EP2269251A2 - Anode for lithium-ion cell and method of making the same - Google Patents

Anode for lithium-ion cell and method of making the same

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Publication number
EP2269251A2
EP2269251A2 EP09729742A EP09729742A EP2269251A2 EP 2269251 A2 EP2269251 A2 EP 2269251A2 EP 09729742 A EP09729742 A EP 09729742A EP 09729742 A EP09729742 A EP 09729742A EP 2269251 A2 EP2269251 A2 EP 2269251A2
Authority
EP
European Patent Office
Prior art keywords
anode
battery
lithium
compound
chalcogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09729742A
Other languages
German (de)
French (fr)
Other versions
EP2269251A4 (en
Inventor
Neal M. Golovin
Taison Tan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EnerDel Inc
Original Assignee
EnerDel Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EnerDel Inc filed Critical EnerDel Inc
Publication of EP2269251A2 publication Critical patent/EP2269251A2/en
Publication of EP2269251A4 publication Critical patent/EP2269251A4/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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

Definitions

  • hybrid vehicles use multiple propulsion systems to provide motive power.
  • the most commonly referenced hybrid vehicles are gasoline-electric hybrid vehicles, which use gasoline (petrol) to power internal-combustion engines (ICEs), and electric batteries to power electric motors.
  • Such hybrid vehicles recharge their batteries by capturing kinetic energy via regenerative braking.
  • ICEs internal-combustion engines
  • Gasoline -electric hybrid vehicles differ from all-electric vehicles, as the latter use batteries charged by an external source (such as from a power grid), or a range extending trailer.
  • nearly all hybrid vehicles still require gasoline as their sole fuel source, although other types of fuel, such as diesel fuel, cthanol, or other plant- based oils, have also seen occasional use.
  • Batteries and cells are important energy storage devices well known in the art. Electrical energy is produced in the battery by the chemical reaction that occurs between two dissimilar electrode plates that are immersed in an electrolyte solution.
  • the largest demand placed on the battery occurs when it must supply current to operate a motive motor at acceleration, such as a situation when a battery is used to start a vehicle.
  • the amperage requirements of the motive motor may be over several hundred amps.
  • Most battery types that have a large volume (or level of current supply) require large packaging which results in large weight of the battery, and is therefore not cost effective. At the same time, such high currents are required for the very limited time, usually seconds. Therefore, so called "high-rate" batteries are required for certain applications.
  • a typical lithium-ion cell consists of a positive electrode (a "cathode” or a “cathode matrix”), a negative electrode (an “anode” or an “anode matrix”) and an electrolyte (a solution or a solid-state product) containing dissociated salts separated by a micro-porous membrane (a "separator").
  • the lithium ions transfer between the two electrodes through the electrolyte.
  • lithium ions are extracted from the cathode matrix, go through the electrolyte and separator and intercalate into the anode matrix.
  • electrons are released from the cathode, go through the external circuit and are accepted by anode compounds.
  • the reverse process occurs during the discharging process.
  • Metal oxides such as lithium metal oxides, have found utility in secondary batteries as cathode and anode intercalating materials.
  • 2 has been found to be an attractive material for electrodes (Colbow et al., J. Power Sources, 26(3-4), pp. 397-402 (1989)).
  • the formal valence of titanium is +4, which is the highest achievable oxidation state possible for titanium (Zachau-Christiansen et al., Solid Stale Ionics, 40-41 part 2, pp. 580-584 (1990)).
  • This Li 4 TisOi 2 material has been found to intercalate lithium ions without strain or shrinkage to the lattice (Ohzuku et al., J Electrochem Soc, 142(5), pp. 1431 -1435 (1995)) making it ideal for hybrid electric vehicle (“HEV”) applications.
  • the lithium insertion reaction (intercalation) at the anode is:
  • This reaction occurs at approximately 1 .5V vs. metallic lithium.
  • the titanium is reduced from the +4 state to the +3 state, with the mean oxidation state of 3.4 (60% Ti + and 40% Ti 4+ ) when fully intercalated.
  • United States Patent No. 4,366,431 to Santini and United States Patent No. 5,126,649 to Osanai teach methods for detecting bubbles in the electrolyte and making adjustments to charging rate accordingly.
  • United States Patent No. 6,437,542 to Liaw et al. and United States Patent No. 6,459,238 to Minamiura et al. teach methods for measuring and monitoring pressure within the cell and control charging based on the cells pressure profile.
  • dopants are also well known in the art as a means to improve the thermal stability and overcharge protection in fully charged lithium metal oxides.
  • Ohzuku et al. J. Electrochem Soc, 142(12), pp. 4033-4039
  • doping lithium nickelates LiAI with Al 3+ and producing improved thermal stability and overcharge protection.
  • United States Patent No. 6,794,085 to Gao et al. United States Patent No. 6,040,089 to Mancv et al.
  • Battery gassing is a constant issue in the battery design and manufacturing process
  • the disclosure of the present application provides a solution to such a problem, with at least one advantage thereof being to provide a highly safe electrode material for a lithium cell that excels in charge-discharge cycle durability while reducing or eliminating gassing during use.
  • the disclosure of the present application provides various compositions, and methods for preparing the same, which may be useful, for example, to prepare one or more anodes of the present disclosure. Such anodes may be useful, for example, to prepare one or more batteries which themselves, for example, may be useful in connection with a vehicle as referenced herein.
  • This disclosure of the present application relates to metal oxide compounds and methods of making the same.
  • the present disclosure relates to doped metal oxide insertion compounds for use in lithium and lithium-ion batteries.
  • the disclosure provides a composition of an anode of spinel-type structure with a dopant material that will replace some of the transition metal, and which may also replace some oxygen in the anode, and yet will maintain the overall potential of the electrode below -1.7V vs. lithium.
  • the effect is the dopant metal would be reduced instead of the primary transition metal during cycling and reduces the gassing caused by the primary transition metal.
  • the anode comprises a lithium-based compound having the formula wherein M comprises a dopant material, and wherein 0 ⁇ y ⁇ 1.
  • the dopant material may comprise molybdenum (Mo), tungsten (W), zirconium (Zr), or hafnium (Hf).
  • the anode comprises a lithium-based compound having the formula LL 4 Ti5.yMyO 12 . z Xz, wherein M comprises a dopant material, wherein X comprises a chalcogen, wherein O ⁇ y ⁇ 1, and wherein O ⁇ z ⁇ 2y.
  • the chalcogen may comprise sulfur (S), selenium (Se) or tellurium (Te).
  • the battery comprises an anode, a cathode, and an electrolyte, wherein the anode comprises a lithium-based compound.
  • the lithium-based compound has the formula Li 4 Ti 5 .yM y Oi 2 , wherein M comprises a dopant material, and wherein O ⁇ y ⁇ 1.
  • the lithium-based compound has the formula wherein M comprises a dopant material, wherein X comprises a chalcogen, wherein O ⁇ y ⁇ 1 , and wherein O ⁇ z ⁇ 2y.
  • the method comprises the step of introducing amounts of a first material, a second material, and a third material to a vessel, wherein the first material comprises lithium, wherein the second material comprises titanium and oxygen, and wherein the third material comprises a dopant material and a chalcogen.
  • a method further comprises the steps of grinding the first material, the second material, and the third material within the vessel, and heating the ground vessel contents for a period of time at an elevated temperature to create the lithium-based composition.
  • the method comprises the steps of preparing a lithium-based composition of the disclosure of the present application, introducing the lithium-based composition, a conductive medium, a graphite source, and a binder to a receptacle, mixing the contents of the receptacle to form a mixture, and placing the mixture on a metallic substrate to form at least a portion of an anode.
  • compositions, and methods for preparing the same which may be useful, for example, to prepare one or more anodes of the present disclosure.
  • Such anodes may be useful, for example, to prepare one or more batteries which themselves, for example, may be useful in connection with a vehicle as referenced herein.
  • the anode comprises a lithium-based compound having the formula Li 4 TiS- J -MyOi 2 , wherein M comprises a dopant material, and wherein 0 ⁇ y ⁇ 1.
  • the dopant material may comprise molybdenum (Mo), tungsten (W), zirconium (Zr), or hafnium (Hf).
  • y 0.1 , so that the lithium-based compound has the formula Li4Ti4.9M0. 1 O 12 .
  • the dopant material comprises molybdenum, so that the lithium-based compound has the formula Li 4 Tis. y M ⁇ yO
  • the lithium-based compound has the formula Li 4 Ti4.9Moo. 1 O 12 .
  • the anode comprises a lithium-based compound having the formula Li 4 Ti5.yMyO1 2 .zXz, wherein M comprises a dopant material, wherein X comprises a chalcogen, wherein O ⁇ y ⁇ 1 , and wherein O ⁇ z ⁇ 2y.
  • the chalcogen may comprise sulfur (S), selenium (Se) or tellurium (Te).
  • the dopant material comprises molybdenum
  • the chalcogen comprises sulfur
  • z 0.2, so that the lithium-based compound has the formula Li 4 Ti 4 9M0 i ⁇
  • said anode comprises at least a portion of a battery.
  • Such a battery may comprise a lithium- ion cell or any other battery wherein such an anode is useful therein.
  • the battery is rechargeable. Any or all of the various features and/or limitations disclosed herein regarding embodiments of an anode, or the various anodes themselves, may be useful in connection with any or all of the various batteries disclosed herein.
  • the battery comprises a cathode, a separator plate positioned at least partially between the anode and the cathode, and an electrolyte, wherein during a charging and discharging battery cycle, at least a portion of the dopant material would be reduced prior to a reduction of titanium.
  • the reduction of at least a portion of the dopant material prior to the reduction of titanium reduces gassing caused by the reduction of titanium.
  • the overall potential is below approximately 1.7V versus lithium.
  • the anode further comprises graphite, and may further comprise a binder effective to bind the lithium- based compound to the graphite.
  • the binder comprises polyvinylidine fluoride (PVDF) and N-methyl pyrolinidone (NMP).
  • PVDF polyvinylidine fluoride
  • NMP N-methyl pyrolinidone
  • the lithium-based compound bound to the graphite may positioned on a metallic substrate, such as copper foil.
  • the battery comprises an anode, a cathode, and an electrolyte, wherein the anode comprises a lithium-based compound.
  • the lithium-based compound has the formula Li4Ti5. y M y Oi 2 , wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium, and wherein 0 ⁇ y ⁇ 1.
  • M comprises Mo, so that the lithium-based compound of the anode of the battery has the formula
  • the lithium-based compound of the anode of the battery has the formula Li 4 TJs. yMyOi 2 . z Xi, wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium, wherein X comprises a chalcogen, wherein O ⁇ y ⁇ I , and wherein O ⁇ z ⁇ 2y.
  • the chalcogen may comprise sulfur, selenium or tellurium.
  • the lithium-based compound of the anode of the battery has the formula Li 4 Ti 5 .
  • the dopant material comprises molybdenum
  • the chalcogen comprises sulfur
  • the battery comprises an anode, a cathode, and an electrolyte, wherein the anode comprises a spinel and at least one dopant selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium.
  • the spinel comprises at least one lithium metal oxide.
  • the lithium metal oxide comprises
  • any or all of the various features and/or limitations disclosed herein regarding embodiments of a battery or portion of a battery, or the various batteries or portions of the various batteries themselves, may be useful in connection with any or all of the various batteries disclosed herein.
  • an exemplary embodiment of an anode referenced herein may be used within an exemplary embodiment of a battery disclosed herein, although the specific anode embodiment and the specific battery embodiment was not specifically referenced in connection with one another.
  • exemplary compound of the present disclosure may have the formula Li 4 Tis. y M y O
  • M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium
  • 0 ⁇ y ⁇ 1 without such a compound having the sole use of being used in connection with the preparation of an anode of the present disclosure.
  • Such compounds may have one or more other uses, and as such, any reference to a compound within the disclosure of the present application is not intended to be, and should not be treated as, having a sole utility in connection with anodes.
  • a vehicle of the present disclosure may comprise a battery of the present disclosure, wherein the battery comprises an anode, a cathode, and an electrolyte, wherein the anode comprises a lithium-based compound having the formula wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium, and wherein 0 ⁇ y ⁇ 1.
  • an exemplary vehicle of the disclosure of the present application comprises a battery comprising an anode comprising a lithium-based compound having the formula wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium, wherein X comprises a chalcogen selected from the group consisting of sulfur, selenium and tellurium, wherein O ⁇ y ⁇ 1 , and wherein O ⁇ z ⁇ 2y.
  • At least one advantage of the disclosure of the present application is to provide materials that can also be used as dopants when mixed with anodic lithium metal oxide that will not reduce the overall cell potential.
  • dopants, or combinations of dopants may be selected to replace some of the transition metal in a LiM y O z system as disclosed herein, but still keep the overall potential below 1.7V.
  • the disclosure of the present application is not limited to any one specific dopant.
  • the titanium can be replaced by molybdenum, tungsten, zirconium, or hafnium (Hf), and still maintain a potential below 1.7V.
  • the formula for the active anode material would be LL)Ti 5 .
  • the disclosure of the present application contains embodiments, in addition to replacing the primary transition metal, which replace some of the oxygen with another dopant material as well, such as with sulfur (S), selenium (Se) or tellurium (Te).
  • S sulfur
  • Se selenium
  • Te tellurium
  • a general objective remains the same in that gassing would be reduced and the overall potential of the electrode would remain below 1.7V.
  • Molybdenum disulfide (M0S 2 ) for example, as an active material has a potential of ⁇ 1.6V vs. Li.
  • Employing the sulfur in place of oxygen will help reduce the material voltage.
  • An exemplary rechargeable lithium-ion battery whose anode comprises such an electrode material layer has significant advantages such that the magnitude of the volume expansion of the anode when lithium is inserted upon charging and the magnitude of the volume shrinkage of the anode when said lithium is released upon discharging are slight.
  • the performance of such an anode is more difficult to deteriorate even when charge- and-discharge cycle is repeated over a long period of time, providing such a rechargeable lithium-ion battery with an improved charge-and-discharge cycle life.
  • An exemplary lithium-based compound of the present disclosure may be prepared as follows.
  • a method for preparing a lithium-based compound comprises the steps of introducing amounts of a first material, a second material, and a third material to a vessel, grinding those ingredients, and heating those ingredients for a period of time at an elevated temperature to create the lithium-based composition.
  • the first material comprises lithium
  • the second material comprises titanium and oxygen
  • the third material comprises a dopant material and a chalcogen.
  • a fourth material namely gas
  • the gas would be introduced to the vessel by providing a flow of the gas to the vessel during the heating step.
  • a gas may comprise air, oxygen gas, or any other suitable gas containing oxygen.
  • the dopant material would comprise molybdenum, tungsten, zirconium, or hafnium, and the chalcogen would comprise sulfur, selenium and tellurium.
  • the following ingredients may be used: lithium carbonate as the first material, titanium dioxide or anatase titanium dioxide as the second material, and/or molybdenum disulfide as the third material.
  • the ingredients may be ground in a vessel using any number of known grinding methods, including the use of a mortar and pestle and/or a ball mill. Such grinding methods illustrated herein are not intended to limit the scope of the present disclosure as other suitable grinding methods may be used.
  • the method would comprise grinding the ingredients in a first vessel, such as a mortar, and heating the ingredients in a second vessel, such as a platinum crucible.
  • the heating step in at least one method of preparing an exemplary lithium-based compound, would last approximately 24 hours at an elevated temperature is approximately 900 0 C.
  • an exemplary lithium-based compound After an exemplary lithium-based compound is prepared, it may be stored in a light-proof plastic container, for example, or it may be used to prepare an anode as referenced herein.
  • the desired lithium-based composition comprises a compound of the formula Li4Ti5.yMyO12.zX2, wherein M comprises the dopant material, wherein X comprises the chalcogen, wherein 0 ⁇ y ⁇ 1, and wherein 0 ⁇ z ⁇ 2y.
  • the dopant material may comprise consisting of molybdenum, tungsten, zirconium, or hafnium, and the chalcogen may comprise sulfur, selenium and tellurium.
  • the dopant material comprises molybdenum
  • the chalcogen comprises sulfur
  • z 0.2.
  • At least one method of preparing an exemplary lithium-based compound is as follows.
  • O n ,S 0 2 are lithium carbonate (Li 2 CO 5 ) as the Li source, anatase titanium dioxide (TiO-) as the titanium and oxygen source, molybdenum disulfide (M0S 2 ) as the molybdenum (dopant material) and sulfur (chalcogen) source, and dry air as the rest of the oxygen.
  • An exemplary anode of the present disclosure may be prepared as follows.
  • a method for preparing at least a portion of an anode comprising the steps of preparing a lithium-based composition of the disclosure of the present application, introducing the lithium-based composition, a conductive medium, a graphite source, and a polymer/binder to a receptacle, mixing those items together, and placing the mixture on a metallic substrate to form at least a portion of an anode.
  • Any or all of the various features, steps, and/or limitations disclosed herein regarding the preparation of a lithium-based composition of the present disclosure may be applicable to the preparation of a lithium-based composition useful to prepare an anode or a portion thereof.
  • the conductive medium may comprise acetylene black ( ⁇ enka black).
  • the polymer/binder may comprise polyvinylidine fluoride (PVDF) and N-methyl pyrolinidone (NMP), and/or the graphite source may comprise SGF6 graphite, also known as Superior Graphite.
  • small aliquots of the polymer/binder may be added over time to the conductive medium, the graphite source, and the lithium-based compound. Mixing may be stopped when the mixture reaches a desired viscosity. In a least one embodiment, the mixing step is completed when the mixture reaches a viscosity between about 5100 cP and about 5300 cP as indicated by a viscometer operating at approximately 20 RPM.
  • the mixture may be positioned on a metallic substrate, such as, for example, copper foil, and dried to prepare at least a portion of an anode.
  • a metallic substrate such as, for example, copper foil
  • the disclosure of the present application is not intended to be limited to any specific metallic substrate, as, for example, one or more other metallic substrates, such as an aluminum foil, may be suitable for the preparation of an exemplary anode, or part of an anode, of the present disclosure.
  • the step of placing the mixture on a metallic substrate comprises feeding the mixture through a fixed-gap slot dye onto the metallic substrate, wherein the metallic substrate is rotated about a spool.
  • the fixed-gap is fixed at 5 ⁇ m.
  • an exemplary method of preparing at least a portion of an anode may further comprise the step of drying the at least a portion of an anode for a period of time at an elevated temperature under a vacuum.
  • the period of time is approximately 15 hours, and wherein the elevated temperature is approximately 12O 0 C.
  • B So 2 are prepared for a lithium-ion cell electrode.
  • 2g of Denka black (acetylene black, a conductive medium) and 2g of SGF6 graphite (Superior Graphite) were combined.
  • 33.73g of 13% PVDF solution in N-methyl pyrolinidone (NMP) (binder) was added to the mixture.
  • NMP N-methyl pyrolinidone
  • a roll of l O ⁇ m thick copper foil was mounted on a source spool and wound through a coating head made up of a driver roller and a fixed gap slot dye. The gap was fixed to 5 ⁇ m, and the mixture/slurry as prepared above was is fed through the dye and onto the copper foil.
  • the NMP was removed by drying in a forced air convection oven in line on the coater.
  • the coated copper foil was transferred to the dry room, and dried at 120 0 C for 15hr under a vacuum.
  • the dried electrode stock was allowed to cool to room temperature under vacuum, and was then sealed in a laminated foil pouch to protect the coating until used.
  • the disclosure may have presented a method and/or process as a particular sequence of steps.
  • the method or process should not be limited to the particular sequence of steps described.
  • other sequences of steps may be possible. Therefore, the particular order of the steps disclosed herein should not be construed as limitations of the present disclosure.
  • disclosure directed to a method and/or process should not be limited to the performance of their steps in the order written, and one skilled in the art can readily appreciate that the sequences may be varied and still remain within the spirit and scope of the present disclosure.

Abstract

The disclosure of the present application provides various compositions, and methods for preparing the same, which may be useful, for example, to prepare one or more anodes of the present disclosure. Such anodes may be useful, for example, to prepare one or more batteries which themselves, for example, may be useful in connection with a vehicle as referenced herein. In at least one embodiment of an anode of the present disclosure, the anode comprises lithium-based compound having the formula Li4≤Ti5-yMyO12-zXz, wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium, wherein X comprises a chalcogen selected from the group consisting of sulfur, selenium, and tellurium, wherein 0 < y ≤1, and wherein 0 < z ≥2y.

Description

ANODE FOR LITHIUM-ION CELL AND METHOD OF MAKING THE SAME
PRIORITY
The present application is related to and claims the benefit of U.S. Provisional Patent Application Serial No. 6,1/033,638, entitled "ANODE FOR LITHIUM ION CELL AND METHOD OF MAKING THE SAME," filed March 4, 2008, the contents of which is incorporated herein by reference in its entirety.
BACKGROUND
Many motor vehicles, such as hybrid vehicles, use multiple propulsion systems to provide motive power. The most commonly referenced hybrid vehicles are gasoline-electric hybrid vehicles, which use gasoline (petrol) to power internal-combustion engines (ICEs), and electric batteries to power electric motors. Such hybrid vehicles recharge their batteries by capturing kinetic energy via regenerative braking. When cruising or idling, some of the output of the combustion engine is fed to a generator (merely the electric motor(s) running in generator mode), which produces electricity to supply the motive electric motor and to charge the batteries. Gasoline -electric hybrid vehicles differ from all-electric vehicles, as the latter use batteries charged by an external source (such as from a power grid), or a range extending trailer. However, nearly all hybrid vehicles still require gasoline as their sole fuel source, although other types of fuel, such as diesel fuel, cthanol, or other plant- based oils, have also seen occasional use.
Batteries and cells are important energy storage devices well known in the art. Electrical energy is produced in the battery by the chemical reaction that occurs between two dissimilar electrode plates that are immersed in an electrolyte solution. The largest demand placed on the battery occurs when it must supply current to operate a motive motor at acceleration, such as a situation when a battery is used to start a vehicle. The amperage requirements of the motive motor may be over several hundred amps. Most battery types that have a large volume (or level of current supply) require large packaging which results in large weight of the battery, and is therefore not cost effective. At the same time, such high currents are required for the very limited time, usually seconds. Therefore, so called "high-rate" batteries are required for certain applications.
A typical lithium-ion cell consists of a positive electrode (a "cathode" or a "cathode matrix"), a negative electrode (an "anode" or an "anode matrix") and an electrolyte (a solution or a solid-state product) containing dissociated salts separated by a micro-porous membrane (a "separator"). The lithium ions transfer between the two electrodes through the electrolyte. During the charging process, lithium ions are extracted from the cathode matrix, go through the electrolyte and separator and intercalate into the anode matrix. Simultaneously, electrons are released from the cathode, go through the external circuit and are accepted by anode compounds. The reverse process occurs during the discharging process.
Metal oxides, such as lithium metal oxides, have found utility in secondary batteries as cathode and anode intercalating materials. The spinel Li4TisO|2 has been found to be an attractive material for electrodes (Colbow et al., J. Power Sources, 26(3-4), pp. 397-402 (1989)). In the lithium titanate spinel-type structure of Li4TJsOi2, the formal valence of titanium is +4, which is the highest achievable oxidation state possible for titanium (Zachau-Christiansen et al., Solid Stale Ionics, 40-41 part 2, pp. 580-584 (1990)). This Li4TisOi2 material has been found to intercalate lithium ions without strain or shrinkage to the lattice (Ohzuku et al., J Electrochem Soc, 142(5), pp. 1431 -1435 (1995)) making it ideal for hybrid electric vehicle ("HEV") applications.
Theoretically, the lithium insertion reaction (intercalation) at the anode is:
3Li+ + Li4Ti5Oi2 ""* > Li7Ti5O12
This reaction occurs at approximately 1 .5V vs. metallic lithium. The titanium is reduced from the +4 state to the +3 state, with the mean oxidation state of 3.4 (60% Ti + and 40% Ti4+) when fully intercalated.
As batteries are charged, they create bubbles of gas produced when the chemical reaction cannot keep up with the energy input. According to Lee et al. (Journal of Power Sources, 132(1 -2), pp. 201-205 (2004)), gassing in lithium ion cells is believed to be caused by the oxidation of the electrolyte at the electrode. Gassing is considered a safety issue because of the risk of toxic gas release and potential explosion of the lithium ion cell/battery itself.
Various attempts to manage the gassing issue have been discussed and implemented. It is known that fast charging secondary cells with fluid electrolytes is effective to about a 80-90% charge. At that point, energy put into the battery is used to breakdown the electrolyte and create heat rather than being stored.
The known art is replete with numerous methods to regulate the charging cycle in order to reduce the gassing effect. For example, United States Patent No. 4,366,431 to Santini and United States Patent No. 5,126,649 to Osanai teach methods for detecting bubbles in the electrolyte and making adjustments to charging rate accordingly. United States Patent No. 6,437,542 to Liaw et al. and United States Patent No. 6,459,238 to Minamiura et al. teach methods for measuring and monitoring pressure within the cell and control charging based on the cells pressure profile.
In other cases, the electrolyte system has been modified through the use of additives. United States Patent No. 7,026,074 to Chen et al. and United States Patent No. 7,217,479 to Park et al. describe the use of various additives to the electrolytes to suppress gas generation. Another means of improving safety is to vent the gases. United States Patent No. 6,278,259 to Kimoto et al. is yet another example of such a feature on the battery used to allow gas to escape when internal pressures get too high. However, as referenced herein, such gases may be toxic, and as such, their release into an engine compartment and/or the atmosphere is not optimal.
The use of dopants is also well known in the art as a means to improve the thermal stability and overcharge protection in fully charged lithium metal oxides. For example, Ohzuku et al. (J. Electrochem Soc, 142(12), pp. 4033-4039) describes doping lithium nickelates (LiAI with Al3+ and producing improved thermal stability and overcharge protection. United States Patent No. 6,794,085 to Gao et al., United States Patent No. 6,040,089 to Mancv et al., and United States Patent No. 6,277,521 to Gao et al. describe using multiple dopants to lithium metal oxide, preferably cobalt or nickel metal based oxides, in order to improve cycling performance and protect the cells from overcharging or overdischarging. In addition to the foregoing, United States Patent No. 6,221 ,531 to Vaughey et al. describes the use of dopants to improve overall conductivity Of Li4TiSUi2 in its lithium depleted phase by partially substituting lithium ions with Al3+ or Mg2+ on the octahedral sites in order to reduce the oxidation state of titanium ions.
Battery gassing is a constant issue in the battery design and manufacturing process, The disclosure of the present application provides a solution to such a problem, with at least one advantage thereof being to provide a highly safe electrode material for a lithium cell that excels in charge-discharge cycle durability while reducing or eliminating gassing during use.
BRIEF SUMMARY
The disclosure of the present application provides various compositions, and methods for preparing the same, which may be useful, for example, to prepare one or more anodes of the present disclosure. Such anodes may be useful, for example, to prepare one or more batteries which themselves, for example, may be useful in connection with a vehicle as referenced herein. This disclosure of the present application relates to metal oxide compounds and methods of making the same. In at least one embodiment of the disclosure of the present application, the present disclosure relates to doped metal oxide insertion compounds for use in lithium and lithium-ion batteries.
In at least one embodiment of the disclosure of the present application, the disclosure provides a composition of an anode of spinel-type structure with a dopant material that will replace some of the transition metal, and which may also replace some oxygen in the anode, and yet will maintain the overall potential of the electrode below -1.7V vs. lithium. The effect is the dopant metal would be reduced instead of the primary transition metal during cycling and reduces the gassing caused by the primary transition metal.
In at least one embodiment of an anode of the disclosure of the present application, the anode comprises a lithium-based compound having the formula wherein M comprises a dopant material, and wherein 0 < y < 1. In exemplary embodiments, the dopant material may comprise molybdenum (Mo), tungsten (W), zirconium (Zr), or hafnium (Hf).
In at least one embodiment of an anode of the disclosure of the present application, the anode comprises a lithium-based compound having the formula LL4Ti5.yMyO12.zXz, wherein M comprises a dopant material, wherein X comprises a chalcogen, wherein O < y < 1, and wherein O < z < 2y. Any or all of the various features and/or limitations disclosed herein regarding embodiments of an anode of the present disclosure may be applicable to other embodiments of anodes disclosed herein. In various embodiments, the chalcogen may comprise sulfur (S), selenium (Se) or tellurium (Te).
In at least one embodiment of a battery of the disclosure of the present application, the battery comprises an anode, a cathode, and an electrolyte, wherein the anode comprises a lithium-based compound. In an exemplary embodiment, the lithium-based compound has the formula Li4Ti5.yMyOi2, wherein M comprises a dopant material, and wherein O < y < 1. In another embodiment, the lithium-based compound has the formula wherein M comprises a dopant material, wherein X comprises a chalcogen, wherein O < y < 1 , and wherein O < z < 2y.
In at least one embodiment of a method for preparing a lithium-based composition of the present disclosure, the method comprises the step of introducing amounts of a first material, a second material, and a third material to a vessel, wherein the first material comprises lithium, wherein the second material comprises titanium and oxygen, and wherein the third material comprises a dopant material and a chalcogen. Such a method further comprises the steps of grinding the first material, the second material, and the third material within the vessel, and heating the ground vessel contents for a period of time at an elevated temperature to create the lithium-based composition.
In at least one embodiment of a method for preparing at least a portion of an anode of the disclosure of the present application, the method comprises the steps of preparing a lithium-based composition of the disclosure of the present application, introducing the lithium-based composition, a conductive medium, a graphite source, and a binder to a receptacle, mixing the contents of the receptacle to form a mixture, and placing the mixture on a metallic substrate to form at least a portion of an anode.
DETAILED DESCRIPTION
The disclosure of the present application provides various compositions, and methods for preparing the same, which may be useful, for example, to prepare one or more anodes of the present disclosure. Such anodes may be useful, for example, to prepare one or more batteries which themselves, for example, may be useful in connection with a vehicle as referenced herein.
In at least one embodiment of an anode of the disclosure of the present application, the anode comprises a lithium-based compound having the formula Li4TiS-J-MyOi2, wherein M comprises a dopant material, and wherein 0 < y < 1. In exemplary embodiments, the dopant material may comprise molybdenum (Mo), tungsten (W), zirconium (Zr), or hafnium (Hf). In at least one embodiment, y = 0.1 , so that the lithium-based compound has the formula Li4Ti4.9M0.1O12. In an exemplary embodiment, the dopant material comprises molybdenum, so that the lithium-based compound has the formula Li4Tis.yMθyO|2. In at least one embodiment, the lithium-based compound has the formula Li4Ti4.9Moo.1O12.
In at least one embodiment of an anode of the disclosure of the present application, the anode comprises a lithium-based compound having the formula Li4Ti5.yMyO12.zXz, wherein M comprises a dopant material, wherein X comprises a chalcogen, wherein O < y < 1 , and wherein O < z < 2y. Any or all of the various features and/or limitations disclosed herein regarding embodiments of an anode of the present disclosure may be applicable to other embodiments of anodes disclosed herein. In various embodiments, the chalcogen may comprise sulfur (S), selenium (Se) or tellurium (Te). In at least one embodiment, the lithium- based compound has the formula Li4Ti5.yMoyO i2-zXz- In another embodiment, z = 0.2, so that the lithium-based compound has the formula LUTi4^M0 IOH.SXO.∑- In an exemplary embodiment, the dopant material comprises molybdenum, the chalcogen comprises sulfur, and z = 0.2, so that the lithium-based compound has the formula Li4Ti49M0 iθ| 1 sSo.∑- In at least one embodiment of an anode of the disclosure of the present application, said anode comprises at least a portion of a battery. Such a battery may comprise a lithium- ion cell or any other battery wherein such an anode is useful therein. In at least one embodiment, the battery is rechargeable. Any or all of the various features and/or limitations disclosed herein regarding embodiments of an anode, or the various anodes themselves, may be useful in connection with any or all of the various batteries disclosed herein.
In an exemplary embodiment of a battery comprising an anode of the disclosure of the present application, the battery comprises a cathode, a separator plate positioned at least partially between the anode and the cathode, and an electrolyte, wherein during a charging and discharging battery cycle, at least a portion of the dopant material would be reduced prior to a reduction of titanium. In an exemplary embodiment, the reduction of at least a portion of the dopant material prior to the reduction of titanium reduces gassing caused by the reduction of titanium. In another embodiment, the overall potential is below approximately 1.7V versus lithium.
In at least one exemplary embodiment of a battery of the present disclosure, the anode further comprises graphite, and may further comprise a binder effective to bind the lithium- based compound to the graphite. In an exemplary embodiment, the binder comprises polyvinylidine fluoride (PVDF) and N-methyl pyrolinidone (NMP). In another embodiment, the lithium-based compound bound to the graphite may positioned on a metallic substrate, such as copper foil.
In at least one embodiment of a battery of the disclosure of the present application, the battery comprises an anode, a cathode, and an electrolyte, wherein the anode comprises a lithium-based compound. In an exemplary embodiment, the lithium-based compound has the formula Li4Ti5.yMyOi2, wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium, and wherein 0 < y < 1. In another embodiment, M comprises Mo, so that the lithium-based compound of the anode of the battery has the formula In at least one embodiment, M comprises Mo, and y = 0.1, so that the lithium-based compound of the anode of the battery has the formula
In at least one exemplary embodiment of a battery of the disclosure of the present application, the lithium-based compound of the anode of the battery has the formula Li4TJs. yMyOi2.zXi, wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium, wherein X comprises a chalcogen, wherein O < y < I , and wherein O < z < 2y. In various embodiments, the chalcogen may comprise sulfur, selenium or tellurium. In at least one embodiment, the lithium-based compound of the anode of the battery has the formula Li4Ti 5.yMoyO|2-zX_. In another embodiment, z = 0.2, so that the lithium-based compound of the anode of the battery has the formula Li4Ti4 9M0 1O1 i gXo 2- In an exemplary embodiment, the dopant material comprises molybdenum, the chalcogen comprises sulfur, and z = 0,2, so that the lithium-based compound of the anode of the battery has the formula Li4Ti49M0.1 On sSo2-
In at least one embodiment of a battery of the disclosure of the present application, the battery comprises an anode, a cathode, and an electrolyte, wherein the anode comprises a spinel and at least one dopant selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium. In an exemplary embodiment, the spinel comprises at least one lithium metal oxide. In at least one embodiment, the lithium metal oxide comprises
Any or all of the various features and/or limitations disclosed herein regarding embodiments of a battery or portion of a battery, or the various batteries or portions of the various batteries themselves, may be useful in connection with any or all of the various batteries disclosed herein. For example, an exemplary embodiment of an anode referenced herein may be used within an exemplary embodiment of a battery disclosed herein, although the specific anode embodiment and the specific battery embodiment was not specifically referenced in connection with one another.
In addition, the various compounds referenced herein in connection with one or more anodes are not intended to be solely useful as anode compounds. For example, and exemplary compound of the present disclosure may have the formula Li4Tis.yMyO|2, wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium, and wherein 0 < y < 1 , without such a compound having the sole use of being used in connection with the preparation of an anode of the present disclosure. Such compounds may have one or more other uses, and as such, any reference to a compound within the disclosure of the present application is not intended to be, and should not be treated as, having a sole utility in connection with anodes.
The various embodiments of compounds, anodes, and batteries of the disclosure of the present application may be useful in connection with one or more vehicles as referenced herein. For example, and in at least one embodiment, a vehicle of the present disclosure may comprise a battery of the present disclosure, wherein the battery comprises an anode, a cathode, and an electrolyte, wherein the anode comprises a lithium-based compound having the formula wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium, and wherein 0 < y < 1. In another embodiment, an exemplary vehicle of the disclosure of the present application comprises a battery comprising an anode comprising a lithium-based compound having the formula wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium, wherein X comprises a chalcogen selected from the group consisting of sulfur, selenium and tellurium, wherein O < y < 1 , and wherein O < z < 2y.
At least one advantage of the disclosure of the present application is to provide materials that can also be used as dopants when mixed with anodic lithium metal oxide that will not reduce the overall cell potential. Several dopants, or combinations of dopants, may be selected to replace some of the transition metal in a LiMyOz system as disclosed herein, but still keep the overall potential below 1.7V. As such, the disclosure of the present application is not limited to any one specific dopant. For example, and in a Li4TJsOi2 anode system of the present disclosure, the titanium can be replaced by molybdenum, tungsten, zirconium, or hafnium (Hf), and still maintain a potential below 1.7V. For such a system, the formula for the active anode material would be LL)Ti5.yMy0|2, wherein O < y ≤ 1, and wherein M = Mo, W, Zr of Hf.
The disclosure of the present application contains embodiments, in addition to replacing the primary transition metal, which replace some of the oxygen with another dopant material as well, such as with sulfur (S), selenium (Se) or tellurium (Te). A general objective remains the same in that gassing would be reduced and the overall potential of the electrode would remain below 1.7V. Molybdenum disulfide (M0S2), for example, as an active material has a potential of ~1.6V vs. Li. Employing the sulfur in place of oxygen will help reduce the material voltage.
Hence, a new chemical formula in accordance with the foregoing is wherein O < y < 1 , wherein O < z < 2y, and wherein M = Mo, W, Zr, or Hf. A more generalized formula in accordance with the foregoing is Li4Ti 5.yMyOi2-zXz> wherein O < y < 1, wherein O < z < 2y, wherein M = Mo, W, Zr, or Hf, and wherein X = S, Se, or Te. In at least one embodiment of such a composition, M = Mo, X = S, y = 0.1, and z = 0.2, so that the formula comprises Li4Ti4^MOo.1On .gS0.2-
An exemplary rechargeable lithium-ion battery whose anode comprises such an electrode material layer has significant advantages such that the magnitude of the volume expansion of the anode when lithium is inserted upon charging and the magnitude of the volume shrinkage of the anode when said lithium is released upon discharging are slight. In addition, the performance of such an anode is more difficult to deteriorate even when charge- and-discharge cycle is repeated over a long period of time, providing such a rechargeable lithium-ion battery with an improved charge-and-discharge cycle life.
An exemplary lithium-based compound of the present disclosure may be prepared as follows. In at least one embodiment, a method for preparing a lithium-based compound comprises the steps of introducing amounts of a first material, a second material, and a third material to a vessel, grinding those ingredients, and heating those ingredients for a period of time at an elevated temperature to create the lithium-based composition. In an exemplary embodiment, the first material comprises lithium, the second material comprises titanium and oxygen, and the third material comprises a dopant material and a chalcogen. Once the ingredients have combined at an elevated temperature, those ingredients may be allowed to cool and/or may be cooled (using a refrigerator, freezer, cold water bath, etc.) and optionally ground, if desired, to produce a room-temperature ground lithium-based compound.
In an exemplary embodiment, a fourth material, namely gas, may be introduced to the vessel prior to and/or during the heating step. In at lease one example, the gas would be introduced to the vessel by providing a flow of the gas to the vessel during the heating step. Such a gas may comprise air, oxygen gas, or any other suitable gas containing oxygen.
In at least one embodiment, the dopant material would comprise molybdenum, tungsten, zirconium, or hafnium, and the chalcogen would comprise sulfur, selenium and tellurium. In various additional examples, one or more of the following ingredients may be used: lithium carbonate as the first material, titanium dioxide or anatase titanium dioxide as the second material, and/or molybdenum disulfide as the third material.
The ingredients may be ground in a vessel using any number of known grinding methods, including the use of a mortar and pestle and/or a ball mill. Such grinding methods illustrated herein are not intended to limit the scope of the present disclosure as other suitable grinding methods may be used. In at least one embodiment, the method would comprise grinding the ingredients in a first vessel, such as a mortar, and heating the ingredients in a second vessel, such as a platinum crucible. The heating step, in at least one method of preparing an exemplary lithium-based compound, would last approximately 24 hours at an elevated temperature is approximately 9000C. After an exemplary lithium-based compound is prepared, it may be stored in a light-proof plastic container, for example, or it may be used to prepare an anode as referenced herein.
In at least one method for preparing a lithium-based composition, the desired lithium-based composition comprises a compound of the formula Li4Ti5.yMyO12.zX2, wherein M comprises the dopant material, wherein X comprises the chalcogen, wherein 0 < y < 1, and wherein 0 < z < 2y. In an exemplary embodiment, the dopant material may comprise consisting of molybdenum, tungsten, zirconium, or hafnium, and the chalcogen may comprise sulfur, selenium and tellurium. In at least one embodiment, y = 0.1 and z = 0.2. In another embodiment, the dopant material comprises molybdenum, the chalcogen comprises sulfur, and z = 0.2.
At least one method of preparing an exemplary lithium-based compound, namely Li4Ti4 9MoO iOn 8So3, is as follows. In at least this example, the starting materials for the preparation of Li4Ti4 , Mo0.|On ,S0 2 are lithium carbonate (Li2CO5) as the Li source, anatase titanium dioxide (TiO-) as the titanium and oxygen source, molybdenum disulfide (M0S2) as the molybdenum (dopant material) and sulfur (chalcogen) source, and dry air as the rest of the oxygen.
In an exemplary batch, 26.62g of Li2CO3, 70.5Og of TiO2, and 2.88g of MoS2 were combined and ground, first by hand in a mortar and pestal. A second grinding in a ball mill was performed to facilitate intimate mixing of the different materials. The ground mixture was then placed in a platinum crucible and fired in a tube furnace at 9000C, under a dry air flow, for 24 hr. The mixture was cooled to room temperature and lightly ground to break up large aggregated clumps of material. The ground material (the resulting lithium-based composition) was then weighed and stored in a light proof plastic container. An expected yield of Li4Ti4 9MOQ. IO , I.8SO 2 for such an exemplary preparation is 84.14g.
An exemplary anode of the present disclosure, or at least a portion of such an anode, may be prepared as follows. In at least one embodiment, a method for preparing at least a portion of an anode, the method comprising the steps of preparing a lithium-based composition of the disclosure of the present application, introducing the lithium-based composition, a conductive medium, a graphite source, and a polymer/binder to a receptacle, mixing those items together, and placing the mixture on a metallic substrate to form at least a portion of an anode. Any or all of the various features, steps, and/or limitations disclosed herein regarding the preparation of a lithium-based composition of the present disclosure may be applicable to the preparation of a lithium-based composition useful to prepare an anode or a portion thereof.
In at least one exemplary embodiment, the conductive medium may comprise acetylene black (ϋenka black). In various embodiments, the polymer/binder may comprise polyvinylidine fluoride (PVDF) and N-methyl pyrolinidone (NMP), and/or the graphite source may comprise SGF6 graphite, also known as Superior Graphite. When mixing the
IO ingredients, small aliquots of the polymer/binder may be added over time to the conductive medium, the graphite source, and the lithium-based compound. Mixing may be stopped when the mixture reaches a desired viscosity. In a least one embodiment, the mixing step is completed when the mixture reaches a viscosity between about 5100 cP and about 5300 cP as indicated by a viscometer operating at approximately 20 RPM.
Once mixed to a desired mixture consistency, said mixture may be positioned on a metallic substrate, such as, for example, copper foil, and dried to prepare at least a portion of an anode. The disclosure of the present application is not intended to be limited to any specific metallic substrate, as, for example, one or more other metallic substrates, such as an aluminum foil, may be suitable for the preparation of an exemplary anode, or part of an anode, of the present disclosure. In an exemplary embodiment, the step of placing the mixture on a metallic substrate comprises feeding the mixture through a fixed-gap slot dye onto the metallic substrate, wherein the metallic substrate is rotated about a spool. In at least one method, the fixed-gap is fixed at 5 μm.
After the mixture is placed on the metallic substrate to form at least a portion of an anode, an exemplary method of preparing at least a portion of an anode may further comprise the step of drying the at least a portion of an anode for a period of time at an elevated temperature under a vacuum. In at least one method, the period of time is approximately 15 hours, and wherein the elevated temperature is approximately 12O0C. Once heated, combination may be cooled under a vacuum, and if desired, it may also be stored within a laminated foil pouch.
In an exemplary anode/electrode preparation, the anode(s) based on Li4Ti4 9Mo0 |O| | BSo 2 are prepared for a lithium-ion cell electrode. Into a planetary paddle mixer, 42.2g of Li4Ti4 9Mθo ιO, I 8S0 2. 2g of Denka black (acetylene black, a conductive medium) and 2g of SGF6 graphite (Superior Graphite) were combined. 33.73g of 13% PVDF solution in N-methyl pyrolinidone (NMP) (binder) was added to the mixture. Small aliquots of NMP were added during mixing, and the mixture was occasionally checked for its viscosity using a Brookfield DV-III viscometer. Mixing was completed when the viscosity reached a value between 5100 and 5300 cP at 20 RPM.
A roll of l Oμm thick copper foil was mounted on a source spool and wound through a coating head made up of a driver roller and a fixed gap slot dye. The gap was fixed to 5μm, and the mixture/slurry as prepared above was is fed through the dye and onto the copper foil. The NMP was removed by drying in a forced air convection oven in line on the coater. The coated copper foil was transferred to the dry room, and dried at 1200C for 15hr under a vacuum. The dried electrode stock was allowed to cool to room temperature under vacuum, and was then sealed in a laminated foil pouch to protect the coating until used.
While various embodiments of compositions, anodes, and batteries been described in considerable detail herein, the embodiments are merely offered by way of non-limiting examples of the disclosure described herein. Many variations and modifications of the embodiments described herein will be apparent to one of ordinary skill in the art in light of this disclosure. It will therefore be understood by those skilled in the art that various changes and modifications may be made, and equivalents may be substituted for elements thereof, without departing from the scope of the disclosure. Indeed, this disclosure is not intended to be exhaustive or to limit the scope of the disclosure.
Further, in describing representative embodiments, the disclosure may have presented a method and/or process as a particular sequence of steps. However, to the extent that the method or process does not rely on the particular order of steps set forth herein, the method or process should not be limited to the particular sequence of steps described. As one of ordinary skill in the art would appreciate, other sequences of steps may be possible. Therefore, the particular order of the steps disclosed herein should not be construed as limitations of the present disclosure. In addition, disclosure directed to a method and/or process should not be limited to the performance of their steps in the order written, and one skilled in the art can readily appreciate that the sequences may be varied and still remain within the spirit and scope of the present disclosure.
It is therefore intended that the disclosure will include all modifications and changes apparent to those of ordinary skill in the art based on this disclosure.

Claims

CLAIMSWe claim:
1. An anode comprising a lithium-based compound having the formula: Li4Ti5-)MyOi2, wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium; and wherein O < y < 1.
2. The anode of claim 1, wherein the dopant material comprises molybdenum.
3. The anode of claim 1 , wherein the dopant material comprises tungsten.
4. The anode of claim 1 , wherein the dopant material comprises zirconium.
5. The anode of claim 1 , wherein the dopant material comprises hafnium.
6. The anode of claim 1 , wherein y = 0.1.
7. The anode of claim 2, wherein y = 0.1.
8. The anode of claim 1 , wherein said anode comprises at least a portion of a battery.
9. The anode of claim 8, wherein the battery comprises a lithium-ion cell.
10. The anode of claim 8, wherein the battery is rechargeable.
1 1. The anode of claim 8, wherein the battery further comprises a cathode, a separator plate positioned at least partially between the anode and the cathode, and an electrolyte.
12. The anode of claim 8, wherein during a charging and discharging battery cycle, at least a portion of the dopant material would be reduced prior to a reduction of titanium.
13. The anode of claim 12, wherein the reduction of at least a portion of the dopant material prior to the reduction of titanium reduces gassing caused by the reduction of titanium.
14. The anode of claim 1, wherein an overall potential is below approximately 1.7V versus lithium.
15. The anode of claim 1 , wherein said anode further comprises graphite.
16. The anode of claim 15, wherein said anode further comprises a binder effective to bind the lithium-based compound to the graphite.
17. The anode of claim 16, wherein the binder comprises polyvinylidine fluoride and N-methyl pyrolinidone.
18. The anode of claim 16, wherein the lithium-based compound bound to the graphite is positioned on a metallic substrate.
19. The anode of claim 18, wherein the metallic substrate comprises copper foil.
20. An anode comprising a compound having the formula: Li<tTi5-yMθyOi2, wherein 0 < y < 1.
21. The anode of claim 20, wherein y = 0.1.
22. An anode comprising a compound having the formula Li,»Ti49M00 1O12.
23. A battery, comprising: an anode; a cathode; and an electrolyte; wherein the anode comprises a lithium-based compound having the formula
Li4Ti5-yMyOi2, wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium; and wherein 0 < y < 1.
24. The battery of claim 23, wherein the dopant material comprises molybdenum.
25. The battery of claim 23, wherein the dopant material comprises tungsten.
26. The battery of claim 23, wherein the dopant material comprises zirconium.
27. The battery of claim 23, wherein the dopant material comprises hafnium.
28. The battery of claim 23, wherein y = 0.1.
29. The battery of claim 24, wherein y = 0.1.
30. The battery of claim 23, wherein the battery comprises a lithium-ion cell.
31. The battery of claim 23, wherein the battery is rechargeable.
32. The battery of claim 23, wherein said battery is charged by extracting lithium ions from the cathode and intercalating said lithium ions into the anode.
33. The battery of claim 23, wherein said battery is discharged by extracting lithium ions from the cathode and intercalating said lithium ions into the cathode.
34. The battery of claim 23, further comprising a separator positioned at least partially between the anode and the cathode.
35. The battery of claim 23, wherein during a charging and discharging battery cycle, at least a portion of the dopant material would be reduced prior to a reduction of titanium.
36. The battery of claim 35, wherein the reduction of at least a portion of the dopant material prior to the reduction of titanium reduces gassing caused by the reduction of titanium.
37. The battery of claim 23, wherein an overall potential is below approximately 1 ,7V versus lithium.
38. The battery of claim 23, wherein said anode further comprises graphite.
39. The battery of claim 38, wherein said anode further comprises a binder effective to bind the lithium-based compound to the graphite.
40. The battery of claim 39, wherein the binder comprises polyvinylidine fluoride and N-methyl pyrolinidone.
41. The battery of claim 39, wherein the lithium-based compound bound to the graphite is positioned on a metallic substrate.
42. A battery, comprising: an anode; a cathode; and an electrolyte; wherein the anode comprises a lithium-based compound having the formula:
Li4Ti 5.yMθyO a, wherein 0 < y < 1.
43. The battery of claim 42, wherein y = 0.1.
44. A battery, comprising: an anode comprising a lithium-based compound having the formula: a cathode; and an electrolyte.
45. An anode comprising a lithium-based compound having the formula: wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium; wherein X comprises a chalcogen; wherein 0 < y < 1 ; and wherein 0 < z < 2y.
46. The anode of claim 45, wherein the dopant material comprises molybdenum.
47. The anode of claim 45, wherein the dopant material comprises tungsten.
48. The anode of claim 45, wherein the dopant material comprises zirconium.
49. The anode of claim 45, wherein the dopant material comprises hafnium.
50. The anode of claim 45, wherein y = 0.1.
51. The anode of claim 46, wherein y = 0.1.
52. The anode of claim 45, wherein the chalcogen is selected from the group consisting of sulfur, selenium and tellurium.
53. The anode of claim 45, wherein the chalcogen comprises sulfur.
54. The anode of claim 45, wherein the chalcogen comprises selenium.
55. The anode of claim 45, wherein the chalcogen comprises tellurium.
56. The anode of claim 45, wherein z = 0.2.
57. The anode of claim 46, wherein the chalcogen comprises sulfur, and wherein z = 0.2.
58. The anode of claim 45, wherein said anode comprises at least a portion of a battery.
59. The anode of claim 58, wherein the battery comprises a lithium-ion cell.
60. The anode of claim 58, wherein the battery is rechargeable.
61. The anode of claim 58, wherein the battery further comprises a cathode, a separator plate positioned at least partially between the anode and the cathode, and an electrolyte.
62. The anode of claim 58, wherein during a charging and discharging battery cycle, at least a portion of the dopant material would be reduced prior to a reduction of titanium.
63. The anode of claim 62, wherein the reduction of at least a portion of the dopant material prior to the reduction of titanium reduces gassing caused by the reduction of titanium.
64. The anode of claim 45, wherein an overall potential is below approximately 1.7V versus lithium.
65. The anode of claim 45, wherein said anode further comprises graphite.
66. The anode of claim 45, wherein said anode further comprises a binder effective to bind the lithium-based compound to the graphite.
67. The anode of claim 66, wherein the binder comprises polyvinylidine fluoride and N-methyl pyrolinidone.
68. The anode of claim 66, wherein the lithium-based compound bound to the graphite is positioned on a metallic substrate.
69. The anode of claim 68, wherein the metallic substrate comprises copper foil.
70. An anode comprising a compound having the formula: Li1)Ti s.yMoyOu.zX., wherein X comprises a chalcogen; wherein 0 < y < 1 ; and wherein 0 < z < 2y.
71. The anode of claim 70, wherein the chalcogen is selected from the group consisting of sulfur, selenium and tellurium.
72. The anode of claim 71 , wherein the chalcogen comprises sulfur.
73. The anode of claim 70, wherein z = 0.2.
74. The anode of claim 72, wherein z = 0.2.
75. An anode comprising a compound having the formula: wherein X comprises a chalcogen.
76. The anode of claim 75, wherein the chalcogen is selected from lhc group consisting of sulfur, selenium and tellurium.
77. The anode of claim 76, wherein the chalcogen comprises sulfur.
78. An anode comprising a compound having the formula ιθn sSo2
79. A battery, comprising: an anode; a cathode; and an electrolyte; wherein the anode comprises a lithium-based compound having the formula: wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium; wherein X comprises a chalcogen; wherein 0 < y < 1; and wherein 0 < z < 2y.
80. The battery of claim 79, wherein the dopant material comprises molybdenum.
81. The battery of claim 79, wherein the dopant material comprises tungsten.
82. The battery of claim 79, wherein the dopant material comprises zirconium.
83. The battery of claim 79, wherein the dopant material comprises hafnium.
84. The battery of claim 79, wherein y = 0.1.
85. The battery of claim 80, wherein y = 0.1.
86. The battery of claim 79, wherein the chalcogen is selected from the group consisting of sulfur, selenium and tellurium.
87. The battery of claim 79, wherein the chalcogen comprises sulfur.
88. The battery of claim 79, wherein the chalcogen comprises selenium.
89. The battery of claim 79, wherein the chalcogen comprises tellurium.
90. The battery of claim 79, wherein z = 0.2.
91. The battery of claim 80, wherein the chalcogen comprises sulfur, and wherein z = 0.2.
92. The battery of claim 79, wherein the battery comprises a lithium-ion cell.
93. The battery of claim 79, wherein the battery is rechargeable.
94. The battery of claim 79, wherein said battery is charged by extracting lithium ions from the cathode and intercalating said lithium ions into the anode.
95. The battery of claim 79, wherein said battery is discharged by extracting lithium ions from the cathode and intercalating said lithium ions into the cathode.
96. The battery of claim 79, further comprising a separator positioned at least partially between the anode and the cathode.
97. The battery of claim 79, wherein during a charging and discharging battery cycle, at least a portion of the dopant material would be reduced prior to a reduction of titanium.
98. The battery of claim 97, wherein the reduction of at least a portion of the dopant material prior to the reduction of titanium reduces gassing caused by the reduction of titanium.
99. The battery of claim 79, wherein an overall potential is below approximately 1.7V versus lithium.
100. The battery of claim 79, wherein said anode further comprises graphite.
101. The battery of claim 100, wherein said anode further comprises a binder effective to bind the lithium-based compound to the graphite.
102. The battery of claim 101 , wherein the binder comprises polyvinylidine fluoride and N-methyl pyrolinidone.
103. The battery of claim 101 , wherein the lithium-based compound bound to the graphite is positioned on a metallic substrate.
104. A battery, comprising: an anode; a cathode; and an electrolyte; wherein the anode comprises a lithium-based compound having the formula:
Li4Ti5.yMoyOn.zX., wherein X comprises a chalcogen; wherein 0 < y < 1 ; and wherein 0 < z < 2y.
105. The battery of claim 104, wherein the chalcogen is selected from the group consisting of sulfur, selenium and tellurium.
106. The battery of claim 105, wherein the chalcogen comprises sulfur.
107. The battery of claim 104, wherein z = 0.2.
108. The battery of claim 106, wherein z = 0.2.
109. A battery, comprising: an anode; a cathode; and an electrolyte; wherein the anode comprises a lithium-based compound having the formula: 8X02, wherein X comprises a chalcogen.
1 10. The battery of claim 109, wherein the chalcogen is selected from the group consisting of sulfur, selenium and tellurium.
1 1 1. The battery of claim 1 10, wherein the chalcogen comprises sulfur.
1 12. An battery, comprising: an anode comprising a compound having the formula Li4TU.9Moo.1O11.8S02; a cathode; and an electrolyte.
1 13. A compound of the formula: Li4Ti5.yMyO|2, wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium; and wherein 0 < y < 1.
1 14. The compound of claim 113, wherein the dopant material comprises molybdenum.
1 15. The compound of claim 1 13, wherein the dopant material comprises tungsten.
1 16. The compound of claim 1 13, wherein the dopant material comprises zirconium.
1 17. The compound of claim 113, wherein the dopant material comprises hafnium.
1 18. The compound of claim 1 13, wherein y = 0.1.
1 19. The compound of claim 114, wherein y = 0.1.
120. The compound of claim 1 13, wherein said compound is an active material of an anode of a lithium-ion battery.
121. A compound of the formula: wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium; wherein X comprises a chalcogen; wherein 0 < y < 1 ; and wherein 0 < z < 2y.
122. The compound of claim 121 , wherein the dopant material comprises molybdenum.
123. The compound of claim 121, wherein the dopant material comprises tungsten.
124. The compound of claim 121, wherein the dopant material comprises zirconium.
125. The compound of claim 121, wherein the dopant material comprises hafnium.
126. The compound of claim 121 , wherein y = 0.1.
127. The compound of claim 122, wherein y = 0.1.
128. The compound of claim 121 , wherein the chalcogen is selected from the group consisting of sulfur, selenium and tellurium.
129. The compound of claim 121, wherein the chalcogen comprises sulfur.
130. The compound of claim 121, wherein the chalcogen comprises selenium.
131. The compound of claim 121 , wherein the chalcogen comprises tellurium.
132. The compound of claim 121 , wherein z = 0.2.
133. The compound of claim 121 , wherein the chalcogen comprises sulfur, and wherein z = 0.2.
134. The compound of claim 121 , wherein said compound is an active material of an anode of a lithium-ion battery.
135. A compound of the formula:
Li4Ti5-yMθyO 12-zXz» wherein X comprises a chalcogen; wherein 0 < y < 1 ; and wherein 0 < z < 2y.
136. The compound of claim 135, wherein the chalcogen is selected from the group consisting of sulfur, selenium and tellurium.
137. The compound of claim 135, wherein the chalcogen comprises sulfur.
138. The compound of claim 135, wherein the chalcogen comprises selenium.
139. The compound of claim 135, wherein the chalcogen comprises lellurium.
140. The compound of claim 135, wherein z = 0.2.
141. The compound of claim 135, wherein the chalcogen comprises sulfur, and wherein z = 0.2.
142. The compound of claim 135, wherein said compound is an active material of an anode of a lithium-ion battery.
143. A compound of the formula:
Li4Ti4.9Moo.1O1 |.8Xθ.2> wherein X comprises a chalcogen.
144. The compound of claim 143, wherein the chalcogen comprises sulfur.
145. The compound of claim 143, wherein the chalcogen comprises selenium.
146. The compound of claim 143, wherein the chalcogen comprises tellurium.
147. The compound of claim 143, wherein said compound is an active material of an anode of a lithium-ion battery.
148. A compound of the formula: Li4Ti49M00. ιθi ).8So.2, wherein said compound is an active material of an anode of a lithium-ion battery.
149. A method of preparing a lithium-based composition, the method comprising the steps of: introducing amounts of a first material, a second material, and a third material to a vessel, wherein the first material comprises lithium, wherein the second material comprises titanium and oxygen, and wherein the third material comprises a dopant material and a chalcogen; grinding the first material, the second material, and the third material within the vessel; and heating the ground vessel contents for a period of time at an elevated temperature to create the lithium-based composition.
150. The method of claim 149, further comprising the step of cooling the vessel contents after the step of heating the ground vessel contents.
151. The method of claim 149, further comprising the step of introducing a fourth material to the vessel, wherein the fourth material comprises a gas.
152. The method of claim 151, wherein the gas comprises air.
153. The method of claim 151 , wherein the gas comprises oxygen gas.
154. The method of claim 149, wherein the dopant material is selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium.
155. The method of claim 149, wherein the chalcogen is selected from the group consisting of sulfur, selenium and tellurium.
156. The method of claim 149, wherein the first material comprises lithium carbonate.
157. The method of claim 149, wherein the second material comprises titanium dioxide.
158. The method of claim 149, wherein the second material comprises anatase titanium dioxide.
159. The method of claim 149, wherein the third material comprises molybdenum disulfide.
160. The method of claim 149, wherein the first material comprises lithium carbonate, wherein the second material comprises anatase titanium dioxide, and wherein the third material comprises molybdenum disulfide.
161. The method of claim 149, wherein the grinding step is performed using a mortar and pestle.
162. The method of claim 149, wherein the grinding step is performed using a ball mill.
163. The method of claim 149, wherein the grinding step comprises grinding in a first vessel, and wherein the heating step comprises heating a second vessel.
164. The method of claim 163, wherein the first vessel comprises a mortar, and wherein the second vessel comprises a platinum crucible.
165. The method of claim 151 , wherein the fourth material is introduced to the vessel by providing a flow of the fourth material to the vessel during the heating step.
166. The method of claim 149, wherein the period of time is approximately 24 hours.
167. The method of claim 149, wherein the elevated temperature is approximately 9000C.
168. The method of claim 150, further comprising the step of grinding the lithium- based composition after the lithium-based composition has cooled below 9000C.
169. The method of claim 150, further comprising the step of storing the lithium- based composition within a plastic container.
170. The method of claim 169, wherein the plastic container is light-proof.
171. The method of claim 149, wherein the lithium-based composition comprises a compound of the formula:
Li4Ti5.yMyOl2-ZXz. wherein M comprises the dopant material, wherein the dopant material is selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium; wherein X comprises the chalcogen, wherein the chalcogen is selected from the group consisting of sulfur, selenium and tellurium; wherein 0 < y < 1 ; and wherein 0 < z < 2y.
172. The method of claim 171 , wherein z = 0.2.
173. The method of claim 121, wherein the dopant material comprises molybdenum, wherein the chalcogen comprises sulfur, and wherein z = 0.2.
174. The method of claim 149, wherein the lithium-based composition comprises
175. A method of preparing a lithium-based composition, the method comprising the steps of: introducing lithium carbonate, anatase titanium dioxide, and molybdenum disulfide to a vessel; grinding lithium carbonate, anatase titanium dioxide, and molybdenum disulfide within the vessel; and heating the ground vessel contents for a period of time at an elevated temperature to create the lithium-based composition.
176. The method of claim 175, further comprising the step of cooling the vessel contents after the step of heating the ground vessel contents.
177. The method of claim 175, wherein the period of time is approximately 24 hours, and wherein the elevated temperature is approximately 9000C.
178. The method of claim 175, wherein the lithium-based composition comprises Li.1Ti49Moo.1O11 δSiθ 2-
179. A method for preparing at least a portion of an anode, the method comprising the steps of: preparing a lithium-based composition, the method comprising the steps of: introducing amounts of a first material, a second material, and a third material to a vessel, wherein the first material comprises lithium, wherein the second material comprises titanium and oxygen, and wherein the third material comprises a dopant material and a chakogen; grinding the first material, the second material, and the third material within the vessel; and heating the ground vessel contents for a period of time at an elevated temperature to create the lithium-based composition; and cooling the lithium-based composition; and introducing the lithium-based composition, a conductive medium, a graphite source, and a binder to a receptacle; mixing the lithium-based composition, a conductive medium, a graphite source, and a binder within the receptacle to form a mixture; and placing the mixture on a metallic substrate to form at least a portion of an anode.
180. The method of claim 179, further comprising the step of introducing a fourth material to the vessel, wherein the fourth material comprises a gas comprising oxygen.
181. The method of claim 180, wherein the fourth material is introduced to the vessel by providing a flow of the fourth material to the vessel during the heating step
182. The method of claim 179, wherein the dopant material is selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium.
183. The method of claim 179, wherein the chalcogen is selected from the group consisting of sulfur, selenium and tellurium.
184. The method of claim 179, wherein the first material comprises lithium carbonate.
185. The method of claim 179, wherein the second material comprises titanium dioxide.
186. The method of claim 179, wherein the second material comprises anatase titanium dioxide.
187. The method of claim 179, wherein the third material comprises molybdenum disulfide.
188. The method of claim 179, wherein the first material comprises lithium carbonate, wherein the second material comprises anatase titanium dioxide, and wherein the third material comprises molybdenum disulfide.
189. The method of claim 179, wherein the period of time is approximately 24 hours.
190. The method of claim 179, wherein the elevated temperature is approximately 9000C.
191 . The method of claim 179, further comprising the step of grinding the lithium- based composition after the lithium-based composition has cooled below 9000C.
192. The method of claim 179, wherein the conductive medium comprises acetylene black.
193. The method of claim 179, wherein the binder comprises polyvinylidine fluoride and N-methyl pyrolinidone.
194. The method of claim 179, wherein the mixing step is completed when the mixture reaches a viscosity between about 5100 cP and about 5300 cP as indicated by a viscometer operating at approximately 20 RPM.
195. The method of claim 179, wherein the metallic substrate comprises copper foil.
196. The method of claim 179, wherein the step of placing the mixture on a metallic substrate comprises feeding the mixture through a fixed-gap slot dye onto the metallic substrate, wherein the metallic substrate is rotated about a spool.
197. The method of claim 196, wherein the fixed-gap is fixed at 5 μm.
198. The method of claim 179, further comprising the step of drying the at least a portion of an anode for a period of time at an elevated temperature under a vacuum.
199. The method of claim 198, wherein the period of time is approximately 15 hours, and wherein the elevated temperature is approximately 1200C.
200. The method of claim 198, further comprising the step of cooling the at least a portion of the anode under a vacuum.
201. The method of claim 200, further comprising the step of storing the at least a portion of an anode within a laminated foil pouch.
202. A battery, comprising: an anode; a cathode; and an electrolyte; wherein the anode comprises a spinel and at least one dopant selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium.
203. The battery of claim 202, wherein the spinel comprises at least one lithium metal oxide.
204. The battery of claim 202, wherein the at least one lithium metal oxide comprises Li4Ti5O^.
205. A vehicle, comprising: a battery, comprising: an anode; a cathode; and an electrolyte; wherein the anode comprises a lithium-based compound having the formula: wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium; and wherein 0 < y < 1.
206. A vehicle, comprising: a battery, comprising: an anode; a cathode; and an electrolyte; wherein the anode comprises a lithium-based compound having the formula: wherein M comprises a dopant material selected from the group consisting of molybdenum, tungsten, zirconium, and hafnium; wherein X comprises a chalcogcn selected from the group consisting of sulfur, selenium and tellurium; wherein 0 < y < 1 ; and wherein 0 < z < 2y.
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