WO2012030639A2 - Très long cycle de vie des batteries au lithium-ion avec des matériaux cathodiques riches en lithium - Google Patents

Très long cycle de vie des batteries au lithium-ion avec des matériaux cathodiques riches en lithium Download PDF

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Publication number
WO2012030639A2
WO2012030639A2 PCT/US2011/049304 US2011049304W WO2012030639A2 WO 2012030639 A2 WO2012030639 A2 WO 2012030639A2 US 2011049304 W US2011049304 W US 2011049304W WO 2012030639 A2 WO2012030639 A2 WO 2012030639A2
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Prior art keywords
battery
voltage
cycle
capacity
lithium
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PCT/US2011/049304
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English (en)
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WO2012030639A3 (fr
Inventor
Shabab Amiruddin
Bing Li
Sujeet Kumar
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Envia Systems, Inc.
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Priority claimed from US13/213,756 external-priority patent/US8928286B2/en
Application filed by Envia Systems, Inc. filed Critical Envia Systems, Inc.
Priority to CN2011800500651A priority Critical patent/CN103168383A/zh
Priority to KR1020137008541A priority patent/KR20130108332A/ko
Priority to JP2013527139A priority patent/JP2013539594A/ja
Priority to EP11822392.4A priority patent/EP2612393A4/fr
Publication of WO2012030639A2 publication Critical patent/WO2012030639A2/fr
Publication of WO2012030639A3 publication Critical patent/WO2012030639A3/fr

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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
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/44—Methods for charging or discharging
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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

Definitions

  • the invention relates to lithium ion batteries with a high capacity lithium rich metal oxide cathode active material that are formed to stabilize cycling out to an enormous number of cycles at moderate capacity utilization.
  • the invention further relates to methods for cycling batteries at moderate capacities to obtain unprecedented moderately high capacity for a very large number of cycles.
  • Rechargeable lithium ion batteries also known as secondary lithium ion batteries are desirable as power sources for a wide range of applications. Their desirability stems from their relative high energy density. The capacities of secondary lithium ion batteries have been greatly improved with the development of high capacity lithium rich metal oxides for use as positive electrode active materials. With cycling, however, secondary lithium ion batteries generally have decreased performance with increased cycle number. For some important applications, such as vehicle application, it is desired that secondary lithium ion batteries be able to charge and recharge for many cycles without a great loss of performance.
  • the invention pertains to a lithium ion battery comprising a positive electrode comprising a lithium rich metal oxide composition, a negative electrode comprising a lithium intercalation/alloying composition and a non-aqueous electrolyte comprising lithium ions, and a separator between the negative electrode and the positive electrode.
  • the battery has been cycled through a formation cycle and wherein at the 500th cycle, the battery has a specific discharge capacity based on the mass of the positive electrode active composition of at least about 100 niAh/g at a discharge rate of C/3 from 4.25V to 2.0V that is at least about 90% of the 5th cycle specific discharge capacity and an average discharge voltage at a discharge rate of C/3 that is at least about 87.5% of the 5 th cycle average discharge voltage.
  • the invention pertains to a method for cycling a lithium ion battery having a positive electrode comprising a lithium rich metal oxide, the method comprising the step of cycling the battery, following an initial formation cycle, with a charge voltage from about 4V to about 4.35V at an average discharge rate from about C/5 to about 2C.
  • the capacity after 2000 cycles is at least about 80 percent of the capacity at the 5th cycle at the same average discharge rate and the average voltage after 2000 cycles is at least about 85 percent of the 5th cycle average voltage at the same average discharge rate.
  • the battery can have a specific discharge capacity at the 5th cycle of at least about 100 mAh/g.
  • the invention pertains to a method for cycling a lithium ion battery having a positive electrode comprising a lithium rich metal oxide, in which the method comprises the step of cycling the battery following an initial formation cycle with a charge voltage from about 3.8 to about 4.25 at an average rate from about C/5 to about 2C.
  • the capacity after 2000 cycles is at least about 80 percent of the capacity at the 5th cycle at the same average rate and the average voltage after 2000 cycles is at least about 85 percent of the 5th cycle average voltage at the same average rate.
  • the invention pertains to a method for cycling a lithium ion battery having a positive electrode comprising a lithium rich metal oxide, in which the method comprises, following an initial formation cycle, cycling the battery with a charge voltage from about 4.25 to about 4.375 at an average rate from about C/5 to about 2C, and in which the battery is discharged to a voltage of no more than about 2.9V at least once every 200 cycles.
  • the capacity after 2000 cycles is at least about 80 percent of the capacity at the 5th cycle at the same average rate
  • the average voltage after 2000 cycles is at least about 85 percent of the 5th cycle average voltage at the same average rate.
  • Fig. 1 is a schematic drawing of a battery structure separated from a container.
  • Fig. 2 is a schematic drawing of a pouch battery.
  • Fig.3 is a plot of voltage as a function of specific capacity for a discharge from 4.5V to 2V at a rate of C/3, which can be used to roughly estimate available capacity over a selected voltage window for cycling.
  • Fig. 15 is a graph containing plots of discharge capacity versus cycle number for an activated and a partially activated cell battery with a lithium foil negative electrode, both cycled between 4.24 V and 2.73 V at a charge rate of 1C and a discharge rate of 2C.
  • Fig. 16 is a graph containing plots of discharge capacity versus cycle number for an activated and partially activated battery, the activated battery cycled between 4.1 V and 3.15 V at charge and discharge rates of 0.75C and the partially activated battery cycled between 4.24 V and 2.73 V at a charge rate of 1C and a discharge rate of 2C.
  • Fig. 17 is a graph containing plots of average discharge voltage versus cycle number for an activated and a partially activated cell battery, both cycled between 4.24 V and 2.73 V at a charge rate of 1C and a discharge rate of 2C.
  • Fig. 18 is a graph containing plots of average discharge voltage versus cycle number for an activated and partially activated battery, the activated battery cycled between 4.1 V and 3.15 V at charge and discharge rates of 0.75C and the partially activated battery cycled between 4.24 V and 2.73 V at a charge rate of 1C and a discharge rate of 2C.
  • a relatively new class of lithium rich mixed metal manganese oxide compositions can exhibit very high capacity with cycling at a high charge voltage.
  • the lithium rich metal oxides of particular interest are believed to form a layered-layered multiple phase material upon synthesis. While these lithium rich metal oxides can exhibit high capacities over moderate levels of cycling, for some applications it is desirable to have very long cycling stability. It has been discovered that an understanding of an irreversible reaction of the lithium rich metal oxides during high voltage cycling can be exploited to obtain very stable long term cycling while accessing a significant fraction of the available capacity.
  • the batteries formed with the lithium rich metal oxides can be formed with charging to a voltage of at least about 90% state of charge (SOC), or generally about 4.45V, to activate the lithium rich materials and then cycled with a lower charge voltage, such as a voltage of no more than about 4.2V to stabilize the cycling while accessing a larger fraction of the capacity due to the activation of the active material.
  • SOC state of charge
  • the battery can be cycled with a charge voltage from about 4.225V to about 4.45V to gradually activate the lithium rich active material that makes a higher voltage phase available for cycling.
  • the battery can be charged in the first cycle to partially activate the lithium rich active material and then cycled to the same or different charge voltage within the voltage window, which may or may not further gradually activate a stable active phase of the material without forming metal oxide phases that degrade with cycling.
  • various variations on the activation and cycling can be used based on these concepts.
  • the activation of the positive electrode active material is believed to involve irreversible changes to one of the initial phases of the material.
  • the stability of the activated phase depends on the subsequent cycling of the battery.
  • Activation of the lithium rich material can be accomplished with an initial charge to an appropriate voltage, and a suitable formation protocol can be used. Partial activation can be accomplished through an initial charge to a voltage that is high enough to induce a partial phase change in one of the initial phases of the lithium rich material. The gradual activation is believed to involve small amounts of phase conversion at each cycle through the reaction of the initial phase to the irreversible product phase.
  • the resulting batteries can be cycled for a dramatically extended number of cycles with a capacity that is at least 80 % of an initial capacity at a reasonable rate of discharge.
  • batteries with good capacities and energy outputs can be formed with desired cycling for greater than a 1500 cycles, which are suitable for vehicle use. It has been found that the batteries can also be cycled well at relatively high rates for desired power output.
  • the stability of the positive electrode active material has been confirmed at long cycling based on an evaluation after cycling the battery for more than a thousand cycling and determining that only very low levels of Mn are found in the negative electrode, which indicates that only low amounts of manganese has dissolved from the positive electrode into the electrolyte after this large number of cycles.
  • Layered-layered lithium rich mixed metal oxides have been found that provide high capacity performance when cycled over a large voltage range.
  • the layered-layered lithium rich metal oxides can be used to construct batteries that have a combination of good cycling performance, high specific capacity, high overall capacity, relatively high average voltage and excellent rate capability.
  • the resulting lithium ion batteries can be used as an improved power source, particularly for high energy applications.
  • the batteries comprise a large cost factor, and for product efficiency, the batteries used in the vehicle are desired to last a long time, generally several thousand cycles without excessive performance decay.
  • the positive electrode materials can exhibit a relatively high average voltage over a discharge cycle so that the batteries can have high energy output along with a high specific capacity.
  • the active materials can have an appropriate coating to provide for an improvement in cycling as well as potentially a reduction in irreversible capacity loss and an increase in specific capacity. While promising results have been presented for these material, as described herein significant improvements in performance are described for these materials such that the materials can be very desirable for an even broader range of commercial applications.
  • the batteries described herein are lithium-based batteries in which a non-aqueous electrolyte solution comprises lithium ions.
  • a non-aqueous electrolyte solution comprises lithium ions.
  • oxidation takes place in the cathode (positive electrode) where lithium ions are extracted and electrons are released.
  • reduction takes place in the cathode where lithium ions are inserted and electrons are consumed.
  • the batteries are formed with lithium ions in the positive electrode material such that an initial charge of the battery transfers a significant fraction of the lithium from the positive electrode material to the negative electrode material to prepare the battery for discharge. Unless indicated otherwise, performance values referenced herein are at room temperature.
  • the intercalation and release of lithium ions from the lattice induces changes in the crystalline lattice of the electroactive material.
  • the capacity of the material does not change significantly with cycling.
  • the capacity of the active materials is observed to decrease with cycling to varying degrees.
  • the performance of the battery falls below acceptable values, and the battery is replaced.
  • the irreversible capacity loss is the difference between the charge capacity of the new battery and the first discharge capacity.
  • the irreversible capacity loss results in a corresponding decrease in the capacity, energy and power for the cell.
  • the irreversible capacity loss generally can be attributed to changes during the initial charge-discharge cycle of the battery materials, which, in general, can occur at both the cathode and the anode.
  • the word "element” is used herein in its conventional way as referring to a member of the periodic table in which the element has the appropriate oxidation state if the element is in a composition and in which the element is in its elemental form, M°, only when stated to be in an elemental form. Therefore, a metal element generally is only in a metallic state in its elemental form or a corresponding alloy of the metal's elemental form. In other words, a metal oxide or other metal composition, other than metal alloys, generally is not metallic.
  • the lithium ion batteries can use a positive electrode active material that is lithium rich relative to a reference homogenous electroactive lithium metal oxide composition.
  • the class of lithium rich positive electrode active materials of interest can be approximately represented with a formula:
  • Lii +b Ni a MnpCo Y A 5 0 2-z F z (1) where b ranges from about 0.01 to about 0.3, a ranges from 0 to about 0.4, ⁇ range from about 0.2 to about 0.65, ⁇ ranges from about 0 to about 0.46, ⁇ ranges from about 0.001 to about 0.15, and z ranges from 0 to about 0.2 with the proviso that both a and ⁇ are not zero, and where A is a metal different from Ni, Mn and Co or a combination thereof.
  • Element A and F fluorine are optional cation and anion dopants, respectively.
  • Elements A can be, for example, Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, or combinations thereof.
  • a fluorine dopant in lithium rich metal oxides to achieve improved performance is described in published U.S. patent application 2010/0086854 to Kumar et al, entitled “Fluorine Doped Lithium Rich Metal Oxide Positive Electrode Battery Materials With High Specific Capacity and Corresponding Batteries,” incorporated herein by reference.
  • a layered Li 2 M0 3 material may be structurally integrated with either a layered LiM'0 2 component, in which a reference structure has M and M' being manganese, although particular compositions of interest have a portion of the manganese cations substituted with other transition metal cations with appropriate oxidation states.
  • the positive electrode material can be represented in two component notation as x Li 2 M0 3 - (l-x)LiM'0 2 where M' is one or more metal cations with an average valence of +3 with at least one cation being a manganese cation or a nickel cation, and where M is one or more metal cations with an average valence of +4.
  • M can be considered to be Mn.
  • the general class of compositions are described further, for example, in U.S. patent 6,680,143 (the ⁇ 43 patent) to Thackeray et al, entitled “Lithium Metal Oxide Electrodes for Lithium Cells and Batteries,” and published U.S. patent application 2011/0052981 A to Lopez et al, entitled “Layer-Layer Lithium Rich Complex Metal Oxides With High Specific Capacity and Excellent Cycling,” both of which are incorporated herein by reference (the '981 application).
  • the lithium manganese oxide (Li 2 Mn0 3 ) component of the compositions can undergo a reaction to release molecular oxygen with an associated release of 2 Li ions as indicated in equation (2):
  • the (Mn0 ) composition Upon discharge, the (Mn0 ) composition takes up a single lithium ion and a single electron to form LiMn0 2 so that there is an overall significant decrease in capacity due to the irreversible reaction of the material during the initial charge.
  • the product composition is written as (Mn0 2 ) because it is not completely clear what this material is. While Eq. (2) is balanced if (Mn0 2 ) is actually Mn0 2 , it is not clear if this is the precise reaction, although oxygen release is observed corresponding to a reduction of the metal. As discussed below, evidence suggests that the reaction schematically represented in Eq. (2) takes place efficiently at voltages above roughly 4.4 volts.
  • the first cycle can be referred to as a formation cycle that involves notable irreversible changes to the battery material.
  • a desirable multiple step formation protocol has been developed, as described in copending U.S. patent application 12/732,520 (hereinafter the '520 application) to Amiruddin et al., entitled “High Voltage Battery Foraiation Protocols and Control of Charging and Discharging for Desirable Long Term Cycling Performance,” incorporated herein by reference.
  • the lithium rich metal oxides have been found to undergo additional structural changes as a result of cycling at high voltages. In particular, when charged to high voltages, the materials undergo continuing, although more gradual, irreversible changes to the structure.
  • the voltage can be used to reference the particular charge state of the battery.
  • SOC state of charge
  • the SOC can in some sense be less precise since there can be flexibility in setting the reference capacity.
  • the upper limit on the state of charge is the charge needed to fully extract the lithium of the pristine positive electrode active material upon initial assembly f the battery, which may require roughly 5V.
  • the fully extractable capacity of the battery is less than the maximum at later cycles of battery use.
  • the material can undergo an initial activation charge to a voltage above about 4.45V.
  • the activation charge then extracts lithium from a high voltage phase (believed to be essentially Li 2 Mn0 3 ) that then undergoes irreversible chemical changes that activate one of the phases of the initial material to form the material denoted as (Mn0 2 ).
  • this activated phase (Mn0 2 ) can be cycled stably with respect to capacity and average voltage over a voltage range that does not extend to high voltages.
  • the initial phase formed during the activation cycle can stably cycle if only a relatively smaller portion of the lithium is extracted during the subsequent charge steps.
  • the capacity as well as the average voltage can remarkably increases somewhat over the initial cycling over a moderate number of cycles of the battery, although at lower values of the charge voltage over cycling, the capacity is essentially flat. With appropriate selection of charge voltages, the capacity and average voltage plateau, and the capacity and average voltage can then be essentially stable out to many thousands of cycles before the capacity drops to 80% of the initial capacity. This is amazing cycling performance that is achieved with good values of specific capacities.
  • the batteries in the examples involve graphitic carbon active materials in the negative electrodes.
  • the improved performance of the positive electrode active materials through the manipulation and appropriate stabilization of the materials can be extended to other negative electrode active materials that intercalate or alloy with lithium.
  • the electrodes can be assembled into appropriate battery formats.
  • Lithium ion batteries generally comprise a positive electrode, a negative electrode, a separator between the negative electrode and the positive electrode and an electrolyte comprising lithium ions.
  • the electrodes are generally associated with metal current collectors.
  • Lithium ion batteries refer to batteries in which the negative electrode active material is a material that takes up lithium during charging and releases lithium during discharging. Referring to Fig. 1, a battery 100 is shown schematically having a negative electrode 102, a positive electrode 104 and a separator 106 between negative electrode 102 and positive electrode 104.
  • a battery can comprise multiple positive electrodes and multiple negative electrodes, such as in a stack, with appropriately placed separators.
  • a battery generally comprises current collectors 108, 110 associated respectively with negative electrode 102 and positive electrode 104.
  • the basic battery structures and compositions are described in this section.
  • Suitable negative electrode (anode) lithium intercalation/ alloying compositions can include, for example, graphite, synthetic graphite, coke, fullerenes, other graphitic carbons, niobium pentoxide, tin alloys, silicon, titanium oxide, tin oxide, and lithium titanium oxide, such as Li x Ti0 2 , 0.5 ⁇ x ⁇ l or Lii +x Ti 2-x 0 4 , 0 ⁇ x ⁇ 1/3.
  • the graphitic carbon and metal oxide negative electrode compositions take up and release lithium through an intercalation or similar process.
  • Silicon and tin alloys form alloys with the lithium metal to take up lithium and release lithium from the alloy to correspondingly release lithium. Additional negative electrode materials are described in published U.S. patent applications 2010/0119942 to Kumar, entitled “Composite Compositions, Negative Electrodes with Composite Compositions and Corresponding Batteries,” and 2009/0305131 to Kumar et al., entitled “High Energy Lithium Ion Batteries with Particular Negative Electrode Compositions,” both of which are incorporated herein by reference. Desirable elemental silicon based negative electrode active materials are described in published U.S.
  • the positive electrode active compositions and negative electrode active compositions generally are powder compositions that are held together in the corresponding electrode with a polymer binder.
  • the binder provides ionic conductivity to the active particles when in contact with the electrolyte.
  • Suitable polymer binders include, for example, polyvinylidine fluoride, polyethylene oxide, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylates, rubbers, e.g. ethylene-propylene-diene monomer (EPDM) rubber or styrene butadiene rubber (SBR), copolymers thereof, or mixtures thereof.
  • the particle loading in the binder can be large, such as greater than about 80 weight percent.
  • the powders can be blended with the polymer in a suitable liquid, such as a solvent for the polymer. The resulting paste can be pressed into the electrode structure.
  • the positive electrode composition generally also comprises an electrically conductive powder distinct from the electroactive composition.
  • Suitable supplemental electrically conductive powders include, for example, graphite, carbon black, metal powders, such as silver powders, metal fibers, such as stainless steel fibers, and the like, and combinations thereof.
  • a positive electrode can comprise from about 1 weight percent to about 25 weight percent, and in further embodiments from about 2 weight percent to about 15 weight percent distinct electrically conductive powder.
  • the electrode generally is associated with an electrically conductive current collector to facilitate the flow of electrons between the electrode and an exterior circuit.
  • the current collector can comprise metal, such as a metal foil or a metal grid.
  • the current collector can be formed from nickel, aluminum, stainless steel, copper or the like.
  • the electrode material can be cast as a thin film onto the current collector.
  • the electrode material with the current collector can then be dried, for example in an oven, to remove solvent from the electrode.
  • the dried electrode material in contact with the current collector foil or other structure can be subjected to a pressure, such as, from about 2 to about 10 kg/cm 2 (kilograms per square centimeter).
  • the separator is located between the positive electrode and the negative electrode.
  • the separator is electrically insulating while providing for at least selected ion conduction between the two electrodes.
  • a variety of materials can be used as separators.
  • Commercial separator materials are generally formed from polymers, such as polyethylene and/or polypropylene that are porous sheets that provide for ionic conduction.
  • Commercial polymer separators include, for example, the Celgard ® line of separator material from Hoechst Celanese, Charlotte, N.C.
  • ceramic-polymer composite materials have been developed for separator applications. These composite separators can be stable at higher temperatures, and the composite materials can significantly reduce the fire risk.
  • the polymer-ceramic composites for separator materials are described further in published U.S.
  • Electrolytes for lithium ion batteries can comprise one or more selected lithium salts.
  • Appropriate lithium salts generally have inert anions.
  • Suitable lithium salts include, for example, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis(trifluoromethyl sulfonyl imide), lithium trifluoromethane sulfonate, lithium tris(trifluoromethyl sulfonyl) methide, lithium tetrafluoroborate, lithium perchlorate, lithium tetrachloroalummate, lithium chloride, lithium difluoro oxalato borate, lithium bis-oxalato borate, and combinations thereof.
  • the electrolyte comprises a 1 M concentration of the lithium salts, although greater or lesser concentrations can be used.
  • a non-aqueous liquid is generally used to dissolve the lithium salt(s).
  • the solvent generally does not dissolve the electroactive materials.
  • Appropriate solvents include, for example, propylene carbonate, dimethyl carbonate, diethyl carbonate, 2-methyl tetrahydrofuran, dioxolane, tetrahydrofuran, methyl ethyl carbonate, ⁇ - butyrolactone, dimethyl sulfoxide, acetonitrile, formamide, dimethyl formamide, triglyme (tri(ethylene glycol) dimethyl ether), diglyme (diethylene glycol dimethyl ether), DME (glyme or 1,2-dimethyloxyethane or ethylene glycol dimethyl ether), nitromethane and mixtures thereof.
  • the electrodes described herein can be incorporated into various commercial battery designs.
  • the cathode compositions can be used for prismatic shaped batteries, wound cylindrical batteries, coin batteries or other reasonable battery shapes.
  • the batteries can comprise a single cathode structure or a plurality of cathode structures assembled in parallel and/or series electrical connection(s).
  • the positive electrode and negative electrode can be stacked with the separator between them, and the resulting stacked structure can be placed into a cylindrical or prismatic configuration to form the battery structure.
  • Appropriate electrically conductive tabs can be welded or the like to the current collectors, and the resulting jellyroll or stack structure can be placed into a metal canister or polymer package, with the negative tab and positive tab welded to appropriate external contacts.
  • Electrolyte is added to the canister, and the canister is sealed to complete the battery.
  • Some presently used rechargeable commercial batteries include, for example, the cylindrical 18650 batteries (18 mm in diameter and 65 mm long) and 26700 batteries (26 mm in diameter and 70 mm long), although other battery sizes can be used.
  • a schematic diagram of a pouch battery is shown in Fig. 2.
  • a pouch cell battery 120 is shown schematically having a negative electrode 122, a positive electrode 124 and a separator 126 between negative electrode 122 and positive electrode 124.
  • a pouch battery can comprise multiple positive electrodes and multiple negative electrodes, such as in a stack, with appropriately placed separators. Electrolyte in contact with the electrodes provides ionic conductivity through the separator between electrodes of opposite polarity.
  • a battery generally comprises current collectors 128, 130 associated respectively with negative electrode 122 and positive electrode 124.
  • the stack of electrodes and separators can be enclosed in a laminated film casing 132.
  • pouch batteries can be constructed as described in published U.S.
  • the positive electrode active materials of particular interest comprise lithium rich compositions that generally are believed to form a layered composite crystal structure.
  • the lithium metal oxide compositions specifically comprise Ni, Co and Mn ions with an optional metal dopant.
  • a lithium rich composition can be referenced relative to a composition LiM0 2 , where M is one or more metals with an average oxidation state of +3.
  • the lithium rich compositions can be represented approximately with a formula Lii +x Mi -y 02, where M represents one or more non-lithium metals, x>0, and y is related to x based on the average valence of the metals. When x is greater than 0, the composition is lithium rich relative to the reference LiM0 2 composition.
  • x is from about 0.01 to about 0.33, and y is from about x-0.2 to about x+0.2 with the proviso that y>0. In the layered-layered composite compositions, x is approximately equal to y.
  • the additional lithium in the lithium rich compositions is accessed at higher voltages such that the initial charge takes place at a relatively higher voltage to access the additional capacity.
  • the material can undergo irreversible changes during an initial high voltage charge step, such that the material that cycles subsequent to the initial charge is not the same material that reacts at high voltage in the initial material.
  • Lithium rich positive electrode active materials of particular interest can be represented approximately by a formula Lii +b Ni a MnpCo y A 5 0 2-z F z , where b ranges from about 0.01 to about 0.3, a ranges from about 0 to about 0.4, ⁇ range from about 0.2 to about 0.65, ⁇ ranges from 0 to about 0.46, ⁇ ranges from 0 to about 0.15 and z ranges from 0 to about 0.2 with the proviso that both a and ⁇ are not zero, and where A is Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, Li or combinations thereof.
  • the positive electrode material with the formula above can be represented approximately in two component notation as x L ⁇ MO ⁇ - (1- x)LiM0 2 where 0 ⁇ x ⁇ l , M is one or more metal cations with an average valence of +3 within some embodiments at least one cation being a Mn ion or a Ni ion and where M' is one or more metal cations, such as Mn +4 , with an average valence of +4.
  • Mn ion or a Ni ion within some embodiments at least one cation being a Mn ion or a Ni ion and where M' is one or more metal cations, such as Mn +4 , with an average valence of +4.
  • the multi-phased material is believed to have an integrated layered-layered composite crystal structure with the excess lithium supporting the stability of the composite material.
  • a Li 2 Mn0 3 material may be structurally integrated with a layered LiM0 2 component where M represents selected non-lithium metal elements or combinations thereof.
  • the positive electrode active materials of particular interest can be represented approximately in two component notation as x Li 2 Mn03 ⁇ (1-x) LiM0 2 , where M is one or more metal elements with an average valence of +3 and with one of the metal elements being Mn and with another metal element being Ni and/or Co.
  • M is one or more metal elements with an average valence of +3 and with one of the metal elements being Mn and with another metal element being Ni and/or Co.
  • 0 ⁇ x ⁇ l but in some embodiments 0.03 ⁇ x ⁇ 0.55, in further embodiments 0.075 ⁇ x ⁇ 0.50, in additional embodiments 0.1 ⁇ x ⁇ 0.45, and in other embodiments 0.15 ⁇ x ⁇ 0.425.
  • M can be a combination of nickel, cobalt and manganese, which, for example, can be in oxidation states Ni +2 , Co +3 , and Mn +4 within the initial lithium manganese oxides.
  • the overall formula for these compositions can be written as ; Li2 ( i+x)/(2+x ) Mn 2x/(2+X) M (2-2x)/ ( 2+X )0 2 .
  • the total- amount of manganese has contributions from both constituents listed in the two component notation. Thus, in some sense the compositions are manganese rich.
  • M can be written as Ni u Mn v Co w A y .
  • y 0
  • M includes Ni, Co, Mn, and optionally A the composition can be written alternatively in two component notation and single component notation as the following.
  • y 0, the average valence of Ni, Co and Mn is +3, and if u ⁇ v, then these elements can have valences of approximately Ni +2 , Co +3 and Mn +4 to achieve the average valence.
  • all of the elements go to a +4 valence.
  • a balance of Ni and Mn can provide for Mn to remain in a +4 valence as the material is cycled in the battery.
  • the composition can be varied around the formula for the material with balanced amounts of Mn and Ni in the LiM0 2 phase of the material such that the approximate formula for the material is x Li 2 Mn0 3 ⁇ (1-x) Li Ni u+A Mn u .
  • a Co w A y 02 where the absolute value of ⁇ generally is no more than about 0.3 (i.e., -0.3 ⁇ 0.3), in additional embodiments no more than about 0.2 (-0.2 ⁇ 0.2) in some embodiments no more than about 0.175 (-0.175 ⁇ 0.175) and in further embodiments no more than about 0.15 (- 0.15 ⁇ 0.15).
  • desirable ranges of parameters are in some embodiments 0 ⁇ w ⁇ l, 0 ⁇ u ⁇ 0.5, 0 ⁇ y ⁇ 0.1 (with the proviso that both ⁇ + ⁇ and w are not zero), in further embodiments, 0.1 ⁇ w ⁇ 0.6, 0.1 ⁇ u ⁇ 0.45, 0 ⁇ y ⁇ 0.075, and in additional embodiments 0.2 ⁇ w ⁇ 0.5, 0.2 ⁇ u ⁇ 0.4, 0 ⁇ y ⁇ 0.05.
  • 0.1 ⁇ w ⁇ 0.6, 0.1 ⁇ u ⁇ 0.45, 0 ⁇ y ⁇ 0.075 in additional embodiments 0.2 ⁇ w ⁇ 0.5, 0.2 ⁇ u ⁇ 0.4, 0 ⁇ y ⁇ 0.05.
  • various processes can be performed for synthesizing the desired lithium rich metal oxide materials described herein having nickel, cobalt, manganese and additional optional metal cations in the composition and exhibiting the high specific capacity performance.
  • sol gel, co-precipitation, solid state reactions and vapor phase flow reactions can be used to synthesize the desired materials.
  • the materials can exhibit a good tap density which leads to high overall capacity of the material in fixed volume applications.
  • lithium rich metal oxide compositions were used in coated forms to generate the results in the Examples below.
  • metal salts are dissolved into an aqueous solvent, such as purified water, with a desired molar ratio.
  • Suitable metal salts include, for example, metal acetates, metal sulfates, metal nitrates, and combination thereof.
  • the concentration of the solution is generally selected between 1M and 3M.
  • the relative molar quantities of metal salts can be selected based on the desired formula for the product materials.
  • the dopant elements can be introduced along with the other metal salts at the appropriate molar quantity such that the dopant is incorporated into the precipitated material.
  • the pH of the solution can then be adjusted, such as with the addition of Na 2 C0 3 and/or ammonium hydroxide, to precipitate a metal hydroxide or carbonate with the desired amounts of metal elements.
  • the pH can be adjusted to a value between about 6.0 to about 12.0.
  • the solution can be heated and stirred to facilitate the precipitation of the hydroxide or carbonate.
  • the precipitated metal hydroxide or carbonate can then be separated from the solution, washed and dried to form a powder prior to further processing. For example, drying can be performed in an oven at about 110°C for about 4 to about 12 hours.
  • the collected metal hydroxide or carbonate powder can then be subjected to a heat treatment to convert the hydroxide or carbonate composition to the corresponding oxide composition with the elimination of water or carbon dioxide.
  • the heat treatment can be performed in an oven, furnace or the like.
  • the heat treatment can be performed in an inert atmosphere or an atmosphere with oxygen present.
  • the material can be heated to a temperature of at least about 350°C and in some embodiments from about 400°C to about 800°C to convert the hydroxide or carbonate to an oxide.
  • the heat treatment generally can be performed for at least about 15 minutes, in further embodiments from about 30 minutes to 24 hours or longer, and in additional embodiments from about 45 minutes to about 15 hours.
  • a further heat treatment can be performed at a second higher temperature to improve the crystallinity of the product material.
  • This calcination step for forming the crystalline product generally is performed at temperatures of at least about 650°C, and in some embodiments from about 700°C to about 1200°C, and in further embodiments from about 700°C to about 1100°C.
  • the calcination step to improve the structural properties of the powder generally can be performed for at least about 15 minutes, in further embodiments from about 20 minutes to about 30 hours or longer, and in other embodiments from about 1 hour to about 36 hours.
  • the heating steps can be combined, if desired, with appropriate ramping of the temperature to yield desired materials.
  • the lithium element can be incorporated into the material at one or more selected steps in the process.
  • a lithium salt can be incorporated into the solution prior to or upon performing the precipitation step through the addition of a hydrated lithium salt.
  • the lithium species is incorporated into the hydroxide or carbonate material in the same way as the other metals.
  • the lithium element can be incorporated into the material in a solid state reaction without adversely affecting the resulting properties of the product composition.
  • an appropriate amount of lithium source generally as a powder, such as LiOH-H 2 0, LiOH, Li 2 C0 3 , or a combination thereof, can be mixed with the precipitated metal carbonate or metal hydroxide. The powder mixture is then advanced through the heating step(s) to form the oxide and then the crystalline final product material.
  • Inorganic coatings such as metal halide coatings and metal oxide coatings, on lithium rich positive electrode active materials have been found to significantly improve the performance of lithium ion batteries, although the coatings are believed to be inert with respect to battery cycling.
  • the cycling properties of the batteries formed from coated lithium metal oxides have been found to significantly improve from the uncoated material.
  • the specific capacity of the batteries also shows desirable properties with the coatings, and the irreversible capacity loss of the first cycle of the battery can be reduced in some embodiments.
  • a coating with a combination of metal and/or metalloid elements can be used for the coating compositions.
  • Suitable metals and metalloid elements for the fluoride coatings include, for example, Al, Bi, Ga, Ge, In, Mg, Pb, Si, Sn, Ti, Tl, Zn, Zr and combinations thereof.
  • Aluminum fluoride can be a desirable coating material since it has a reasonable cost and is considered environmentally benign.
  • Metal fluoride coatings are described generally in published PCT application WO 2006/109930A to Sun et al., entitled "Cathode Active Materials Coated with Fluorine Compound for Lithium Secondary Batteries and Method for Preparing the Same," incorporated herein by reference.
  • metal/metalloid fluoride coatings can significantly improve the performance of lithium rich layered compositions for lithium ion secondary batteries. See, for example, the '853 application and the '332 application cited above, as well as published U.S. patent application 2011/0111298 (the '298 application) to Lopez et al., entitled “Coated Positive Electrode Materials For Lithium Ion Batteries,” incorporated herein by reference. Desirable performance results for non-fluoride metal halide coatings have been described in copending U.S.
  • the coating improves the specific capacity of the batteries even though the coating itself is not electrochemically active.
  • the coatings also influence other properties of the active material, such as the average voltage, thermal stability and impedance.
  • the selection of the coating properties can incorporate additional factors related to the overall range of properties of the material.
  • the coatings can have an average thickness of no more than 25 nm, in some embodiments from about 0.5 nm to about 20 nm, in other embodiments from about 1 nm to about 12 nm, in further embodiments from 1.25 nm to about 10 nm and in additional embodiments from about 1.5 nm to about 8 nm.
  • additional ranges of coating material within the explicit ranges above are contemplated and are within the present disclosure.
  • the amount of coating materials to achieve desired improvement in battery performance can be related to the particle size and surface area of the uncoated material. Further discussion of the effects of coating thickness on the performance properties for coated lithium rich lithium metal oxides is found in the '298 application cited above.
  • a metal fluoride coating can be deposited using a solution based precipitation approach.
  • a powder of the positive electrode material can be mixed in a suitable solvent, such as an aqueous solvent.
  • a soluble composition of the desired metal/metalloid can be dissolved in the solvent.
  • NH 4 F can be gradually added to the dispersion/solution to precipitate the metal fluoride.
  • the total amount of coating reactants can be selected to form the desired thickness of coating, and the ratio of coating reactants can be based on the stoichiometry of the coating material.
  • the coating mixture can be heated during the coating process to reasonable temperatures, such as in the range from about 60°C to about 100°C for aqueous solutions from about 20 minutes to about 48 hours, to facilitate the coating process.
  • the material After removing the coated electroactive material from the solution, the material can be dried and heated to temperatures generally from about 250°C to about 600°C for about 20 minutes to about 48 hours to complete the formation of the coated material.
  • the heating can be performed under a nitrogen atmosphere or other substantially oxygen free atmosphere.
  • An oxide coating is generally formed through the deposition of a precursor coating onto the powder of active material.
  • the precursor coating is then heated to form the metal oxide coating.
  • Suitable precursor coating can comprise corresponding metal hydroxides, metal carbonates or metal nitrates.
  • the metal hydroxides and metal carbonate precursor coating can be deposited through a precipitation process since the addition of ammonium hydroxide and/or ammonium carbonate can be used to precipitate the corresponding precursor coatings.
  • a metal nitrate precursor coating can be deposited through the mixing of the active cathode powder with a metal nitrate solution and then evaporating the solution to dryness to form the metal nitrate precursor coating.
  • the powder with a precursor coating can be heated to decompose the coating for the formation of the corresponding metal oxide coating.
  • a metal hydroxide or metal carbonate precursor coating can be heated to a temperature from about 300°C to about 800°C for generally from about 1 hr to about 20 lii-s.
  • a metal nitrate precursor coating generally can be heated to decompose the coating at a temperature from about 250°C to about 550°C for at least about 30 minutes.
  • a person of ordinary skill in the art can adjust these processing conditions based on the disclosure herein for a specific precursor coating composition. Cycling of Batteries With Activation
  • an initial charge of the battery to a voltage of about 4.45V or greater is found to activate a substantial fraction of the high voltage phase of the active material and to correspondingly drive irreversible changes to the positive electrode active material. If it is desired to essentially fully activate the material, the battery can be initially charged to about 4.6V or greater voltage, to limit the amount of additional gradual activation over the first several cycles of the battery. Thus, generally full activation can be accomplished with a charge to a voltage of at least about 4.45V, in other embodiments over a voltage in the range of about 4.45V to about 5.0V, and in further embodiments from about 4.475 to about 4.8V.
  • additional voltage ranges within the explicit ranges above are contemplated and are within the present disclosure.
  • the initially formed active material which is denoted above as (Mn0 2 )
  • cycles with a relatively high average voltage and specific capacity cycles with a relatively high average voltage and specific capacity.
  • further cycling of the battery can result in additional structural changes to the active material that can gradually reduce the battery capacity as well as the average voltage. It has been discovered that lowering the charge voltage to a value of no more than about 4.25V during cycling of the activated battery can result in a capture of a significant fraction of the discharge capacity while dramatically reducing further degradation of capacity with cycling while also stabilizing the average voltage of the material.
  • the charge voltage can be selected to be no more than about 4.25 V, in some embodiments from about 3.8V to about 4.25V, in further embodiments from about 3.9V to about 4.24V, and in additional embodiments from about 4.0V to about 4.23V.
  • additional voltage ranges within the explicit ranges above are contemplated and are within the present disclosure.
  • the materials are observed to undergo at least partially reversible losses of capacity if the discharge voltage during cycling is no less than about 2.9V.
  • the charge voltage can be in the range from about 4.25V to about 4.35V, in other embodiment from about 4.25V to about 4.34V and in additional embodiments from abut 4.25V to about 4.34V.
  • a decision can be made to recharge the battery before the battery is discharged below a certain voltage. The battery can then be managed to ensure at least occasional discharge below a certain voltage, as described further below.
  • the at least occasional discharge voltage can be no more than about 2.8V, in other embodiments no more than about 2.75V and in additional embodiments from about 1.5V to abut 2.6V.
  • additional ranges of charge voltages and discharge voltages within the explicit ranges above are contemplated and are within the present disclosure.
  • the reversible changes to the active material observed at an intermediate charge voltage can be recovered in significant part through subsequent discharge to a lower voltage.
  • Fig. 3 For an activated battery, plot of the voltage as a function of discharge capacity is shown in Fig. 3 for a discharge at a rate of C/3.
  • battery capacity can be delivered over a wide voltage range following activation of the battery.
  • the battery had a specific discharge capacity of about 230 mAli/g when discharged from about 4.5 V to about 2.0 V.
  • the plot is relatively linear with an approximately constant slope over most of the capacity range, although the plot turns downward below about 2.5 V.
  • the plot in Fig. 3 can provide some rough guidance with respect to the capacity available over a particular voltage range. For example, if a cycling voltage window is selected that discharges the battery from 4.0 V to about 3.0 V, as indicated by the vertical lines in Fig. 3, the battery would have a discharge capacity of about 124 mAh/g.
  • a two step formation cycle can be advantageous for batteries having a lithium rich active material that is charged to a high voltage during the formation cycle.
  • the battery can be first charged to a lower voltage of no more than about 4.3V, then letting the battery rest in an open voltage format before charging the battery to a second voltage of at least about 4.35 V.
  • This improved formation protocol is described further in the '520 application cited above.
  • the two step formation protocol can schematically involve the reaction of a Li 2 Mn0 3 phase of the material to form (Mn0 2 ) with the release of molecular oxygen, which is observed in the second charge step.
  • the specific capacity of the battery is less if the charge voltage is lowered, although the cycling stability can be greater.
  • the cycling stability generally can also depend slightly on the particular stoichiometry of the positive electrode active material and on the charge and discharge rates, although the effects on cycling stability of the charge and discharge rate are observed generally to be small over rates from about C/5 to about 2 C.
  • the capacity and average voltage are found to exhibit outstanding stability with cycling with moderately high capacities.
  • design targets of maintenance of 80% of initial capacity for at least 2000 cycles can be achieved with a fixed charge voltage.
  • the battery management system can be programmed to necessarily discharge the battery to a target low value according to a prescribed protocol. The discharge can be performed, for example, with a controlled discharge shunt to dissipate the discharged energy in a controlled manner.
  • the battery management system can be have a protocol that discharges the battery to the target low voltage at least one cycle of every 200 cycles, in some embodiments at least one cycle every 150 cycles, in further embodiments at least one cycle every 125 cycles, and in other embodiments at least one cycle every 100 cycles.
  • a person or ordinary skill in the art will recognize that additional ranges of period for discharging the battery within the specific ranges above are contemplated and are within the present disclosure. Further information on battery management systems to accomplish this form of battery management are described in the '520 application.
  • the cycling advantages can be directly exploited in commercial applications in which a user may select the discharge voltage cutoff based on their own usage behavior and their personal choice.
  • a battery pack control system has been described that at least occasionally ensures that the discharge voltage is selected to be sufficiently low to result in an increase in the discharge capacity. In either case, the cycling can be selected to achieve a relatively high capacity with excellent cycling stability.
  • the high voltage phase can be partially activated during an initial charge and/or gradually activated during cycling to achieve unprecedented cycling stability with moderately high discharge capacities.
  • Control of the activation can be achieved through charging of the battery to values generally between about 4.225V and about 4.45V. Within this range, the voltage can be raised to achieve greater activation of the high voltage phase and lowered to reduce the activation of the high voltage phase.
  • an initially greater charge voltage can be used to initially partially activate the active material.
  • the charge voltage may or may not be selected to further gradually activate the active material during cycling.
  • the initial charge voltage may or may not be the same as the charge voltage during subsequent cycling and, the voltage window during cycling can be changed for specific cycles or for subsequent cycling to achieve desired discharge capacities.
  • discharge capacity fade to 80% of the initial capacity can be extended out to thousands of cycles while maintaining the average voltage with little decay.
  • the partial activation of a high voltage phase of the lithium rich positive electrode active material can take place if the initial charge voltage is between 4.225V and 4.45V, in further embodiments from about 4.24V to about 4.4V and in additional embodiments from about 4.25V to about 4.375V.
  • the partial activation of the high voltage active phase provides an increase of the specific discharge capacity due to the activation of the material to provide an appropriate cycling phase. If the battery is then cycled over a suitable voltage window, the positive electrode active material can be very stable for subsequent cycling. In particular, if the battery is cycled with a low enough charge voltage, the battery discharge capacity and average voltage can be very stable while achieving moderate values of specific discharge capacity.
  • the charge voltage may or may not be reduced after the first cycle, which can result in the further stabilization of the cycling. If the active material is sufficiently activated during the first charge, i.e., formation step, then a subsequent charge voltage can be selected that provides little or no further activation of the high voltage phase of the active material during cycling. At these voltages, the partially activated positive electrode active material at most only very slowly undergoes further phase changes since the material can cycle a large number of cycles without significant loss of discharge capacity or average voltage.
  • the charge voltage during cycling can be reduced somewhat relative to the initial charge voltage, but the charge voltage during cycling can still gradually activate the high voltage phase of the positive electrode active material during cycling.
  • the gradual activation can correspondingly gradually increase capacity with cycling, which can compensate for some fade or can actually result in significantly increasing capacity over a significant number of cycles.
  • the charge voltage can be adjusted to achieve a desired degree of gradual activation.
  • the voltages for gradual activation can be lower than voltages that correspondingly result in significant degradation of the performance through the destabilization of the activated material.
  • the activated capacity of the material can be maintained over a very large number of cycles with gradual activation.
  • the battery can be cycled with a charge voltage from about 4.05V to about 4.35V, in further embodiment from about 4.075V about 4.325V and in additional embodiments from about 4.1V to about 4.3V.
  • a charge voltage from about 4.05V to about 4.35V, in further embodiment from about 4.075V about 4.325V and in additional embodiments from about 4.1V to about 4.3V.
  • a significant advantage of the partial and/or gradual activation procedures is that the release of oxygen during the formation cycle is significantly reduced.
  • the release of oxygen during the formation cycle can introduce additional processing steps and complication the completion of a commercial battery.
  • production costs can be reduced.
  • the performance of the battery can be extended for both discharge capacity and average voltage out to thousands of cycles before there is a drop of 80% relative to initial values.
  • the discharge cutoff may be controlled by a user at varying voltage values, which can be based on extent use and selective choices by the user.
  • the cycling discharge capacity can be evaluated based on the number of cycle until the capacity reaches about 80% of the initial cycling discharge capacity at the same discharge rate.
  • batteries can be cycled to roughly 5000 cycles or more based on reasonable extrapolations before reaching the 80% capacity decrease at reasonable rates and capacities as well as appropriately stable average discharge voltages.
  • the batteries can be cycled for roughly 25,000 cycles based on reasonable extrapolations before reaching the 80%> drop in capacity at reasonable rates and capacities as well as appropriately stable average discharge voltages.
  • the charge voltage can be increased at a larger number of cycles to boost the capacity to compensate for some capacity fade.
  • the increase in charge voltage can have relatively small increments in value, such as from about 0.01V to about 0.25V and in further embodiments from about 0.025V to about 0.15V, which can be incremented, for example, after 500 cycle, 1000 cycles, 2000 cycles or 2500 cycles, and can be performed once or repeated after sufficient cycling.
  • a person of ordinary skill in the art will recognize that additional ranges within the explicit ranges related to incremental voltage increases above are contemplated and are within the present disclosure.
  • an activated battery can have a specific discharge capacity, relative to the weight of the positive electrode active material, of at least about 100 mAh/g, in other embodiments at least about 110 mAh g and in further embodiments at least about 115 mAh/g when discharged from 4.1V to 2.0V at a rate of C/3.
  • the batteries can exhibit a discharge capacity at 500 cycles that is at least about 85% and in further embodiments at least about 90% of the 5th cycle discharge capacity when discharged at a rate of C/3 when discharged from 4.25V to 2.0V.
  • the average voltage values are sensitive to composition and voltage window for cycling. However, the stability of the average voltage can be very good for an activated batter and may actually increase slightly with cycling.
  • an activated battery discharged from 4.25V to 2.0V can exhibit at least about 87.5%) at 500 cycles of the 5th cycle average discharge voltage, in additional embodiments at least about 90%) and in further embodiments at least about 90%) when discharged at a rate of C/3.
  • a person of ordinary skill in the art will recognize that additional ranges of performance of activated batteries within the explicit ranges above are contemplated and are within the present disclosure.
  • an activated battery is charged to a selected voltage and generally discharged to selected degrees before recharging, hi general, a reasonable charge voltage can be selected within a range, and suitable performance can be selected without significant dependence on the discharge voltage over suitable ranges. Also, as shown herein, the fade is not significantly dependent on the discharge rate. Therefore, performance fade can be referenced over a range of charge voltages and discharge rates to describe the outstanding cycling described herein.
  • the batteries after formation can be cycled with a charge voltage within ranges described above at an average rate from C/5 to about 2C such that the capacity after 2000 cycles is at least about 80 percent of the discharge capacity at the fifth cycle, in further embodiments at least about 82.5 percent and in other embodiments at least about 85% of the discharge capacity at the fifth cycle at the same average rate.
  • the batteries after formation can be cycled with a charge voltage within ranges described above at an average rate from C/5 to about 2C such that the average discharge voltage after 2000 cycles is at least about 85 percent of the average voltage at the fifth cycle, in further embodiments at least about 87.5 percent and in other embodiments at least about 90% of the average voltage at the fifth cycle at the same average rate.
  • batteries with partial/gradual activation can achieve at least about 100 mAl /g in other embodiments at least about 1 10 mAh/g, in further embodiments at least about 120 mAh/g, and in additional embodiments from about 125 to about 145 mAh/g when discharged from 4.25V to 2.0V at a rate of C/3 at the 500th discharge cycle, based on the weight of the positive electrode active material.
  • the batteries can exhibit a coulombic efficiency corresponding to a capacity at the 500th discharge cycle that is at least about 90%, in further embodiments at least about 92.5% in other embodiments at least about 95%, in additional embodiments at least about 97.5% relative to the 5th cycle discharge capacity when discharged at a rate of C/3 from 4.25V to 2.0V.
  • the batteries can exhibit a coulombic efficiency corresponding to a capacity at the 1000th discharge cycle that is at least about 87.5%, in further embodiments at least about 90%, in additional embodiments at least about 92.5% and in other embodiments at least about 95%o relative to the 5th cycle discharge capacity when discharged at a rate of 2C from 4.25V to 2.0V.
  • the batteries can exhibit a coulombic efficiency corresponding to a capacity at the 2500th discharge cycle that is at least about 87%>, in further embodiments at least about 90%>, and in other embodiments at least about 92.5% relative to the 5th cycle discharge capacity when discharged at a rate of 2C from 4.25V to 2.0V.
  • a battery with partial/gradual activation discharged from 4.25V to 2.0V can exhibit at least about 87.5% at 500 cycles of the 5th cycle average voltage, in additional embodiments at least about 90%, in other embodiments at least about 92.5% and in further embodiments at least about 95% when discharged at a rate of C/3.
  • a battery with partial/gradual activation discharged from 4.25V to 2.0V can exhibit at least about 85%) at 1000 cycles of the 5th cycle average voltage, in additional embodiments at least about 90% and in further embodiments at least about 95% when discharged at a rate of 2C.
  • a battery with partial/gradual activation discharged from 4.25V to 2.0V can exhibit at least about 85% at 2500 cycles of the 5th cycle average voltage, in additional embodiments at least about 90% and in further embodiments at least about 95%> when discharged at a rate of 2C.
  • a partially activated battery is charged to a selected voltage and generally discharged to selected degrees before recharging.
  • a reasonable charge voltage can be selected within a range, and suitable performance can be selected without significant dependence on the discharge voltage over suitable ranges.
  • the fade is not significantly dependent on the discharge rate. Therefore, performance fade can be referenced over a range of charge voltages and discharge rates to describe the outstanding cycling described herein.
  • the batteries after formation can be cycled with a charge voltage within ranges described above at an average discharge rate from C/5 to about 2C such that the capacity after 2000 cycles is at least about 80 percent of the discharge capacity at the fifth cycle, in further embodiments at least about 82.5 percent and in other embodiments at least about 85%) of the discharge capacity at the fifth cycle at the same average rate.
  • the batteries after formation can be cycled with a charge voltage within ranges described above at an average rate from C/5 to about 2C such that the average discharge voltage after 2000 cycles is at least about 85 percent of the average voltage at the fifth cycle, in further embodiments at least about 87.5 percent and in other embodiments at least about 90% of the average voltage at the fifth cycle at the same average rate.
  • the batteries can be cycled over 2000 cycles while achieving low levels of manganese in the negative electrode, which indicates a low amount of manganese dissolution from the positive electrodes with cycling.
  • the negative electrode can have amounts of no more than about 1 weight percent, in further embodiments no more than about 2500 parts per million by weight (ppm) and in other embodiments no more than about 1000 ppm.
  • ppm parts per million by weight
  • This example demonstrates the formation of a desired positive electrode active material using a carbonate or hydroxide co-precipitation process.
  • the materials were used for the formation of test batteries as described below.
  • the aqueous transition metal solution had a concentration from 1M to 3M, and the aqueous Na 2 C0 3 /NH 4 0H solution had a Na 2 C0 3 concentration of 1M to 4M and/or a NH 4 OH concentration of 0.2-2M.
  • the metal carbonate or hydroxide precipitate was filtered, washed multiple times with distilled water, and dried at 1 10°C for about 16hrs to form a metal carbonate or hydroxide powder.
  • Specific ranges of reaction conditions for the preparation of the samples are further outlined in Table 1, where the solution may not include both Na 2 C0 3 and NH 4 OH. Table 1
  • L12CO3 powder was combined with the dried metal carbonate or hydroxide powder and thoroughly mixed with a Jar Mill, double planetary mixer, or dry powder rotary mixer to form a homogenous powder mixture.
  • a portion, e.g. 5 grams, of the homogenized powders was calcined in a step to form the oxide, followed by an additional mixing step to further homogenize the powder.
  • the further homogenized powder was again calcined to form the highly crystalline lithium composite oxide.
  • Specific ranges of calcination conditions are further outlined in Table 2 (scfh is a standard cubic foot per hour).
  • the positive electrode composite material particles thus formed generally have a substantially spherical shape and are relatively homogenous in size.
  • a discussion of the synthesis and testing of a range of cathode active materials with similar stoichiometries can be found in published U.S.
  • the lithium metal oxide (LMO) particles prepared in Example 1 were coated with a thin layer of aluminum halide (A1X 3 ) usmg a solution-based method, where X is F, except for materials used in Example 7 where X is Br.
  • A1X 3 aluminum halide
  • X F
  • X Br
  • the metal oxide particles were then added into the aluminum nitrate solution to form a mixture.
  • the mixture was mixed vigorously for a period of time to homogenize. The length of mixing depends on the volume of the mixture.
  • ammonium halide i.e., ammonium fluoride or ammonium bromide
  • ammonium fluoride or ammonium bromide was added to the homogenized mixture to form aluminum halide precipitate as a coating on the particles.
  • the mixture was stirred at about 80°C for 3-10 h.
  • the mixture was then filtered and the solid obtained was washed repeatedly to remove any un-reacted materials.
  • the solid was calcined in nitrogen atmosphere at 300-600°C for 3-10h to form the aluminum halide coated metal oxide material.
  • This example demonstrates the formation of coin cell batteries and pouch batteries comprising a positive electrode comprising lithium metal oxide (LMO) and a negative electrode.
  • LMO lithium metal oxide
  • a positive electrode was formed from LMO oxide powders.
  • LMO powders with an aluminum fluoride coating were synthesized as described in Examples 1 and 2.
  • the LMO powders were mixed thoroughly with acetylene black (Super PTM from Timcal, Ltd, Switzerland) and graphite (KS 6TM from Timcal, Ltd) to form a homogeneous powder mixture.
  • acetylene black Super PTM from Timcal, Ltd, Switzerland
  • graphite KS 6TM from Timcal, Ltd
  • Polyvinylidene fluoride PVDF KF1300TM from Kureha Corp., Japan
  • N-methyl-pyrrolidone Sigma-Aldrich
  • the homogeneous powder mixture was then added to the PVDF-NMP solution and mixed for about 2 hours to form homogeneous slurry.
  • the slurry was applied onto an aluminum foil current collector to form a thin wet film and a positive electrode material was formed by drying the laminated current collector in a vacuum oven at 110 °C for about two hours to remove NMP.
  • the positive electrode material was pressed between rollers of a sheet mill to obtain a positive electrode with desired thickness.
  • the mixture comprised at least about 75 weight percent active metal oxide, at least about 3 weight percent acetylene black, at least about 1 weight percent graphite, and at least about 2 weight percent polymer binder.
  • a negative electrode was formed from graphitic carbon or elemental lithium.
  • the graphitic carbon based negative electrodes comprised at least about 75 weight percent graphite and at least about 1 weight percent acetylene black with the remaining portion of the negative electrode being polymer binder.
  • the acetylene black was initially mixed with NMP solvent to form a uniform dispersion.
  • the graphite and polymer were added to the dispersion to form a slurry.
  • the slurry was applied as a thin-film to a copper foil current collector.
  • a negative electrode was formed by drying the copper foil current collector with the thin wet film in vacuum oven at 110°C for about two hours to remove NMP.
  • the negative electrode material was pressed between rollers of a sheet mill to obtain a negative electrode with desired thickness.
  • Elemental lithium negative electrodes were formed from lithium foil (FMC Lithium) having thickness of 125-150 microns.
  • Coin cell batteries were formed by placing the positive electrode and negative electrode inside an argon filled glove box. A trilayer (polypropylene/polyethylene/polypropylene) micro-porous separator (2320 from Celgard, LLC, NC, USA) soaked with the selected electrolyte was placed between the positive electrode and the negative electrode. A few additional drops of the selected electrolyte were added between the electrodes. The electrodes were then sealed inside a 2032 coin cell hardware (Hohsen Corp., Japan) using a crimping process to form a coin cell battery. The resulting coin-cell battery was rested for 24 hours.
  • a trilayer (polypropylene/polyethylene/polypropylene) micro-porous separator (2320 from Celgard, LLC, NC, USA) soaked with the selected electrolyte was placed between the positive electrode and the negative electrode. A few additional drops of the selected electrolyte were added between the electrodes. The electrodes were then sealed inside a 2032 coin cell hardware (Hohsen Corp.,
  • Pouch cell batteries were constructed with 22 negative electrode plates alternating with 21 positive electrode plates such that a negative electrode plate was positioned at both ends of the stack. Electrodes were formed as described above with the current collectors coating on both sides and with a portion of the aluminum and copper current collectors left uncoated to serve as tab attachment points.
  • the negative electrodes had a surface area of about 3.1 cm x 4.35 cm and the positive electrodes had a surface area of about 3 cm x 4.25 cm.
  • the positive and negative electrodes were alternately stacked and a single trilayer (polypropylene/polyethylene/ polypropylene) micro-porous separator (2320 from Celgard, LLC, NC, USA) was folded in a Z-pattern with an appropriate electrode in each fold and a negative electrode at the surface of the folded structure so that a negative electrode is located at the ends of the stacks.
  • Nickel and aluminum tabs were then attached to the negative and positive electrodes, respectively, and the stack was place in a pouch bag and sealed at three edges. Electrolyte was then added to the stack through the fourth, open edge and the fourth edge was then sealed.
  • the battery was designed to have an approximate lAh total capacity at full discharge.
  • the batteries were activated through an initial charge to a voltage of 4.6V during the first battery charge.
  • a two step high voltage charge was used in the activation step as described in the '520 application cited above.
  • coin cell batteries were formed as described in Example 3 above.
  • four sets of batteries were formed, each set comprising six batteries.
  • the batteries were fabricated from a lithium foil as the negative electrode and a positive electrode comprising coated LMO particles.
  • the batteries were cycled within specific cycling voltage windows at a rate of C/10, C/5, C/3, C, 2C, and 9 mA for cycles 1 - 5, 6 - 10, 11 - 15, 16 - 20, 21 - 25, and 25 - 30, respectively.
  • Tables 3 - 6 display the particular cycling voltage window of each battery as well as specific discharge capacities and average discharge voltages at selected cycle numbers. TABLE 3
  • This example demonstrates the longer cycling performance of activated coin cell batteries. Specifically, the example demonstrates the initial cycling capacities of activated cell coin cell batteries with graphitic carbon anode active materials. After an initial formation cycle, the batteries were cycled over a selected voltage window. The batteries were activated through an initial charge to a voltage of 4.6V during the first battery charge. A two step high voltage charge was used in the activation step as described in the '520 application cited above.
  • This Example demonstrates the effect of charging a coin cell battery to an activation voltage subsequent to cycling, and an activated cell is cycled for comparison.
  • Fig. 8 is a plot of the specific discharge capacity versus cycle number for the first and second batteries. Fig. 8 shows that after about the 525th cycle, the first and second batteries had substantially similar discharge capacities and capacity fade. This result is consistent with a positive electrode active material with at least a high voltage phase and a low voltage phase.
  • the example demonstrates changes in the charge activity and discharge activity of full cell batteries as a function of cycle number
  • the batteries with a charge voltage lower than 4.5V were not activated. Specific discharge capacity versus cycle number was tested for each battery and results are plotted in Fig. 9 for reference.
  • non-activated cell coin cell batteries This example demonstrates the cycling performance of non-activated cell coin cell batteries.
  • non-activated batteries were not subjected to a fomiation step during the first charge to a high voltage value of 4.6V prior to cycling.
  • non-activated cells that are subsequently cycled to upper voltage values above 4.2 volts become partially activated during cycling.
  • This Example demonstrates the effect of partial activation on capacity and average discharge voltage.
  • Fig. 12 is a graph showing plots of the specific discharge capacity versus cycle number for the batteries tested in this example and results are tabulated in Table 9. Values in Table 9 denoted with an "*" reflect predicted values based on an extrapolation from earlier cycles.
  • the best over-all performing battery was the partially activated battery cycled between 3.1V and 4.3V.
  • the performance of the battery cycled between 3.1V and 4.3V was notable in that the battery showed an increase in capacity retention over 350 cycles and had specific capacity nearly as large as the battery cycled between 2.8V and 4.4V, despite having a smaller cycling voltage window.
  • This example demonstrates the long cycle performance of activated pouch cell batteries.
  • Fig. 13a is a graph containing plots of discharge capacity as a function of cycle number and average discharge voltage as a function of cycle number, for the battery cycled between 2.0V and 4.5V.
  • Fig. 13b is a graph containing analogous plots for the battery cycled between 3.15V and 4.1V.
  • Fig. 13a reveals that after 250 cycles, the battery cycled between 2.0V and 4.5V retained about 88.5% of its capacity and had a drop in average discharge voltage of about 5.6%.
  • Fig. 13b reveals that after 250 cycles, the battery cycled between 3.15V and 4.1V retained 93% of its capacity and had no appreciable drop in average discharge voltage.
  • Fig. 14 is a graph containing plots of differential charge/discharge capacities as a function as a function of charge/discharge voltage for both batteries. In particular, results are plotted for cycles 2, 50, 200, and 250. Referring to Fig. 14, for the battery cycled between 2.0V and 4.5V there was increased activity in the low voltage range of the cycling window and decreased activity in the high voltage range of the cycling window with increased cycle numbers. On the other hand, the activity of battery cycled between 3.1V and 4.1V was predominantly derived from the high voltage range of the cycling window for all cycles. These results are consistent with the development of a low voltage phase in the positive electrode active material at high upper cycling voltages.
  • Example 10 Comparison of Long Term Cycling Performance of Activated and Partially Activated Batteries
  • the example demonstrates the long term cycling performance of activated and partially activated batteries.
  • a first activated battery and the partially activated battery were cycled between about 4.25V and about 2.73V with a charge rate of about 1C and a discharge rate of about 2C.
  • a second activated battery was cycled between about 4.1V and about 3.14V with charge and discharge rates of about 0.75C. Cycling results for all three batteries are displayed in Figs. 15 - 18.
  • Figs. 15 and 16 are graphs showing plots of discharge capacity versus cycle nmnber for the fully and partially activated batteries.
  • the discharge capacity of the activated battery was larger than that of the partially activated battery to about 1500 cycles, although the partially activated battery displayed improved capacity retention.
  • improved battery capacity was observed to 2000 cycles, relative to the partially activated battery.
  • capacity retention the partially activated battery outperformed both activated batteries, although capacity retention was excellent in all cases.
  • Figs. 17 and 18 are graphs showing plots of average discharge voltage versus cycle number for the activated and partially activated batteries. Figs. 17 and 18 reveal that given identical cycling voltage windows and cycling rates, the partially activated battery cycled with higher average discharge voltages than the activated battery with comparable stability. On the other hand, the activated battery cycled between 4.1V and 3.15V at a rate of 0.75C cycled with improved average discharge voltages and stability relative to the partially activated battery. In all cases, cycling performance with respect to average discharge voltage was excellent.
  • Example 11 Positive Electrode Stability
  • This Example demonstrates the effects cycling window voltages on the stability of the positive electrode.
  • batteries 1 pouch batteries and 1 coin cell battery were formed as described in Example 3 above.
  • Batteries 1 and 2 for this example were the same as the batteries 1 and 2 in Example 10.
  • batteries 1 and 3 were subjected to a two-step formation process with a charge voltage of 4.6V as described in copending U.S. patent application 12/732,520 to Amiruddin et al., entitled "High Voltage Battery Formation Protocols and Control of Charging and Discharging for Desirable Long Term Cycling Performance," incorporated herein by reference.
  • batteries 1 and 3 were fully activated, and battery 2 was charged to 4.3V. Batteries 1 and 2 were cycled for 2500 cycles at a rate of C/3 between 2.73 V and 4.24V, and the specific capacity and average voltage for these batteries is described in Example 10. Battery 3 was cycled for 550 cycles at a rate of 1C charge and 2C discharge between 2V and 4.5V. Batteries 1 and 2 were cycled for cycles 2-4 over a voltage range intermediate between the formation voltage range the long term cycling voltage range.
  • the transition metal concentration in the negative electrode of the battery cycled between 2V and 4.5V was as much as 4 orders of magnitude higher than the transition metal concentration in the batteries cycled between 2.73V and 4.24V. Taking into account that battery 3 was cycled for significantly fewer cycles than batteries 1 and 2, the results indicate that the positive electrode of battery 3 cycled much less stably relative the positive electrodes in batteries 1 and 2.

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Abstract

La présente invention se rapporte à des batteries à lithium-ion qui peuvent être activées et ensuite utilisées pour exploiter une petite fraction de la capacité du cycle de décharge de telle sorte que la capacité de décharge et la tension de décharge moyenne restent dans des valeurs initiales pendant plusieurs milliers de cycles. Une meilleure performance de cycle d'utilisation a été obtenue à des vitesses de décharge relativement élevées et pour des formats de batterie pratiques. On peut également obtenir une performance de batterie à lithium-ion présentant une meilleure performance de cycle d'utilisation avec des batteries partiellement activées de telle sorte que les bonnes capacités de décharge et la tension de décharge moyenne chutent de plus de 20 % par rapport aux valeurs initiales. Le matériau actif pour l'électrode positive peut être un oxyde métallique riche en lithium. L'activation de la batterie peut comprendre des changements de phase des matériaux actifs. Comme décrit dans les présentes, les changements de phase peuvent être manipulés pour exploiter une fraction raisonnable de la capacité élevée disponible du matériau tout en assurant une stabilité remarquable du cycle d'utilisation.
PCT/US2011/049304 2010-09-03 2011-08-26 Très long cycle de vie des batteries au lithium-ion avec des matériaux cathodiques riches en lithium WO2012030639A2 (fr)

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CN2011800500651A CN103168383A (zh) 2010-09-03 2011-08-26 具有富含锂的阴极材料的极长循环锂离子电池
KR1020137008541A KR20130108332A (ko) 2010-09-03 2011-08-26 리튬 풍부한 캐소드 물질을 가진 리튬 이온 전지의 매우 긴 사이클링
JP2013527139A JP2013539594A (ja) 2010-09-03 2011-08-26 リチウムリッチカソード材料を用いたリチウムイオン電池の非常に長期のサイクリング
EP11822392.4A EP2612393A4 (fr) 2010-09-03 2011-08-26 Très long cycle de vie des batteries au lithium-ion avec des matériaux cathodiques riches en lithium

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JP2014534574A (ja) * 2011-10-21 2014-12-18 コリア インスティテュート オブ インダストリアル テクノロジー 電気自動車用リチウム二次電池用の高エネルギー密度の正極複合素材合成及び電極製造技術
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JP2015084303A (ja) * 2013-10-25 2015-04-30 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ．，Ｌｔｄ． リチウムイオン二次電池
CN103840151B (zh) * 2013-12-13 2016-04-13 山东海特电子新材料有限公司 一种特殊单晶结构的三元正极材料及其制备方法
CN104749525B (zh) * 2013-12-31 2017-11-17 华为技术有限公司 电池老化状态检测装置、系统、方法
KR102152370B1 (ko) * 2013-12-31 2020-09-07 삼성에스디아이 주식회사 양극 활물질 및 이를 포함하는 리튬 이차전지
FR3017489B1 (fr) * 2014-02-11 2016-01-29 Renault Sas Batterie lithium-ion comprenant une cathode riche en lithium et une anode a base de graphite
CN104319419A (zh) * 2014-11-10 2015-01-28 海宁兰博电源科技有限公司 一种高电压异形锂聚合物软包装电池
CN106469838A (zh) * 2015-08-14 2017-03-01 深圳市比克动力电池有限公司 圆柱动力锂离子电池的充电方法及装置
KR102010015B1 (ko) * 2015-08-31 2019-08-12 주식회사 엘지화학 리튬 이차전지 및 그의 구동방법
KR102010014B1 (ko) * 2015-08-31 2019-08-12 주식회사 엘지화학 리튬 이차전지 및 그의 구동방법
JP6699473B2 (ja) * 2015-09-14 2020-05-27 トヨタ自動車株式会社 全固体電池システム及びその製造方法
KR102473532B1 (ko) * 2015-12-31 2022-12-05 삼성전자주식회사 양극 활물질 및 상기 양극 활물질을 채용한 양극과 리튬 전지
KR102589963B1 (ko) 2016-04-12 2023-10-13 삼성에스디아이 주식회사 배터리의 충방전 제어 장치 및 그 제어 방법
CN105810934B (zh) * 2016-05-09 2019-07-05 北京工业大学 一种稳定富锂层状氧化物材料晶畴结构方法
CN106025256B (zh) * 2016-05-09 2019-10-29 北京工业大学 一种“双晶畴”富锂层状氧化物材料及制备方法
KR102659679B1 (ko) * 2019-04-22 2024-04-19 주식회사 엘지에너지솔루션 배터리의 미분 전압 커브를 결정하기 위한 장치 및 방법과, 상기 장치를 포함하는 배터리 팩
TWI711203B (zh) 2019-12-19 2020-11-21 國立臺灣科技大學 非水性電解液的處理方法以及電池的製造方法
WO2024058440A1 (fr) * 2022-09-15 2024-03-21 에스케이온 주식회사 Batterie secondaire au lithium et son procédé de fonctionnement

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EP2619828A2 (fr) * 2010-09-22 2013-07-31 Envia Systems, Inc. Revêtements d'halogénure de métal sur des matériaux électrode positive de batterie lithium-ion et batteries correspondantes
EP2619828A4 (fr) * 2010-09-22 2014-12-24 Envia Systems Inc Revêtements d'halogénure de métal sur des matériaux électrode positive de batterie lithium-ion et batteries correspondantes
JP2014534574A (ja) * 2011-10-21 2014-12-18 コリア インスティテュート オブ インダストリアル テクノロジー 電気自動車用リチウム二次電池用の高エネルギー密度の正極複合素材合成及び電極製造技術
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US10128675B2 (en) 2015-09-14 2018-11-13 Toyota Jidosha Kabushiki Kaisha All-solid-state battery system and method of manufacturing the same
US10651667B2 (en) 2015-09-14 2020-05-12 Toyota Jidosha Kabushiki Kaisha All-solid-state battery system and method of manufacturing the same

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