Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—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
  • 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
• • 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
  • H01M4/362—Composites
  • H01M4/366—Composites as layered products
• • 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
  • H01M4/48—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
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T10/00—Road transport of goods or passengers
  • Y02T10/60—Other road transportation technologies with climate change mitigation effect
  • Y02T10/70—Energy storage systems for electromobility, e.g. 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

Definitions

• Rechargeable batteries such as lithium-ion rechargeable batteries
• battery-powered portable electronic devices such as cellular telephones, portable computers, camcorders, digital cameras, PDAs and the like.
• a typical lithium-ion battery pack for such portable electronic devices employs multiple cells that are configured in parallel and in series.
• a lithium-ion battery pack may include several blocks connected in series where each block includes one or more cells connected in parallel. Each block typically has an electronic control that monitors voltage levels of the block. In an ideal configuration, each of the cells included in the battery pack is identical.
• lithium-ion rechargeable batteries employ solely LiCo ⁇ 2-type materials as the active component of lithium-ion battery cathodes.
• the charge voltage is usually 4.20V.
• the capacity is lower, which corresponds to lower utilization of active LiCoO 2 materials.
• the cell is less safe.
• Lowering charge voltage is one option to maximize sagfety. However, this will lower the cell capacity, and in turn lower cell energy density.
• increasing the number of cells in one battery pack may be another alternative to increasing the charge voltage.
• an increase in the number of cells can result in increased probability of unbalance among the cells, which can cause over-charge or over-discharge during normal operation, as discussed above.
• the largest mainstream cell that is typically used in the industry currently is a so-called " 18650" cell.
• This cell has an outer diameter of about 18 mm and a length of 65 mm.
• the 18650 cell utilizes LiCoO 2 and has a capacity between 1800 mAh and 2400 rnAh but cells as high as 2600 mAh are currently being used. It is generally believed that it is not safe to use LiCoO 2 in a cell larger than the 18650 cell because of safety concerns associated with LiCoO 2 .
• the present invention is generally directed to (1) an active cathode material that includes a mixture of a lithium cobaltate and a spinel type lithium manganate, (2) a lithium- ion battery having such an active cathode material, (3) a method of forming such a lithium-ion battery, (4) a battery pack comprising one or more cells, each of the cells including such an active cathode material, and (5) a system that includes such a battery pack or lithium-ion battery, and a portable electronic device.
• the active cathode material includes a cathode mixture that includes a lithium cobaltate and a spinel type lithium manganate, wherein the lithium cobaltate and the lithium manganate are in a weight ratio of lithium cobaltate: lithium manganate between about 0.95:0.05 and about 0.55:0,45, and wherein a ratio of the mean particle diameter of the lithium cobaltate to the mean particle diameter of the lithium manganate is in a range of between about 1 :0.35 and about 1 : 1.4.
• the present invention can be used in mobile electronic devices such as portable computers, cell phones and portable power tools.
• the present invention can also be used in batteries for hybrid electric vehicles. BRIEF DESCRIPTION OF THE DRAWINGS
• FIG. 1 is a schematic view of a prismatic battery of the invention.
• FIG. 2A shows a top view of the prismatic battery of FIG. 1.
• FIG. 2B shows a side view of the lid of the prismatic battery of FIG. 1.
• FIG. 3 shows a schematic view of a cylindrical battery of the invention.
• FIG. 4 is a schematic circuitry showing how individual cells in the invention are preferably connected when arranged together in a battery pack of the invention.
• the present invention relates to an active cathode material mixture that can be employed in an electrode of a lithium-ion battery that allows lithium to be reversibly intercalated and extracted.
• the active cathode material comprises a mixture that includes a lithium cobaltate and a spinel type lithium manganate ("lithium manganate spinel").
• the lithium cobaltate and the lithium manganate spinel are in a weight ratio of lithium cobaltate: lithium manganate spinel between about 0.95:0.05 and about 0.55:0.45.
• the lithium cobaltate and the lithium manganate spinel are in a weight ratio of lithium cobaltate: lithium manganate spinel between about 0.95:0.05 and about 0.65:0.35.
• the lithium cobaltate and the lithium manganate spinel are in a weight ratio of lithium cobaltate: lithium manganate spinel between about 0.95:0.05 and about 0.7:0.3. In another specific embodiment, the lithium cobaltate and the lithium manganate spinel are in a weight ratio of lithium cobaltate: lithium manganate spinel between about 0.85:0.15 and about 0.75:0.25. In another specific embodiment, the mixture includes about 80 wt% of the lithium cobaltate and about 20 wt% of the lithium manganate spinel.
• a ratio of the mean particle diameter of the lithium cobaltate to the mean particle diameter of the lithium manganate spinel is in a range of between about 1 :0.35 and about 1 : 1.4.
• a "mean particle diameter" typically is determined by averaging the maximum and minimum axes of individual particles appearing in a scanning electron microscope (SEM) examination field, typically encompassing several hundred particles. Each particle's average axis is then averaged over the entire field, thus calculating the "mean particle diameter.”
• SEM scanning electron microscope
• Commercial software packages for example, Olympus-SIS Platinum, can be utilized to perform the measurements and calculations resulting in the mean particle diameter.
• the ratio of the mean particle diameter of the lithium cobaltate to the mean particle diameter of the lithium manganate spinel is in a range of between about 1 :0.35 and about 1 : 1.4. In another specific embodiment, the ratio of the mean particle diameter of the lithium cobaltate to the mean particle diameter of the lithium manganate spinel is in a range of between about 1 :0,4 and about 1 : 1.2.
• the mean particle diameter of the lithium cobaltate is greater than the mean particle diameter of the lithium manganate spinel.
• the ratio of the mean particle diameter of the lithium cobaltate to the mean particle diameter of the lithium manganate spinel is in a range of between about 1 :0.5 and about 1 :0.9, between about 1 :0.6 and about 1 :0.9, or between about 1 :0.6 and about 1 :0.8 (e.g., about 1 :0.7, about 1 : 0.73, about 1 : 0.75, about 1 :0.78, or about 1 :0.8).
• the mean particle diameter of the lithium cobaltate is in a range between about 1 micron and about 20 microns. In a specific embodiment, the mean particle diameter of the lithium cobaltate is in a range between about 1 micron and about 10 microns. In another specific embodiment, the mean particle diameter of the lithium cobaltate is in a range between about 3 microns and about 8 microns. In yet another specific embodiment, the mean particle diameter of the lithium cobaltate is in a range between about 4 microns and about 8 microns (e.g., about 6 microns).
• the mean particle diameter of the lithium manganate spinel is in a range between about 1 micron and about 20 microns. In a specific embodiment, the mean particle diameter of the lithium manganate spinel is in a range between about 1 micron and about 10 microns. In another specific embodiment, the mean particle diameter of the lithium manganate spinel is in a range between about 3 microns and about 8 microns. In yet another specific embodiment, the mean particle diameter of the lithium manganate spinel is in a range between about 3 microns and about 6 microns (e.g., about 4 microns).
• lithium cobaltates that can be employed in the invention include LiCoC> 2 that is optionally modified by at least one of modifiers of Li and Co atoms.
• Li modifiers include barium (Ba), magnesium (Mg), calcium (Ca), strontium (Sr) and sodium (Na).
• Co modifiers include the modifiers for Li and aluminum (Al), manganese (Mn) and boron (B).
• Other examples include nickel (Ni) and titanium (Ti).
• lithium cobaltates Another type of the lithium cobaltates that can be employed in the invention is represented by an empirical formula of Li(i t- X8 )CoO Z8 , wherein x8 is equal to or greater than zero and equal to or less than 0.2, and wherein z8 is equal to or greater than 1.9 and equal to or less than 2.1.
• a common example is LiCoO 2 optionally coated with ZrO 2 or A1 2 (PO 4 ) 3 .
• the lithium cobaltates employed in the invention have a spherical-like morphology as this improves packing and production characteristics.
• a crystal structure of the lithium cobaltates is independently a R-3m type space group (rhombohedral, including distorted rhombohedral).
• Lithium manganate spinel compounds that can be employed in the invention have a manganese base, such as LiMn 2 O 4 . While the manganate spinel compounds typically have low specific capacity (e.g., in a range of about 120 to 130 mAh/g), they generally have high power delivery when formulated into electrodes and are typically safe in terms of chemical reactivity at higher temperatures. Another advantage of the manganate spinel compounds is their relatively low cost.
• lithium manganate spinel compounds that can be employed in the invention is represented by an empirical formula of Li(i t- x i)(Mni.yiA' y2 ) 2-x2 O z i, wherein A' is one or more of Mg, Al, Co, Ni and Cr; xl and x2 are each independently equal to or greater than 0.01 and equal to or less than 0.3; yl and y2 are each independently equal to or greater than 0.0 and equal to or less than 0.3; zl is equal to or greater than 3.9 and equal to or less than 4.1.
• A' includes a M 34 ion, such as Al 3+ , Co 3+ , Ni 3+ and Cr 3+ , more preferably Al + .
• the lithium manganate spinel compounds of Li ( i +x i ) (Mni -y i A 1 J ⁇ - X2 O 7J can have enhanced cyclability and power compared to those of LiMn 2 O 4
• xl is equal to or greater than 0.01 and equal to or less than 0.3.
• xl is equal to or greater than 0.01 and equal to or less than 0.2.
• xl is equal to or greater than 0.05 and equal to or less than 0.15.
• lithium manganate spinel compounds that can be employed in the invention is represented by an empirical formula of Li(i +x i)(Mni- y iA' y2 ) 2 - x2 ⁇ z i ; wherein yl and y2 are each independently greater than 0.0 and equal to or less than 0.3, and the other values are the same as described above for Li ( i +x i ) (Mni_ y iA' y2 ) 2 - x2 0 7 i.
• can be found in U.S. Patent Nos. 4,366,215; 5,196,270; and 5,316,877 (the entire teachings of which are incorporated herein by reference).
• the active cathode materials of the invention can be prepared by mixing the lithium cobaltate and the lithium manganate spinel compound, preferably in a powdered form.
• the battery has a greater than about 2.2 Ah/cell capacity. More preferably, the battery has a greater than about 3.0 Ah/cell capacity, such as equal to or greater than about 3.3 Ah/cell; equal to or greater than about 3.5 Ah/cell; equal to or greater than about 3.8 Ah/cell; equal to or greater than about 4.0 Ah/cell; equal to or greater than about 4.2 Ah/cell; between about 3.0 Ah/cell and about 6 Ah/cell; between about 3.3 Ah/cell and about 6 Ah/cell; between about 3.3 Ah/cell and about 5 Ah/cell; between about 3.5 Ah/cell and about 5 Ah/cell; between about 3.8 Ah/cell and about 5 Ah/cell; or between about 4.0 Ah/cell and about 5 Ah/cell.
• the battery (or cell) of the invention can be cylindrical (e.g., 26650, 18650, or 14500 configuration) or prismatic (stacked or wound, e.g., 183665 or 103450 configuration). Preferably, they are prismatic, and, more preferably, of a prismatic shape that is oblong. Although the present invention can use all types of prismatic cell casings, an oblong cell casing is preferred partly due to the two features described below.
• the available internal volume of an oblong shape is larger than the volume of two 18650 cells, when comparing stacks of the same external volume.
• the oblong cell When assembled into a battery pack, the oblong cell fully utilizes more of the space that is occupied by the battery pack. This enables novel design changes to the internal cell components that can increase key performance features without sacrificing cell capacity relative to that found in the industry today. Due to the larger available volume, one can elect to use thinner electrodes, which have relatively higher cycle life and a higher rate capability.
• an oblong can has larger flexibility. For instance, an oblong shape can flex more at the waist point compared to a cylindrically shaped can, which allows less flexibility as stack pressure increases upon charging.
• the increased flexibility decreases mechanical fatigue on the electrodes, which, in turn, causes higher cycle life. Also, clogging of pores of a separator in batteries can be improved by employing a relatively low stack pressure.
• a particularly desired feature, allowing relatively higher safety, is available for the oblong shaped battery compared to the prismatic battery. The oblong shape provides a snug fit to the jelly roll, which minimizes the amount of electrolyte necessary for the battery. The relatively low amount of electrolyte results in less available reactive material during a misuse scenario and hence higher safety. In addition, the cost is lower due to employment of a lower amount of electrolyte.
• cell building for a battery (or cell) of the invention utilizes a larger format in terms of Ah/cell than that is currently used in the industry, such as in the case for 18650 cells (e.g., cylindrical cells).
• a battery (or cell) of the invention has an 183665 form factor (e.g., prismatic cell).
• the battery (or cell) of the invention has an oblong shape with a thickness of about 17 mm or about 18 mm, a width of about 44 mm or about 36 mm, a height of about 64 mm or about 65 mm.
• a battery (or cell) has a thickness of about 17 mm, a width of about 44 mm and a height of about 64 mm; a thickness of about 18 mm, a width of about 36 mm and a height of about 65 mm; or a thickness of about 18 mm, a width of about 27 mm and a height of about 65 mm.
• a battery (or cell) of the invention has an 1865 form factor as in an 18650 cell.
• FIG. 1 shows one specific embodiment, battery 10, of the invention, wherein battery 10 has an oblong cross-sectional shape.
• FIGs. 2A and 2B show a top view and cross-sectional view of the lid of battery 10 of FIG. 1, respectively.
• battery 10 includes first electrode 12 and second electrode 14.
• First electrode 12 is electrically connected to feed- through device 16, which includes first component 18, which is proximal to first electrode 12, and second component 20, which is distal to first electrode 12.
• Feed-through device 16 can further include conductive layer 26.
• the electrodes 12 and 14 are placed inside battery can 21 that includes cell casing 22 and lid 24, i.e., internal space 27 defined by cell casing 22 and lid 24. Cell casing 22 and lid 24 of battery 10 are in electrical communication with each other.
• Battery 10 of the invention can optionally include current interrupt device (CID) 28, as shown in FIG. 1.
• CID 28 can be activated at an internal gauge pressure in a range of, for example, between about 4 kg/cm and about 15 kg/cm 2 (e.g., between about 4 kg/cm 2 and
• activation of the CID means that current flow of an electronic device through the CID is interrupted.
• the CID of the invention includes a fist conductive component and a second conductive component in electrical communication with each other (e.g., by welding, crimping, riveting, etc.).
• activation means that the electrical communication between the first and second conductive components is interrupted.
• the first and second components of the CID can be in any suitable form, such as a plate or disk.
• CID 28 typically includes first conductive component 30 and second conductive component 32 in electrical communication with each other (e.g., by welding, crimping, riveting, etc).
• Second conductive component 32 is in electrical communication with second electrode 14, and first conductive component 30 is in electrical contact with battery can 21 , for example, lid 24.
• Battery can 21, i.e., cell casing 22 and lid 24, is electrically insulated from a first terminal of battery 10 (e.g., electrically conductive layer 26), and at least a portion of battery can 21 is at least a component of a second terminal of battery 10, or is electrically connected to the second terminal.
• first conductive component 30 includes a cone- or dome-shaped part. In another specific embodiment, at least a portion of the top (or cap) of the cone-or dome-shaped part is essentially planar. In yet another specific embodiment, first and second conductive components 30 and 32 of CID 28 are in direct contact with each other at a portion of the essentially planar cap, In yet another specific embodiment, first conductive component 30 includes a frustum having an essentially planar cap, as described in U.S. Provisional Application No. 60/936,825, filed on June 22, 2007 (the entire teachings of which are incorporated herein by reference).
• CID 28 can further include insulator 34 (e.g., insulating layer or insulating gasket) between a portion of first conductive component 30 and second conductive component 32.
• insulator 34 e.g., insulating layer or insulating gasket
• at least one of second conductive component 32 and insulator 34 of CID 28 includes at least one hole (e.g., holes 36 or 38 in FIG. 1) through which gas within battery 10 is in fluid communication with first conductive component 30.
• CID 28 further includes end component 40 disposed over first conductive component 30, and defining at least one hole 42 through which first conductive component 30 is in fluid communication with the atmosphere outside the battery.
• End component 40 e.g., a plate or disk
• end component 40 can be a part of battery can 21, as shown in FIG. 1 where end component 40 is a part of lid 24 of battery can 21.
• end component 40 can be a separate component from battery can 21 , and be placed at battery can 21 , for example, over, under or at lid 24 of battery can 21.
• terminals of the batteries of the invention mean the parts or surfaces of the batteries to which external electric circuits are connected.
• the batteries of the invention typically include a first terminal in electrical communication with a first electrode, and a second terminal in electrical communication with a second electrode.
• the first and second electrodes are contained within a cell casing, for example, in a "jelly roll" form.
• the first terminal can be either a positive terminal in electrical communication with a positive electrode of the battery, or a negative terminal in electrical communication with a negative electrode of the battery, and vice versa for the second terminal.
• the first terminal is a negative terminal in electrical communication with a negative electrode of the battery
• the second terminal is a positive terminal in electrical communication with a positive electrode of the battery.
• electrochemical contacted means certain parts are in communication with each other by flow of electrons through conductors, as opposed to electrochemical communication which involves flow of ions, such as Li + , through electrolytes.
• electrochemical communication means communication between certain parts through electrolyte media and involves flows of ions, such as Li + .
• FIG. 3 shows another embodiment, battery 50, of the invention, wherein battery 50 has a cylindrical cross-sectional shape.
• battery 50 includes battery can 21 that includes cell casing 22 and lid 24, first electrode 12 and second electrode 14, and optionally CID 28.
• First electrode 12 is in electrical communication with a first terminal of the battery (e.g., conductive component 58), and second electrode 14 is in electrical communication with a second terminal of the battery (e.g., lid 24).
• Cell casing 22 and lid 24 are in electrical contact with each other.
• the tabs (not shown in FIG.
• first electrode 12 are electrically connected (e.g., by welding, crimping, riveting, etc.) to electrically-conductive, first component 54 of feed-through device 52.
• the tabs (not shown in FIG. 3) of second electrode 14 are in electrically connected (e.g., by welding, crimping, riveting, etc.) to second conductive component 32 of CID 28,
• Feed-through device 52 includes first conductive component 54, which is electrically conductive, insulator 56, and second conductive component 58, which can be the first terminal of battery 50.
• battery can 21 i.e., cell casing 22 and lid 24, is electrically insulated from a first terminal of battery 50 (e.g., conductive component 58), and at least a portion of battery can 21 is at least a component of a second terminal of battery 50, or is electrically connected to the second terminal,
• a portion of Hd 24 or the bottom of cell casing 22 serves as the second terminal of battery 50
• conductive component 58 serves as the first terminal of battery 50.
• FIGs, 1 -3 show CID assemblies where CID 28 is in electrical communication with second electrode 14, a CID assembly where a CID, such as CID 28, is in electrical communication with first electrode 12 can also be employed in the invention.
• first electrode 12 and second electrode 14 can be the negative and positive electrodes described above, or vice versa.
• the negative electrode of a battery (or cell) of the invention can include any suitable material allowing lithium to be inserted in or removed from the material.
• suitable materials include carbonaceous materials, for example, non-graphitic carbon, artificial carbon, artificial graphite, natural graphite, pyrolytic carbons, cokes such as pitch coke, needle coke, petroleum coke, graphite, vitreous carbons, or a heat treated organic polymer compound obtained by carbonizing phenol resins, furan resins, or similar, carbon fibers, and activated carbon.
• metallic lithium, lithium alloys, and an alloy or compound thereof are usable as the negative active materials.
• the metal element or semiconductor element allowed to form an alloy or compound with lithium may be a group IV metal element or semiconductor element, such as but not limited to, silicon or tin.
• Oxides allowing lithium to be inserted in or removed from the oxide at a relatively low potential such as iron oxide, ruthenium oxide, molybdenum oxide, tungsten oxide, titanium oxide, and tin oxide, and nitrides can be similarly usable as the negative active materials.
• amorphous tin optionally doped with a transition metal, such as cobalt or iron/nickel, is employed in the invention.
• I he positive electrode of a battery (or cell) of the invention includes an active cathode material of the invention described above. It is noted that the suitable cathode materials described herein are characterized by empirical formulas that exist upon manufacture of lithium-ion batteries in which they are incorporated. It is understood that their specific compositions thereafter are subject to variation pursuant to their electrochemical reactions that occur during use (e.g., charging and discharging).
• the positive electrode of a battery (or cell) of the invention has a packing density in a range of between about 2.6 g/cm 3 and about 3.7 g/cm 3 . In one specific embodiment, the positive electrode of a battery (or cell) of the invention has a packing density in a range of between about 3.0 g/cm 3 and about 3.7 g/cm 3 . In another specific embodiment, the positive electrode of a battery (or cell) of the invention has a packing density in a range of between about 3.3 g/cm 3 and about 3.6 g/cm 3 .
• the positive electrode of a battery (or cell) of the invention has a packing density in a range of between about 3.5 g/cm 3 and about 3.6 g/cm 3 .
• the positive electrode with the aforementioned density can be made by any suitable method known in the art.
• the cathode material is mixed with other ingredients, such as a conductive agent (e.g. acetylene black), a binder (e.g., PVDF), etc.
• a solvent e.g., N-methyl-2- pyrrolidone (NMP)
• NMP N-methyl-2- pyrrolidone
• This slurry is then applied to both surfaces of an aluminum current collector foil, and dried.
• the dried electrode is then pressed (e.g., calendered) by a roll press, to obtain a compressed positive electrode with the desired density.
• non-aqueous electrolytes examples include a non-aqueous electrolytic solution prepared by dissolving an electrolyte salt in a non-aqueous solvent, a solid electrolyte (inorganic electrolyte or polymer electrolyte containing an electrolyte salt), and a solid or gel- like electrolyte prepared by mixing or dissolving an electrolyte in a polymer compound or the like.
• the non-aqueous electrolytic solution is typically prepared by dissolving a salt in an organic solvent.
• the organic solvent can include any suitable type that has been generally used for batteries of this type. Examples of such organic solvents include propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), 1 ,2- dimethoxyethane, 1 ,2-diethoxyethane, ⁇ -butyrolactone, tetrahydrofuran, 2-methyl tetrahydrofuran, 1 ,3-dioxolane, 4-methyl-l ,3-dioxolane, diethyl ether, sulfolane, methylsulfolane, acetonitrile, propionilrile, anisole, acetate, butyrate, propionate and the like. It is preferred to use cyclic carbonates such as propylene carbonate, or chain carbonates such as dimethyl carbonate and diethyl carbonate. These organic
• Additives or stabilizers may also be present in the electrolyte, such as VC (vinyl carbonate), VEC (vinyl ethylene carbonate), EA (ethylene acetate), TPP (triphenylphosphate), phospha/enes, biphenyl (BP), cyclohexylbenzene (CHB), 2,2-diphenylpropane (DP), lithium bis(oxalato)borate (LiBoB), ethylene sulfate (ES) and propylene sulfate.
• VC vinyl carbonate
• VEC vinyl ethylene carbonate
• EA ethylene acetate
• TPP triphenylphosphate
• DP cyclohexylbenzene
• LiBoB 2,2-diphenylpropane
• LiBoB lithium bis(oxalato)borate
• ES ethylene sulfate
• propylene sulfate propylene sulfate
• the solid electrolyte can include an inorganic electrolyte, a polymer electrolyte and the like insofar as the material has lithium-ion conductivity.
• the inorganic electrolyte can include, for example, lithium nitride, lithium iodide and the like.
• the polymer electrolyte is composed of an electrolyte salt and a polymer compound in which the electrolyte salt is dissolved.
• the polymer compounds used for the polymer electrolyte include ether-based polymers such as polyethylene oxide and cross-linked polyethylene oxide, polymethacrylate ester-based polymers, acrylate-based polymers and the like. These polymers may be used singly, or in the form of a mixture or a copolymer of two kinds or more.
• a matrix of the gel electrolyte may be any polymer insofar as the polymer is gelated by absorbing the above-described non-aqueous electrolytic solution.
• the polymers used for the gel electrolyte include fluorocarbon polymers such as polyvinylidene fluoride (PVDF), polyvinylidene-co-hexafluoropropylene (PVDF-HFP) and the like.
• Examples of the polymers used for the gel electrolyte also include polyacrylonitrile and a copolymer of polyacrylonitrile.
• Examples of monomers (vinyl based monomers) used for copolymerization include vinyl acetate, methyl methacrylate, butyl methacylate, methyl acrylate, butyl acrylate, itaconic acid, hydrogenated methyl acrylate, hydrogenated ethyl acrylate, acrlyamide, vinyl chloride, vinylidene fluoride, and vinylidene chloride.
• polymers used for the gel electrolyte further include acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene-styrenc copolymer resin, acrylonitrile-chlorinated polyethylene-propylenediene-styrene copolymer resin, acrylonitrile-vinyl chloride copolymer resin, acrylonitrile-melhacylate resin, and acrlylonitrile-acrylate copolymer resin.
• acrylonitrile-butadiene copolymer rubber acrylonitrile-butadiene-styrenc copolymer resin
• acrylonitrile-chlorinated polyethylene-propylenediene-styrene copolymer resin acrylonitrile-vinyl chloride copolymer resin
• acrylonitrile-melhacylate resin acrylonitrile-melhacylate resin
• acrlylonitrile-acrylate copolymer resin
• polymers used for the gel electrolyte include ether based polymers such as polyethylene oxide, copolymer of polyethylene oxide, and cross-linked polyethylene oxide.
• monomers used for copolymerization include polypropylene oxide, methyl methacrylate, butyl methacylate, methyl acrylate, butyl acrylate.
• a fluorocarbon polymer is preferably used for the matrix of the gel electrolyte.
• the electrolyte salt used in the electrolyte may be any electrolyte salt suitable for batteries of this type.
• the electrolyte salts include LiClO 4 , LiAsFe, LiPF 6 , LiBF 4 , LiB(C 6 Hs) 4 , LiB(C 2 O 4 ) 2 , CH 3 SO 3 Li, CF 3 SO 3 Li, LiCl, LiBr and the like.
• a separator separates the positive electrode from the negative electrode of the batteries.
• the separator can include any film-like material having been generally used for forming separators of non-aqueous electrolyte secondary batteries of this type, for example, a microporous polymer film made from polypropylene, polyethylene, or a layered combination of the two.
• a microporous separator made of glass fiber or cellulose material can in certain cases also be used. Separator thickness is typically between about 9 microns and about 25 microns.
• DEC solvents with IM LiPF 6 and suitable additives at 0.5 - 3 wt.% each, such as VC, LiBOB, PF, LiTFSI or BP, is vacuum filled in battery can 21 ⁇ see FIGs. 1 and 3) having the spirally wound "jelly roll".
• the positive electrode of a battery (or cell) of the invention is produced by mixing the cathode material at about 94 wt % together with about 3 wt % of a conductive agent (e.g. acetylene black), and about 3 wt % of a binder (e.g., PVDF).
• a conductive agent e.g. acetylene black
• a binder e.g., PVDF
• NMP N-methyl-2-pyrrolidone
• This slurry is then applied to both surfaces of an aluminum current collector foil, which typically has a thickness of about 20 urn, and dried at about 100-150 0 C.
• the dried electrode is then calendered by a roll press, to obtain the compressed positive electrode.
• the negative electrode is prepared by mixing about 93 wt% of graphite as a negative active material, about 3 wt% of conductive carbon (e.g. acetylene black), and about 4 wt% of a binder (e.g. PVDF).
• the negative electrode is then prepared from this mix in a process similar to that described above for positive electrode except that a copper current collector foil, typically of about 10 - 15 ⁇ m thickness, is used.
• the positive electrode is produced by mixing the cathode powders at a specific ratio. About 90 wt % of this blend is then mixed together with about 5 wt % of acetylene black as a conductive agent, and about 5 wt % of PVDF as a binder. The mix is dispersed in N-methyl-2-pyrrolidone (NMP) as a solvent, in order to prepare slurry. This slurry is then applied to both surfaces of an aluminum current collector foil, having a typical thickness of about 20 ⁇ m, and dried at about 100-150° C. The dried electrode is then calendared by a roll press, to obtain a compressed positive electrode.
• NMP N-methyl-2-pyrrolidone
• the negative electrode can be prepared by mixing about 93 Wt% of graphite as a negative active material, about 3 wt% acetylene black, and about 4 wt% of PVDF as a binder.
• the negative mix is also dispersed in N-methyl-2-pyrrolidone as a solvent, in order to prepare the slurry,
• the negative mix slurry was uniformly applied on both surfaces of a strip-like copper negative current collector foil, having a typical thickness of about 10 ⁇ m.
• the dried electrode is then calendared by a roll press to obtain a dense negative electrode.
• the negative and positive electrodes, and a separator e.g., about 25 microns thick
• a separator formed of, for example, a polyethylene film with micro pores are generally laminated and spirally wound to produce a spiral type electrode element.
• one or more positive lead current carrying tabs are attached to the positive electrode and welded to feed-through device 16 (see FIGs. 1 and 3).
• a negative lead made of nickel metal, connects the negative electrode to the bottom or the lid of battery can 21 (see FIGs. 1 and 3).
• feed-through includes any material or device that connects electrode 12, within the internal space defined by cell casing 22 and lid 24, with a component of the battery external to that defined internal space.
• feed-through device 16 or 52 extends through a pass-through hole defined by lid 24.
• Feed-through device 16 or 52 also can pass through lid 24 without deformation, such as bending, twisting and/or folding, and can increase cell capacity.
• Any other suitable means known in the art can also be used in the invention to connect electrode 12 with a component of the battery external to battery can 21, e.g., a terminal of the battery.
• feed- through devices 16 and 52 are electrically insulated from battery can 21 , for example, lid 24, for example, by an insulating gasket (not shown in FIGs. 1-2B, insulator 56 of FIG. 3).
• the insulating gasket is formed of a suitable insulating material, such as polypropylene, polyvinylfluoride (PVF), etc.
• Components 18, 20 and 26 of feed-through device 16, and components 54 and 58 of feed-through device 52 can be made of any suitable conductive material known in the art, for example, nickel.
• first conductive component 30 when first conductive component 30 separates from second conductive component 32, no rupture occurs in first conductive component 30 so that gas inside battery 10 or 50 does not go out through first conductive component 30.
• the gas can exit battery 10 or 50 through one or more venting means 56 (e g, at cell wall or the bottom part of cell casing 22, or first conductive component 30), when the internal pressure keeps increasing and reaches a predetermined value for activation of venting means 56.
• the predetermined gauge pressure value for activation of venting means 56 (e.g., between about 10 kg/cm 2 and about 20 kg/cm ) is higher than that for activation of CID 28 (e.g., between about 5 kg/cm 2 and about 10 kg/cm 2 ).
• This feature helps prevent premature gas leakage, which can damage neighboring batteries (or cells) which are operating normally. So, when one of a plurality of cells in the battery packs of the invention is damaged, the other healthy cells are not damaged.
• gauge pressure values or sub-ranges suitable for the activation of CID 28 and those for activation of venting means 56 are selected from among the predetermined gauge pressure ranges such that there is no overlap between the selected pressure values or sub-ranges.
• the values or ranges of gauge pressure for the activation of CID 28 and those for the activation of venting means 56 differ by at least about 2 kg/cm 2 pressure difference, more preferably by at least about 4 kg/cm , even more preferably by at least about 6 kg/cm , such as by about 7 kg/cm 2 .
• First conductive component 30, second conductive component 32 and end component 40 of CID 28 can be made of any suitable conductive material known in the art for a battery. Examples of suitable materials include aluminum, nickel and copper, preferably aluminum.
• battery can 21 e.g., cell casing 22 and lid 24
• first conductive component 30 and second conductive component 32 are made of substantially the same metals.
• substantially same metals means metals that have substantially the same chemical and electrochemical stability at a given voltage, e.g., the operation voltage of a battery.
• first conductive component 30 and second conductive component 32 are made of the same metal, such as aluminum (e.g., Aluminum 3003 series, such as Aluminum 3003 H- 14 series and/or Aluminum 3003 H-O series).
• CID 28 can be made by any suitable method known in the art, for example, in WO
• CID 28 is attached to battery can 21 via welding, and more preferably by welding first conductive component 30 onto end component 40 (or Hd 24 itself).
• Cell casing 22 can be made of any suitable electrically-conductive material which is essentially stable electrically and chemically at a given voltage of batteries, such as the lithium-ion batteries of the invention.
• suitable materials of cell casing 22 include metallic materials, such as aluminum, nickel, copper, steel, nickel-plated iron, stainless steel and combinations thereof.
• cell casing 22 is of, or includes, aluminum.
• lid 24 examples are the same as those listed for cell casing 22.
• Hd 24 is made of the same material as cell casing 22.
• both cell casing 22 and Hd 24 are formed of, or include, aluminum. Lid 24 can hermetically seal cell casing 22 by any suitable method known in the art
• cell casing 22 includes at least one venting means 56 as a means for venting interior gaseous species when necessary (e.g., when an internal gauge pressure is in a range of between about 10 kg/cm 2 and about 20 kg/cm , such as between about 12 kg/cm and about 20 kg/cm or between about 10 kg/cm and about 18 kg/cm ).
• venting means any suitable type of venting means can be employed as long as the means provide hermetic sealing in normal battery operation conditions.
• Various suitable examples of venting means are described in U.S. Provisional Application No. 60/717,898, filed on September 16, 2005, the entire teachings of which are incorporated herein by reference.
• venting means include vent scores.
• the term "score” means partial incision of section(s) of a cell casing, such as cell casing 104, that is designed to allow the cell pressure and any internal cell components to be released at a defined internal pressure.
• venting means 1 12 is a vent score, more preferably, vent score that is directionally positioned away from a user/or neighboring cells. More than one vent score can be employed in the invention. In some embodiments, patterned vent scores can be employed. The vent scores can be parallel, perpendicular, diagonal to a major stretching (or drawing) direction of the cell casing material during creation of the shape of the cell casing. Consideration is also given to vent score properties, such as depth, shape and length (size).
• the batteries of the invention can further include a positive thermal coefficient layer (PTC) in electrical communication with either the first terminal or the second terminal, preferably in electrical communication with the first terminal.
• PTC positive thermal coefficient layer
• Suitable PTC materials are those known in the art. Generally, suitable PTC materials are those that, when exposed to an electrical current in excess of a design threshold, its electrical conductivity decreases with increasing temperature by several orders of magnitude (e.g., 10 4 to 10 or more). Once the electrical current is reduced below a suitable threshold, in general, the PTC material substantially returns to the initial electrical resistivity.
• the PTC material includes small quantities of semiconductor material in a polycrystalline ceramic, or a slice of plastic or polymer with carbon grains embedded in it.
• the semiconductor material or the plastic or polymer with embedded carbon grains forms a barrier to the flow of electricity and causes electrical resistance to increase precipitously.
• the temperature at which electrical resistivity precipitously increases can be varied by adjusting the composition of the PTC material, as is known in the art.
• An "operating temperature" of the PTC material is a temperature at which the PTC exhibits an electrical resistivity about half way between its highest and lowest electrical resistance.
• the operating temperature of the PTC layer employed in the invention is between about 70° Celsius and about 150° Celsius.
• specific PTC materials include polycrystalline ceramics containing small quantities of barium titanate (BaTiO 3 ), and polyolefins including carbon grains embedded therein.
• Examples of commercially available PTC laminates that include a PTC layer sandwiched between two conducting metal layers include LTP and LR4 series manufactured by Raychem Co, Generally, the PTC layer has a thickness in a range of about 50 ⁇ m and about 300 ⁇ m.
• the PTC layer includes an electrically conductive surface, the total area of which is at least about 25% or at least about 50% (e.g., about 48% or about 56%) of the total surface area of lid 24 or the bottom of battery 10 or 50.
• the total surface area of the electrically conductive surface of the PTC layer can be at least about 56% of the total surface area of lid 24 or the bottom of battery 10 or 50. Up to 100% of the total surface area of lid 24 of battery 10 or 50 can occupied by the electrically conductive surface of the PTC layer. Alternatively, the whole, or part, of the bottom of battery 10 or 50 can be occupied by the electrically conductive surface of the PTC layer.
• the PTC layer can be positioned externally to the battery can, for example, over a lid
• the PTC layer is between a first conductive layer and a second conductive layer and at least a portion of the second conductive layer is at least a component of the first terminal, or is electrically connected to the first terminal.
• the first conductive layer is connected to the feed-through device.
• a battery of the invention includes battery can 21 that includes cell casing 22 and lid 24, at least one CID, such as CID 28 described above, in electrical communication with either of the first or second electrodes of the battery, and at least one venting means 56 on cell casing 22.
• battery can 21 is electrically insulated from the first terminal that is in electrical communication with the first electrode of the battery.
• At least a portion of battery can 21 is at least a component of the second terminal that is in electrical communication with the second electrode of the battery.
• Lid 24 is welded on cell casing 22 such that the welded lid is detached from cell casing 22 at an internal gauge pressure greater than about 20 kg/cm 2 .
• the CID includes a first conductive component (e g., first conductive component 30) and a second conductive component (e g., second conductive component 32) in electrical communication with each other, preferably by a weld.
• This electrical communication is interrupted at an internal gauge pressure between about 4 kg/cm 2 and about 10 kg/cm 2 , (e.g., between about 5 kg/cm 2 and about 9 kg/cm 2 or between about 7 kg/cm 2 and about 9 kg/cm 2 ).
• the first and second conductive components are welded, e.g., laser welded, to each other such that the weld ruptures at the predetermined gauge pressure.
• At least one venting means 56 is formed to vent interior gaseous species when an internal gauge pressure in a range of between about 10 kg/cm 2 and about 20 kg/cm 2 or between about 12 kg/cm 2 and about 20 kg/cm 2 .
• gauge pressure values or sub-ranges suitable for the activation of CID 28 and those for activation of venting means 56 are selected from among the predetermined gauge pressure ranges such that there is no overlap between the selected pressure values or sub-ranges.
• the values or ranges of gauge pressure for the activation of CID 28 and those for the activation of venting means 56 differ by at least about 2 kg/cm 2 pressure difference, more typically by at least about 4 kg/cm 2 , even more preferably by at least about 6 kg/cm 2 , such as by about 7 kg/cm 2 .
• gauge pressure values or sub-ranges suitable for the rupture of the welded lid 24 from cell casing 22 and those for activation of venting means 56 are selected from among the predetermined gauge pressure ranges such that there is no overlap between the selected pressure values or sub-ranges.
• the battery of the invention is rechargeable.
• the battery of the invention is a rechargeable lithium-ion battery.
• the battery of the invention such as a lithium-ion battery, has an internal gauge pressure of less than or equal to about 2 kg/cm 2 under a normal working condition.
• the active electrode materials can be first activated prior to hermetical sealing of the battery can.
• FIG. 4 is a schematic circuitry of the invention, showing how individual cells or batteries (e g,, battery 10 of FIG. 1 or battery 50 of FIG. 3) are arranged together in a battery pack.
• Charger 70 is employed to charge cells 1, 2 and 3.
• a plurality of lithium-ion batteries of the invention can be connected in a battery pack, wherein each of the batteries (cells) is connected with each other in series, parallel, or in series and parallel.
• each of the batteries cells
• at least one cell has a prismatic shaped cell casing, and more preferably, an oblong shaped cell casing, as shown in FIG. 1.
• the capacity of the cells in the battery pack is typically equal to or greater than about 3.0 Ah, more preferably equal to or greater than about 4.0 Ah.
• the internal impedance of the cells is preferably less than about 50 milli-ohms, and more preferably less than 30 milli-ohms.
• the present invention also includes a method of producing a lithium-ion battery, such as a rechargeable lithium-ion battery, of the invention as described above.
• the method includes forming an active cathode material of the invention described above.
• a positive electrode is formed with the active cathode material, and a negative electrode in electrical contact with the positive electrode via an electrolyte is formed, as described above, thereby forming the lithium- ion battery.
• the present invention also includes a system that includes a portable electronic device and a cell or battery (e.g., lithium-ion battery), and battery pack as described above. Examples of the portable electronic devices include portable computers, power tools, toys, portable phones, camcorders, PDAs and hybrid-electric vehicles.
• the system includes a battery pack of the invention. Features of the battery pack are as described above.

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• 2009
  • 2009-04-15 US US12/386,266 patent/US20090297937A1/en not_active Abandoned
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