typical deep discharge curve for a zero volt battery in accordance with the present invention using LiNiXCo,_XOZ (0<x<_ 1 ) as the positive electrode active material;
Figure 5 is a table showing preliminary test results of various battery configurations in accordance with the present invention; and Figure 6 schematically depicts a battery in accordance with the invention contained within an implantable medical device housing.
DETAILED DESCRIPTION
The following description discloses presently contemplated preferred embodiments for practicing the invention. This description is not to be taken in a limited sense, but is offered for the purpose of describing the preferred modes of the invention. The scope of the invention should be determined with reference to the claims.
Figures 1A and 1 B schematically depict a typical lithium ion battery construction 10 comprising a prismatic case 12 containing a positive electrode 14 and a negative electrode 16, rolled around a mandrel 18. Separator sheets 20, 22 are incorporated in the rolling to electrically separate the electrodes. The case 12 also typically includes electrolyte material (not shown) and positive and negative feed through pins (i.e., terminals) 26, 28 which are respectively connected to the electrodes 14, 16 and extend externally of the case 12.
The positive electrode 14 is typically comprised of a thin metal substrate, e.g., aluminum, carrying a layer of positive active material, e.g., lithium cobalt dioxide LiCo02 mixed with a binder, and coated on both faces of the substrate.
The negative electrode 16 is typically comprised of a thin metal substrate, e.g., copper, carrying a layer of negative active material, e.g., graphite coated on both faces of the substrate.
Two layers of separator 20, 22 electrically separate the electrodes 14, 16 from each other, enabling the electrodes to be rolled around mandrel 18. Each separator layer can comprise a micro porous membrane made of a combination of polypropylene and is approximately 25pm thick. The electrolyte is most commonly a 1:1 mixture of EC:DEC in a 1.0 M salt of LiPF6.
Figure 2 shows typical deep discharge performance curves for a conventional lithium ion battery. The y-axis represents voltage relative to a lithium reference (Li/Li+) or counter electrode and the x-axis represents time.
Curves 50 and 52 respectively depict the discharge curves for the positive and negative electrodes. The battery output voltage is the difference between the positive electrode voltage and the negative electrode voltage. During discharge, the positive electrode voltage decreases relative to Li/Li+ and the negative voltage increases, primarily near the end of discharge. Typically, a protection or management circuit stops the discharge when the battery voltage reaches 2.5 Volts. If the management circuit does not stop the discharge, the negative electrode potential will rise until it reaches the potential of the positive electrode which constitutes the Zero Volt Crossing Potential (ZCP) and is typically about 3.6 volts in conventional lithium ion battery constructions. The negative electrode potential at ZCP, relative to Li/Li+, can exceed the dissolution potential of the negative electrode substrate (SDP) , e.g., 3.3volts for copper, and cause dissolution and permanent damage to the substrate. The present invention is directed to battery improvements to assure that the value of SDP is greater than the value of ZCP, as represented in Figure 3.
DISCHARGED TO ZERO VOLTS
RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application 60/199895 filed April 26, 2000.
FIELD OF THE INVENTION
This invention relates generally to rechargeable batteries and more particularly to a rechargeable lithium battery capable of discharging to zero volts without causing damage to the battery.
BACKGROUND OF THE INVENTION
Rechargeable lithium batteries are widely discussed in the literature and are readily commercially available. They typically consist of a positive electrode and a negative electrode spaced by a separator, an electrolyte, a case, and feedthrough pins respectively connected to the electrodes and extending externally of the case. Each electrode is typically formed of a metal substrate that is coated with a mixture of an active material, a binder, and a solvent.
In a typical battery design, the electrodes comprise sheets which are rolled together, separated by separator sheets, and then placed in a prismatic case. Positive and/or negative feed through pins (i.e., terminals) are then connected to the respective electrodes and the case is sealed.
The negative electrode is typically formed of a copper substrate carrying graphite as the active material. The positive electrode is typically formed of an aluminum substrate carrying lithium cobalt dioxide as the active material. The electrolyte is most commonly a 1.1 mixture of EC:DEC in a 1.0 M salt of LiPFs.
The separator is frequently a micro porous membrane made of a polyolephine, such as a combination of polyethylene and/or polypropylene which can, for example, be approximately 25pm thick.
It is typical to use protection circuitry with lithium ion batteries to avoid potential deleterious effects. Thus, protection circuitry is frequently employed to terminate charging if the voltage or temperature of the battery(or any cell) exceeds a certain level. Moreover, it is common to incorporate a low voltage cutoff to disconnect the battery from its load if the voltage of the battery (or any cell) falls below a certain lower level. This latter precaution is taken to prevent permanent damage to the battery which can occur if a voltage greater than a Damage Potential Threshold (DPT) is applied to one of the electrodes. For example, corrosion or decomposition of the negative electrode substrate can occur if a voltage greater than a Substrate Dissolution Potential (SDP) is applied to the negative electrode..
SUMMARY OF THE INVENTION
The present invention is directed to a rechargeable lithium ion battery particularly configured to be able to discharge to a very low voltage, e.g.
zero volts, without causing permanent damage to the battery. More particularly, a battery in accordance with the invention is configured to define a Zero Volt Crossing Potential (ZCP) which is lower than the battery's Damage Potential Threshold (DPT) and more specifically its Substrate Dissolution Potential (SDP), to thus avoid low voltage substrate damage.
The ZCP refers to the voltage of each of the electrodes relative to a lithium reference (Li/Li+) when the battery potential, i.e., the potential between the electrodes, is zero. The SDP refers to the dissolution potential of the negative electrode substrate relative to the lithium reference (Li/Li+). A
conventional lithium ion battery typically exhibits a ZCP of about 3.6 volts which can slightly exceed the battery's SDP.
In accordance with the present invention, the material selected for the negative electrode substrate has a dissolution potential greater than the ZCP.
Commercially pure titanium and titanium alloys are preferred. Nickel, nickel alloys, and stainless steel can also be used.
In the normal operation of a lithium ion battery, a solid electrolyte interface (SEI) layer, i.e., a passivation layer, is formed on the negative electrode, attributable to a reaction between the negative electrode and the electrolyte. The SEI layer comprises an insulating membrane that tends to inhibit the continuing reaction of the negative electrode and electrolyte. It has been recognized that this SEI layer can dissolve at a voltage above a certain level, i.e., Film Dissolution Potential (FDP), which can lead to permanent damage to the negative electrode. In accordance with a preferred embodiment of the invention, the battery is configured to assure a ZCP lower than said FDP.
A battery's ZCP level relative to the lithium reference is dependent in part on the materials used for the positive and/or negative electrodes. In accordance with a preferred embodiment of the invention, a positive electrode active material, e.g., LiNiXCo,_xOZ (0<x<_ 1 ), is selected which exhibits a discharge curve appropriate to achieve a relatively low ZCP level. This feature of the preferred embodiment facilitates the implementation of a battery in accordance with the invention characterized by a Zero Crossing Potential (ZCP) less than its Substrate Dissolution Potential (SDP) and/or its Film Dissolution Potential (FDP).
Batteries in accordance with the present invention are particularly suited for use in critical applications where physical access to the battery may be difficult. For example, batteries in accordance with the invention find application in medical devices configured to be implanted under the skin in a patient's body.
Such a medical device is typically comprised of a hermetically sealed housing formed of biocompatible material and dimensioned sufficiently small as to be able to be implanted without interfering with normal bodily function. A
battery in accordance with the invention includes a case configured for mounting in the device housing. The battery case can be of a variety of shapes, e.g., prismatic or cylindrical, and typically defines a volume of between .05 cc and 30 cc.
Batteries within this range exhibit capacities between 1.0 milliamp hours and amp hours. An exemplary battery for use in such a device includes a prismatic hermetically sealed battery casing having dimensions of 35 mm x l7mm x_5.5 mm. The device is intended to be implanted in the lower back region to help alleviate back pain using neurostimulation techniques.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other features and uniqueness of the invention will be better visualized from the following drawings and schematics.
Figure 1 A schematically depicts positive and negative battery electrodes rolled around a mandrel for placement in a battery case and Figure 1 B depicts in cross-section a complete battery;
Figure 2 shows a typical deep discharge curve for a conventional lithium ion battery using copper as the negative electrode substrate and lithium cobalt dioxide LiCo02 as the positive electrode active material;
Figure 3 shows a typical deep discharge curve for a zero volt battery in accordance with the present invention using titanium as the negative electrode substrate;
Figure 4 shows a typical deep discharge curve for a zero volt battery in accordance with the present invention using LiNiXCo,_XOZ (0<x<_ 1 ) as the positive electrode active material;
Figure 5 is a table showing preliminary test results of various battery configurations in accordance with the present invention; and Figure 6 schematically depicts a battery in accordance with the invention contained within an implantable medical device housing.
DETAILED DESCRIPTION
The following description discloses presently contemplated preferred embodiments for practicing the invention. This description is not to be taken in a limited sense, but is offered for the purpose of describing the preferred modes of the invention. The scope of the invention should be determined with reference to the claims.
Figures 1A and 1 B schematically depict a typical lithium ion battery construction 10 comprising a prismatic case 12 containing a positive electrode 14 and a negative electrode 16, rolled around a mandrel 18. Separator sheets 20, 22 are incorporated in the rolling to electrically separate the electrodes. The case 12 also typically includes electrolyte material (not shown) and positive and negative feed through pins (i.e., terminals) 26, 28 which are respectively connected to the electrodes 14, 16 and extend externally of the case 12.
The positive electrode 14 is typically comprised of a thin metal substrate, e.g., aluminum, carrying a layer of positive active material, e.g., lithium cobalt dioxide LiCo02 mixed with a binder, and coated on both faces of the substrate.
The negative electrode 16 is typically comprised of a thin metal substrate, e.g., copper, carrying a layer of negative active material, e.g., graphite coated on both faces of the substrate.
Two layers of separator 20, 22 electrically separate the electrodes 14, 16 from each other, enabling the electrodes to be rolled around mandrel 18. Each separator layer can comprise a micro porous membrane made of a combination of polypropylene and is approximately 25pm thick. The electrolyte is most commonly a 1:1 mixture of EC:DEC in a 1.0 M salt of LiPF6.
Figure 2 shows typical deep discharge performance curves for a conventional lithium ion battery. The y-axis represents voltage relative to a lithium reference (Li/Li+) or counter electrode and the x-axis represents time.
Curves 50 and 52 respectively depict the discharge curves for the positive and negative electrodes. The battery output voltage is the difference between the positive electrode voltage and the negative electrode voltage. During discharge, the positive electrode voltage decreases relative to Li/Li+ and the negative voltage increases, primarily near the end of discharge. Typically, a protection or management circuit stops the discharge when the battery voltage reaches 2.5 Volts. If the management circuit does not stop the discharge, the negative electrode potential will rise until it reaches the potential of the positive electrode which constitutes the Zero Volt Crossing Potential (ZCP) and is typically about 3.6 volts in conventional lithium ion battery constructions. The negative electrode potential at ZCP, relative to Li/Li+, can exceed the dissolution potential of the negative electrode substrate (SDP) , e.g., 3.3volts for copper, and cause dissolution and permanent damage to the substrate. The present invention is directed to battery improvements to assure that the value of SDP is greater than the value of ZCP, as represented in Figure 3.
Figure 3 depicts deep discharge performance curves for a lithium ion battery in accordance with the present invention in which the negative electrode substrate is formed of titanium instead of copper. The use of titanium increases the knee of the negative electrode curve 54 to position the SDP above the ZCP. This relationship considerably reduces potential damage to the negative electrode substrate. In addition to commercially pure titanium, i.e., titanium CP, other materials can be used to raise the SDP sufficiently, e.g. titanium alloys, nickel, nickel alloys, and stainless steel.
Figure 3 demonstrates how the SDP level can be increased relative to the ZCP by proper choice of the negative electrode substrate material.
Alternatively, or additionally, the ZCP level can be decreased relative to the SDP
by proper choice of the positive electrode active material, as depicted in Figure 4.
More particularly, Figure 4 shows the discharge curve 60 for a positive electrode using lithium nickel cobalt dioxide LiNi,~Co,_X (where 0<x<_ 1 ) as the active material, i.e., as the intercalation compound. Note that the curve of Figure 4 exhibits a greater negative slope than the analogous curve 50 of Figure 2 representing the standard intercalation compound LiCoO~ The effect of the increased negative slope is to lower the ZCP level relative to the lithium reference and the SDP. As was the case in connection with Figure 3, this reduces the potential damage to the negative electrode substrate.
Additionally, however, the ZCP level also falls below a Film Dissolution Potential (FDP) which is the voltage above which a solid electrolyte interface (SEI) layer begins to dissolve. The SEI, or film, comprises a passivation layer which forms on the negative electrode and functions to inhibit a continuing reaction between the negative electrode active material and the electrolyte. Dissolution of the SEI
can noticeably damage the negative electrode active material.
Experiments have been performed at two difFerent temperatures employing the aforedescribed techniques depicted in Figures 3 and 4. The preliminary results are summarized in the table of Figure 5. Four different battery configurations were constructed as shown. Configuration (1 ) corresponds to the conventional arrangement represented in Figure 2 comprising a copper substrate for the negative electrode and LiCo02 for the positive active material. The battery was built and then recycled once to get an initial capacity measurement. The battery was then shorted between the positive and negative leads to achieve a zero volt state. This zero volt condition was held for one week and then recharged and discharged to get a capacity measurement after zero-volt storage. The capacity retention is calculated by dividing the discharge capacity after zero volt storage by the initial capacity and multiplying by 100%. In this manner, this percentage reflects any damage that had occurred to the battery while in the zero volt state.
As represented in Figure 5, the capacity retention for battery configuration (1 ) is below 80%, thus suggesting that damage had been done to the battery. After opening the battery and examining the electrodes, it was seen that copper dissolution had occurred. This battery (1 ) configuration performed poorly at both temperature settings.
The battery configuration (2) used LiCoOz as the positive active material and a titanium substrate as the negative substrate corresponding to the arrangement represented in Figure 3. The results show that at 25° C the capacity retention was at about 98% after the zero volt condition. However, at a higher temperature (37°C), performance deteriorates to below 80%.
This suggests that perhaps the zero volt crossing potential was sufficiently below SDP to avoid substrate dissolution but still high enough to exceed FDP and cause damage to the negative electrode active material. Accordingly, attempts were made to lower ZCP further to avoid damage both to the negative active material and the negative electrode substrate.
The battery configuration (3) utilizes LiNiXCo,_XOZ (0<x<_ 1 ) as the positive active material with copper negative electrode substrate. The results show that at 37°C the capacity retention is quite high at 90%. However, examination after the test, revealed that some copper dissolution occurred. Battery configuration (4) uses both LiNiXCo,_XOa (0<x<_ 1 ) as the positive active material and the titanium as the negative electrode substrate material. Results show that this configuration gives the best capacity retention after zero volt storage.
Figure 3 demonstrates how the SDP level can be increased relative to the ZCP by proper choice of the negative electrode substrate material.
Alternatively, or additionally, the ZCP level can be decreased relative to the SDP
by proper choice of the positive electrode active material, as depicted in Figure 4.
More particularly, Figure 4 shows the discharge curve 60 for a positive electrode using lithium nickel cobalt dioxide LiNi,~Co,_X (where 0<x<_ 1 ) as the active material, i.e., as the intercalation compound. Note that the curve of Figure 4 exhibits a greater negative slope than the analogous curve 50 of Figure 2 representing the standard intercalation compound LiCoO~ The effect of the increased negative slope is to lower the ZCP level relative to the lithium reference and the SDP. As was the case in connection with Figure 3, this reduces the potential damage to the negative electrode substrate.
Additionally, however, the ZCP level also falls below a Film Dissolution Potential (FDP) which is the voltage above which a solid electrolyte interface (SEI) layer begins to dissolve. The SEI, or film, comprises a passivation layer which forms on the negative electrode and functions to inhibit a continuing reaction between the negative electrode active material and the electrolyte. Dissolution of the SEI
can noticeably damage the negative electrode active material.
Experiments have been performed at two difFerent temperatures employing the aforedescribed techniques depicted in Figures 3 and 4. The preliminary results are summarized in the table of Figure 5. Four different battery configurations were constructed as shown. Configuration (1 ) corresponds to the conventional arrangement represented in Figure 2 comprising a copper substrate for the negative electrode and LiCo02 for the positive active material. The battery was built and then recycled once to get an initial capacity measurement. The battery was then shorted between the positive and negative leads to achieve a zero volt state. This zero volt condition was held for one week and then recharged and discharged to get a capacity measurement after zero-volt storage. The capacity retention is calculated by dividing the discharge capacity after zero volt storage by the initial capacity and multiplying by 100%. In this manner, this percentage reflects any damage that had occurred to the battery while in the zero volt state.
As represented in Figure 5, the capacity retention for battery configuration (1 ) is below 80%, thus suggesting that damage had been done to the battery. After opening the battery and examining the electrodes, it was seen that copper dissolution had occurred. This battery (1 ) configuration performed poorly at both temperature settings.
The battery configuration (2) used LiCoOz as the positive active material and a titanium substrate as the negative substrate corresponding to the arrangement represented in Figure 3. The results show that at 25° C the capacity retention was at about 98% after the zero volt condition. However, at a higher temperature (37°C), performance deteriorates to below 80%.
This suggests that perhaps the zero volt crossing potential was sufficiently below SDP to avoid substrate dissolution but still high enough to exceed FDP and cause damage to the negative electrode active material. Accordingly, attempts were made to lower ZCP further to avoid damage both to the negative active material and the negative electrode substrate.
The battery configuration (3) utilizes LiNiXCo,_XOZ (0<x<_ 1 ) as the positive active material with copper negative electrode substrate. The results show that at 37°C the capacity retention is quite high at 90%. However, examination after the test, revealed that some copper dissolution occurred. Battery configuration (4) uses both LiNiXCo,_XOa (0<x<_ 1 ) as the positive active material and the titanium as the negative electrode substrate material. Results show that this configuration gives the best capacity retention after zero volt storage.
From the foregoing table (Figure5), it appears that a performance gain is achieved by configuration (2) using a titanium negative electrode substrate and by configuration (3) using lithium nickel cobalt dioxide as the positive active material. However, maximum performance gain appears in configuration (4) which combines both of these features.
Figure 6 schematically depicts a battery 60 in accordance with the invention mounted in a housing 64 (shown partially open for the purposes of illustration) of a medical device 66 configured for implanting in a patient's body.
The housing 64 is preferably formed of biocompatible material and hermetically sealed. The device 66 is typically used for monitoring and/or affecting body parameters. For example, the device can be used to electrically stimulate nerves. The casing 68 of battery 64 can, for example, have dimensions of 35 mm x 17 mm x 5.5 mm.
While the invention has been described with reference to specific exemplary embodiments and applications, it should be recognized that numerous modifications and variations will occur to those skilled in the art without departing from the spirit and scope of the invention set forth in the appended claims.
Figure 6 schematically depicts a battery 60 in accordance with the invention mounted in a housing 64 (shown partially open for the purposes of illustration) of a medical device 66 configured for implanting in a patient's body.
The housing 64 is preferably formed of biocompatible material and hermetically sealed. The device 66 is typically used for monitoring and/or affecting body parameters. For example, the device can be used to electrically stimulate nerves. The casing 68 of battery 64 can, for example, have dimensions of 35 mm x 17 mm x 5.5 mm.
While the invention has been described with reference to specific exemplary embodiments and applications, it should be recognized that numerous modifications and variations will occur to those skilled in the art without departing from the spirit and scope of the invention set forth in the appended claims.
Claims (16)
1. ~A rechargeable battery comprising:
a positive electrode;
a negative electrode said positive electrode comprising a metal substrate having a lithium based active material formed thereon;
said negative electrode comprising a metal substrate having a lithium based active material formed thereon;
said positive and negative electrodes defining a Zero Volt Crossing Potential (ZCP) relative to a reference level when the voltage between said electrodes is zero;
said negative electrode substrate being susceptible of permanent damage when a voltage potential exceeding a Substrate Dissolution Potential (SDP) is applied thereto; and wherein said positive and negative electrodes are configured to establish ZCP at a lower level than SDP.
a positive electrode;
a negative electrode said positive electrode comprising a metal substrate having a lithium based active material formed thereon;
said negative electrode comprising a metal substrate having a lithium based active material formed thereon;
said positive and negative electrodes defining a Zero Volt Crossing Potential (ZCP) relative to a reference level when the voltage between said electrodes is zero;
said negative electrode substrate being susceptible of permanent damage when a voltage potential exceeding a Substrate Dissolution Potential (SDP) is applied thereto; and wherein said positive and negative electrodes are configured to establish ZCP at a lower level than SDP.
2. The battery of claim 1 wherein said negative electrode substrate is formed of a material from the group titanium and titanium alloy.
3. The battery of claim 1 wherein said negative electrode substrate is formed of stainless steel.
4. The battery of claim 1 wherein said negative electrode substrate is formed of a material from the group nickel and nickel alloy.
5. The battery of claim 1 wherein said positive electrode active material comprises a lithium-nickel-cobalt compound, LiNi x Co1-x O2 where 0 <
X
<= 1.
X
<= 1.
6. The battery of claim 1 further including an electrolyte; and wherein said negative electrode can react to said electrolyte to form a solid electrolyte interface (SEI) layer, said SEI layer being susceptible of permanent damage when a voltage potential exceeding a Film Dissolution Potential (FDP) is applied thereto; and wherein said positive and negative electrodes are configured to establish ZCP at a lower level than FDP.
7. The battery of claim 1 further including a case for housing said positive and negative electrodes; and wherein said case is configured for implanting in a patient's body.
8. The battery of claim 7 wherein said case is hermetically sealed.
9. The battery of claim 7 wherein said case has a volume of less then 30 cc.
10. A rechargeable battery capable of discharging to zero volts without damaging the battery, said battery comprising:
a positive electrode and a negative electrode;
at least one of said electrodes being susceptible of permanent damage when a voltage exceeding a Damage Potential Threshold (DPT) is applied thereto;
said positive and negative electrodes defining a Zero Volt Crossing Potential Threshold when the voltage between said electrodes is zero;
and wherein said positive and negative electrodes are configured to define a value of ZCP which is less than the value of DPT
a positive electrode and a negative electrode;
at least one of said electrodes being susceptible of permanent damage when a voltage exceeding a Damage Potential Threshold (DPT) is applied thereto;
said positive and negative electrodes defining a Zero Volt Crossing Potential Threshold when the voltage between said electrodes is zero;
and wherein said positive and negative electrodes are configured to define a value of ZCP which is less than the value of DPT
11. The battery of claim 10 wherein said negative electrode comprises a metal substrate having a lithium based active material formed thereon, said negative electrode substrate being susceptible of permanent damage when a voltage exceeding a Substrate Dissolution Potential (SDP) is applied thereto;
and wherein the value of SDP is greater than said value of ZCP.
and wherein the value of SDP is greater than said value of ZCP.
12. The battery of claim 11 wherein said negative electrode substrate is formed of a material from the group titanium and titanium alloy.
13. The battery of claim 11 wherein said negative electrode substrate is formed of stainless steel.
14. The battery of claim 11 wherein said negative electrode substrate is formed of a material from the group nickel and nickel alloy.
15. The battery of claim 11 wherein said positive electrode comprised a metal substrate having a lithium based active material formed thereon; and wherein said positive electrode active material comprises a lithium-nickel-cobalt compound.
16. The battery of claim 11 further including an electrolyte; and wherein said negative electrode can react to said electrolyte to form a solid electrolyte interface (SEI) layer, said SEI layer being susceptible of permanent damage when a voltage potential exceeding a Film Dissolution Potential (FDP) is applied thereto; and wherein said positive and negative electrodes are configured to establish ZCP at a lower level than FDP.
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US60/199,895 | 2000-04-26 | ||
US09/675,287 US6596439B1 (en) | 2000-04-26 | 2000-09-29 | Lithium ion battery capable of being discharged to zero volts |
US09/675,287 | 2000-09-29 | ||
PCT/US2001/013308 WO2001082398A1 (en) | 2000-04-26 | 2001-04-25 | Lithium ion battery capable of being discharged to zero volts |
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Publication Number | Publication Date |
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CA2406410A1 true CA2406410A1 (en) | 2001-11-01 |
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ID=26895268
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CA002406410A Abandoned CA2406410A1 (en) | 2000-04-26 | 2001-04-25 | Lithium ion battery capable of being discharged to zero volts |
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US (5) | US6596439B1 (en) |
EP (1) | EP1287570A1 (en) |
JP (1) | JP4111714B2 (en) |
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CA (1) | CA2406410A1 (en) |
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US7993781B2 (en) | 2011-08-09 |
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US20030025482A1 (en) | 2003-02-06 |
US20030000074A1 (en) | 2003-01-02 |
WO2001082398A1 (en) | 2001-11-01 |
EP1287570A1 (en) | 2003-03-05 |
US8535831B2 (en) | 2013-09-17 |
US7101642B2 (en) | 2006-09-05 |
AU2001257245A1 (en) | 2001-11-07 |
JP2004508659A (en) | 2004-03-18 |
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