New! View global litigation for patent families

US20090035663A1 - Stabilized lithium metal powder for li-ion application, composition and process - Google Patents

Stabilized lithium metal powder for li-ion application, composition and process Download PDF

Info

Publication number
US20090035663A1
US20090035663A1 US11870544 US87054407A US2009035663A1 US 20090035663 A1 US20090035663 A1 US 20090035663A1 US 11870544 US11870544 US 11870544 US 87054407 A US87054407 A US 87054407A US 2009035663 A1 US2009035663 A1 US 2009035663A1
Authority
US
Grant status
Application
Patent type
Prior art keywords
lithium
metal
powder
oil
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11870544
Inventor
Marina Yakovleva
Yuan Gao
Kenneth Brian Fitch
B. Troy Dover
Prakash Thyaga Palepu
Jian-Xin Li
Brian Anthony Christopher Carlin
Yangxing Li
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.)
FMC Corp
Original Assignee
FMC Corp
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

Links

Images

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F1/00Special treatment of metallic powder, e.g. to facilitate working, to improve properties; Metallic powders per se, e.g. mixtures of particles of different composition
    • B22F1/0003Metallic powders per se; Mixtures of metallic powders; Metallic powders mixed with a lubricating or binding agent
    • B22F1/0059Metallic powders mixed with a lubricating or binding agent or organic material
    • B22F1/0062Powders coated with organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F1/00Special treatment of metallic powder, e.g. to facilitate working, to improve properties; Metallic powders per se, e.g. mixtures of particles of different composition
    • B22F1/02Special treatment of metallic powder, e.g. to facilitate working, to improve properties; Metallic powders per se, e.g. mixtures of particles of different composition comprising coating of the powder
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H01M4/1315Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134Electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387Tin or alloys based on tin
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40Alloys based on alkali metals
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F1/00Special treatment of metallic powder, e.g. to facilitate working, to improve properties; Metallic powders per se, e.g. mixtures of particles of different composition
    • B22F1/0003Metallic powders per se; Mixtures of metallic powders; Metallic powders mixed with a lubricating or binding agent
    • B22F1/0059Metallic powders mixed with a lubricating or binding agent or organic material
    • B22F1/0077Mixtures obtained by warm mixing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M2004/026Electrodes composed of or comprising active material characterised by the polarity
    • H01M2004/027Negative electrodes

Abstract

The present invention provides a lithium metal powder protected by a wax. The resulting lithium metal powder has improved stability and improved storage life.

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • [0001]
    This application claims priority to U.S. Provisional Application Ser. No. 60/829,378, filed Oct. 13, 2006, the disclosure of which is incorporated by reference in its entirety.
  • FIELD OF INVENTION
  • [0002]
    The present invention relates to stabilized lithium metal powder (“SLMP”) having better stability and a longer storage life. Such improved SLMP can be used in a wide variety of applications including organo-metal and polymer synthesis, rechargeable lithium batteries, and rechargeable lithium ion batteries.
  • BACKGROUND OF THE INVENTION
  • [0003]
    The high surface area of lithium metal can be a deterrent for its use in a variety of applications because of its pyrophoric nature. It is known to stabilize lithium metal powder by passivating the metal powder surface with CO2 such as described in U.S. Pat. Nos. 5,567,474, 5,776,369, and 5,976,403, the disclosures of which are incorporated herein in their entireties by reference. The CO2-passivated lithium metal powder, however, can be used only in air with low moisture levels for a limited period of time before the lithium metal content decays because of the reaction of the lithium metal and air. Thus there remains a need for stable lithium metal with an improved storage life.
  • SUMMARY OF THE INVENTION
  • [0004]
    The present invention provides a lithium metal powder protected by a wax. A continuous wax layer provides improved protection such as compared to, for example, CO2 passivation. The resulting lithium metal powder has improved stability and improved storage life. Furthermore, the wax-protected lithium metal powder exhibits better stability in N-methyl-2-pyrrolidone (NMP), which is widely used as a solvent in the electrode fabrication process in the rechargeable lithium-ion battery industry. Similarly, the wax-protected lithium metal powder of the invention exhibits better stability in gamma-butyrolactone (GBL).
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [0005]
    FIG. 1 is a stability comparison of the wax-coated lithium metal powder of Example 1 and a CO2-stabilized lithium metal powder in dry NMP.
  • [0006]
    FIG. 2 is a comparison of the cycle performance of graphite electrode with wax as an additive and without wax additive.
  • [0007]
    FIG. 3 is a side-by-side comparison of ARSST stability test temperature profiles for the wax-coated lithium metal powder and of CO2-coated lithium metal powder in 0.6 percent water-doped NMP.
  • [0008]
    FIG. 4 is a stability comparison of Example 1 and CO2-stabilized lithium metal powder in 0.6 percent water-doped NMP.
  • [0009]
    FIG. 5 is an accelerated hygroscopisity tested conducted at 25° C. and 75 percent relative humidity for NMP and GBL.
  • DETAILED DESCRIPTION OF THE INVENTION
  • [0010]
    In the drawings and the following detailed description, preferred embodiments are described in detail to enable practice of the invention. Although the invention is described with reference to these specific embodiments, it will be understood that the invention is not limited to these embodiments. But to the contrary, the invention includes numerous alternatives, modifications and equivalents as will become apparent from consideration of the following detailed description and accompanying drawing.
  • [0011]
    The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. As used herein, the singular forms “a”, “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
  • [0012]
    Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein
  • [0013]
    In accordance with the present invention, lithium dispersions are prepared by heating the lithium metal powder in a hydrocarbon oil to a temperature above its melting point, subjecting the lithium metal powder to conditions sufficient to disperse the molten lithium (e.g., agitating or stirring vigorously), and contacting the dispersed lithium metal powder with a wax at a temperature that is between this temperature and the melting point of the wax. Other alkali metals such as sodium and potassium can be coated according to the present invention.
  • [0014]
    A variety of hydrocarbon oils may be used in the present invention. The term hydrocarbon oil, as used herein, includes various oily liquids consisting chiefly or wholly of mixtures of hydrocarbons and includes mineral oils, i.e., liquid products of mineral origin having viscosity limits recognized for oils and hence includes but is not limited to petroleum, shale oils, paraffin oils and the like. There are many manufacturers of these useful hydrocarbon oils. Among these useful hydrocarbon oils are highly refined oils, such as, Peneteck manufactured by Penreco Division of Pennzoil Products Inc., which has a viscosity in the range of 43-59 pascal-sec at 100° F. and a flash point of 265° F., Parol 100, which has a viscosity of 213-236 pascal-sec at 100° F. and a flash point of 360° F. (available from Penreco, Div. of Pennzoil Products), and Carnation white oil (viscosity=133-165 pascal-sec at 100° F.) made by Sonneborn Div. of Witco. Even certain purified hydrocarbon solvents which boil in a range encompassing the melting point of lithium or sodium metal may be used, such as UNOCAL's 140 Solvent. In addition, unrefined oils, such as Unocal's 460 Solvent and Hydrocarbon Seal oil and Exxon's Telura 401 and Telura 407 may also be used. The selection of a hydrocarbon oil will be within the skill of one in the art.
  • [0015]
    Suitable waxes can be natural wax such as 12-hydroxystearic acid, synthetic wax such as low molecular weight polyethylene, petroleum waxes such as paraffin wax, and microcrystalline waxes. The wax can be introduced to contact the lithium droplets during the dispersion, or at a lower temperature after the lithium dispersion has cooled. It is understood that combinations of different types of waxes with different chemical compositions, molecular weights, melting points and hardness could be used to achieve specific coating characteristics for particular applications. For example, degree of stickiness could be controlled to allow introduction of the SLMP using a “transfer release paper” concept, wherein a certain degree of stickiness is required.
  • [0016]
    Furthermore, it is beneficial to combine the wax or wax mixtures of the invention with other inorganic coatings, for example, Li2CO3, LiF, Li3PO4, SiO2, Li4SiO4, LiAlO2, Li2TiO3, LiNbO3 and the like, to improve both air stability and polar solvent stability that would allow both safer handling and possibility of using commonly used polar solvents that dissolve commonly used polymer binders. It is recognized that most waxes are soluble in non-polar solvents at elevated temperatures and solubility at room temperature is above 0.5%. For example, wax is soluble in NMP at room temperature at about 0.1% level.
  • [0017]
    Suitable waxes described above could produce two types of coatings on lithium particles: first type representing physical or adhesive type where non-polar waxes are used and a second type, representing chemically bonded coatings where waxes with functional groups, having both hydrophobic and hydrophilic features, are used. The coating thickness could vary in the range of about 20 nm to about 200 nm.
  • [0018]
    By altering the process parameters and the order of the reagents addition to the lithium dispersion or lithium dry powder, the wax-coated lithium metal powder of the invention can have distinct surface properties. For example, waxes could be introduced at or below melting point of lithium followed by the addition of other dispersants above the melting point of lithium, and, therefore, the wax serves as dispersant/coating reagents. Other suitable dispersants include oleic acid, linoleic acid, sodium oleate, lithium oleate, linseed oil, CO2, N2, NH3, telura oil, stearic acid, oxalic acid, tanic acid, CO, and other waxes. Waxes or wax mixtures could be introduced above the melting point of lithium before or after other dispersants and coating reagents additions, for example the reagents that result in formation of the coatings such as Li2CO3, LiF, Li3PO4, SiO2, Li4SiO4, LiAlO2, Li2TiO3, and LiNbO3, and the like, to enhance the chemical bonding and uniformity of protecting layer by changing the reaction interfaces. The cooling profile could be used to control degree of crystallinity and obtain samples with pre-determined degree of stickiness.
  • [0019]
    Alternatively, stabilized lithium metal powder could be dispersed into the melted non-polar paraffin-like waxes or a mixture of waxes, and poured into the candle type mold for crystallization and the concentration of lithium powder could be calculated as a function of length or volume. Consequently, a piece of a “candle” could serve as a lithium carrier and used for organo-metallic and or polymer syntheses; the inert wax could be extracted with a solvent or allowed to crystallize out and filtered out upon reaction completion.
  • [0020]
    In another embodiment, stabilized lithium metal powder could be dispersed into the melted non-polar paraffin-like waxes or a mixture of waxes with mineral oil to form a lithium powder containing slurry or paste that could be used in a caulk-gun like apparatus for lithium powder delivery.
  • [0021]
    The process produces lithium dispersions having metal particle sizes in the range of 10 to 500 microns. Moreover, the tendency of the lithium particles to float to the top of the slurry is obviated by practice of the present invention. It is recognized that one skilled in the art will be able to choose the appropriate particle size depending on the intended use of the lithium dispersion. On cooling, the resulting lithium dispersions are readily filtered to remove the bulk of the dispersant hydrocarbon oil and the metal can then be washed with a solvent such as hexane to remove residual oil, after which, the metal powder can be dried. The hydrocarbon oil filtrate is clear and colorless and may be recycled, without further treatment, to the metal dispersion process. This is in contrast to the prior art processes which require clay column purification of the oil before reuse. The dried metal powders are unexpectedly stable to ambient atmosphere allowing their safe transfer in such atmospheres from one container to another.
  • [0022]
    Lithium metal used with various embodiments of the present invention may be provided as lithium powder. The lithium powder may be treated or otherwise conditioned for stability during transportation. For instance, dry lithium powder may be formed in the presence of carbon dioxide as conventionally known. It may be packaged under an inert atmosphere such as argon. The dry lithium powder may be used with the various embodiments of the present invention. Alternatively, the lithium powder may be formed in a suspension, such as in a suspension of mineral oil solution or other solvents. Formation of lithium powder in a solvent suspension may facilitate the production of smaller lithium metal particles, for example, wherein 100 percent of particles are less than 100 micron. In some embodiments of the present invention, a lithium powder may be formed in a solvent that may be used with various embodiments of the present invention. The lithium metal powder formed in the solvent may be transported in the solvent. Further, the lithium metal powder and solvent mixture may be used with embodiments of the present invention, wherein the step of drying SLMP is eliminated. This may decrease production costs and allow the use of smaller or finer lithium metal powder particles with the embodiments of the present invention.
  • [0023]
    Alternatively the stabilized lithium metal powder can be produced by spraying the molten metal through an atomizer nozzle, and the waxing step can take place after the powder has been collected. For example, lithium powder could be collected into lithium compatible solvent containing dry wax or pre-dissolved wax and the mixture brought to or above the temperature of the clear point of wax in the solvent, and in one embodiment above the melting point of lithium. The solvent can be stripped away, using rotary evaporator, as an example, causing wax to crystallize onto the lithium particles. Solvents used with embodiments of the invention must also be non-reactive with the lithium metal and the binder polymers (binders could be soluble in the solvents compatible with lithium) at the temperatures used in the anode production process. Preferably, a solvent or co-solvent possesses sufficient volatility to readily evaporate from a slurry to promote the drying of a slurry applied to a current collector. For example, solvents may include acyclic hydrocarbons and cyclic hydrocarbons including NMP, GBL, n-hexane, n-heptane, cyclohexane, and the like, aromatic hydrocarbons, such as toluene, xylene, isopropylbenzene (cumene), and the like symmetrical, unsymmetrical, and cyclic ethers, including di-n-butyl ether, methyl t-butyl ether, and the like.
  • [0024]
    In one embodiment, the lithium metal powder protected with wax coating enables the use of dry NMP solvent.
  • [0025]
    The stabilized lithium metal powder can be used in a secondary battery such as described in U.S. Pat. No. 6,706,447 B2, the disclosure of which is incorporated by reference in its entirety. A typical secondary battery comprises a positive electrode or cathode, a negative electrode or anode, a separator for separating the positive electrode and the negative electrode, and an electrolyte in electrochemical communication with the positive electrode and the negative electrode. The secondary battery also includes a current collector that is in electrical contact with the cathode and a current collector that is in electrical contact with the anode. The current collectors are in electrical contact with one another through an external circuit. The secondary battery can have any construction known in the art such as a “jelly roll” or stacked construction.
  • [0026]
    The cathode is formed of an active material, which is typically combined with a carbonaceous material and a binder polymer. The active material used in the cathode is preferably a material that can be lithiated at a useful voltage (e.g., 2.0 to 5.0 V versus lithium). Preferably, non-lithiated materials such as MnO2, V2O5 or MoS2, certain transition metal phosphates, certain transition metal fluorides, or mixtures thereof, can be used as the active material. However, lithiated materials such as LiMn2O4 that can be further lithiated can also be used. The non-lithiated active materials are selected because they generally have higher specific capacities, better safety, lower cost and broader choice than the lithiated active materials in this construction and thus can provide increased power over secondary batteries that use only lithiated active materials. Furthermore, because the anode includes lithium as discussed below, it is not necessary that the cathode includes a lithiated material for the secondary battery to operate. The amount of active material provided in the cathode is preferably sufficient to accept the removable lithium metal present in the anode.
  • [0027]
    The anode is formed of a host material capable of absorbing and desorbing lithium in an electrochemical system with the stabilized lithium metal powder dispersed in the host material. For example, the lithium present in the anode can intercalate in, alloy with or be absorbed by the host material when the battery (and particularly the anode) is recharged. The host material includes materials capable of absorbing and desorbing lithium in an electrochemical system such as carbonaceous materials; materials containing Si, Sn, tin and silicon oxides or composite tin and or silicon alloys or intermetallics; transition metal oxides such as cobalt oxide; lithium metal nitrides such as Li3-xCoxN where 0<x<0.5, and lithium metal oxides such as Li4Ti5O12.
  • [0028]
    An alternative use of the stabilized lithium metal powder is in the preparation of organo lithium products in good yields. The thin wax layer is believed to not significantly retard reactivity but does protect the metal from reaction with ambient atmosphere.
  • [0029]
    The following examples are merely illustrative of the invention, and are not limiting thereon.
  • EXAMPLES Comparative Example 1
  • [0030]
    Battery grade lithium metal 405 grams was cut into 2×2 inch pieces and charged under constant flow of dry argon at room temperature to a 3 liter stainless steel flask reactor with a 4″ top fitted with a stirring shaft connected to a fixed high speed stirrer motor. The reactor was equipped with top and bottom heating mantles. The reactor was then assembled and 1041.4 g of Peneteck™ oil (Penreco, Division of the Penzoil Products Company) was added. The reactor was then heated to about 200° C. and gentle stirring was maintained in the range of 250 rpm to 800 rpm to ensure all metal was molten, argon flow was maintained through out the heating step. Then the mixture was stirred at high speed (up to 10,000 rpm) for 2 minutes. Oleic acid, 8.1 g was charged into the reactor and high speed stirring continued for another 3 minutes followed by the 5.1 g CO2 addition. Then the high speed stirring was stopped, heating mantles removed and dispersion was allowed to cool to about 50° C. and transferred to the storage bottles. Further, lithium dispersion was filtered and washed three times with hexane and once with n-pentane in an enclosed, sintered glass filter funnel to remove the hydrocarbon oil medium while under argon flow. The funnel was heated with a heat gun to remove traces of the solvents and the resulting free-flowing powder was transferred to a tightly capped storage bottles.
  • Example 1
  • [0031]
    Lithium dispersion in oil, 55.72 grams, (11.275%) containing 6.28 grams of lithium with a medium particle size of 58 micron was charged into 120 ml hastelloy can equipped with a 1″ Teflon coated stir bar. The solution was heated to 75° C. and 0.63 grams of Luwax A (BASF) in a form of 10% solution in p-xylene (Aldrich) pre-dissolved at 72° C. was added to the lithium dispersion. This mixture was continuously stirred at 200 rpm for 22 hours. Sample was allowed to cool to the room temperature and transferred to the storage bottle. Further, lithium dispersion was filtered and washed three times with hexane in an enclosed, sintered glass filter funnel and twice with n-pentane to remove the hydrocarbon oil medium. The funnel was heated with a heat gun to remove traces of the solvents and the resulting free-flowing powder was transferred to a tightly capped storage bottles.
  • [0032]
    FIG. 1 shows that no exothermic effects were observed when Example 1 was mixed at room temperature in dry NMP (<100 ppm H2O). Moreover, unlike sample described in Comparative Example 1 that had no metallic lithium left after four days of exposure to dry NMP solvent, 54 percent metallic lithium was still present in Example 1. Furthermore, unlike sample described in Comparative Example 1, wax-coated lithium powder is even stable with NMP with the amount of moisture of 0.6 percent. FIG. 2 illustrates that when 1 wt % wax is introduced into the battery, (addition is calculated based on a fully lithiated carbon using 10% wax-coated SLMP) there are no adverse effects. Half cells of Li/Carbon were tested using Arbin battery cycler BT-2043. The cells were cycled at 0.50 mA/cm2 with a potential window of 0.01˜1.5 V.
  • [0033]
    FIG. 3 shows an ARSST (advanced reactive screening system tool) calorimeter test where samples were exposed to the 0.6 percent water doped NMP under continuous stirring and three days isothermal hold at room temperature was followed by the 2 days isothermal hold at 55° C. Runaway reaction was observed for the CO2-coated lithium powder at about 48 hours of hold at room temperature while no exothermic effect was observed for the wax-coated lithium metal powder of Example 1. Upon completion of these types of tests, the lithium metallic concentration for the wax-coated samples is at least 40 percent. FIG. 4 shows the metallic lithium concentration measured for the wax-coated sample followed by their exposure to the 0.6 percent water doped NMP over the period of 10 days at room temperature.
  • [0034]
    Solvent hygroscopisity causes quality and performance issues for the Li-ion batteries (for example, high moisture content might cause binder polymer to re-crystallize, thus reducing its binding properties, thus causing electrode film to crack, delaminate, thus causing failure of the battery). FIG. 5 shows accelerated hygroscopicity test results conducted at 25° C. and 75 percent relative humidity. For example, while NMP absorbs ˜0.6 percent of moisture within 7 hours of exposure, GBL absorbs only 0.23 percent of moisture. This shows that the wax-coated lithium metal powder is even more stable in GBL.
  • Example 2
  • [0035]
    Lithium dispersion in oil, 780 g, (32.1%) that contained 250 g of lithium with a medium particle size of 63 micron was charged under constant flow of dry argon at room temperature to a 5 liter three neck glass flask reactor fitted with a stirring shaft connected to a fixed high speed stirrer motor. The reactor was equipped with bottom heating mantles. The reactor was then heated to about 75° C. and gentle stirring was maintained to ensure uniform distribution and heat transfer. 25 g of Luwax A (BASF) in a form of a 10% solution pre-dissolved in p-xylene at 72° C. was charged into the reactor and stirring continued for another 8 hours. The solution was then cooled slowly and kept at room temperature while being further stirred for 14 hrs and then transferred to the storage bottles. Further, lithium dispersion was filtered and washed three times with hexane in an enclosed, sintered glass filter funnel and twice with n-pentane to remove the hydrocarbon oil medium. The funnel was heated with a heat gun to remove traces of the solvents and the resulting free-flowing powder was transferred to a tightly capped storage bottles.
  • [0036]
    A pyrophoricity test (Method 1050 of DOT regulations for the transport of spontaneously combustible materials, Code of Federal Regulations part 173, Appendix E) performed on this material showed it to be non-pyrophoric.
  • Example 3
  • [0037]
    Lithium dispersion in mineral oil 21.45 grams (27.5%) that contained 5.90 g of lithium and had medium particle size of 63 microns and 0.62 g Luwax A powder were charged under constant flow of dry argon at room temperature to a 125 ml glass flask reactor with a magnetic stirrer bar controlled by super magnetic stirrer. The reactor was equipped with bottom heating mantle. The reactor was then heated to the temperature range of 90° C. to 100° C. and stirring was maintained at ˜400 rpm to ensure uniform distribution and heat transfer for a period of about 1 hour followed by a natural cooling.
  • Example 4
  • [0038]
    Lithium dispersion in mineral oil 21.56 grams (27.5%) that contained 5.93 g of lithium and had medium particle size of 63 microns and 0.61 g Luwax A powder were charged under constant flow of dry argon at room temperature to a 125 ml glass flask reactor with a magnetic stirrer bar controlled by super magnetic stirrer. Gentle stirring was maintained ˜50 rpm to ensure uniform distribution and heat transfer before temperature was increased to 90° C. The reactor was equipped with bottom heating mantle. The reactor was then heated to the temperature range of 90° C. to 100° C. and then the stirring was increased to ˜200 rpm, and the mixture was kept under stirring for about 15 minutes. Then, the heating mantle was taken off and the reactor was allowed to cool naturally.
  • Example 5
  • [0039]
    Lithium dispersion in mineral oil, 21.72 grams (27.5%) that contained 5.97 g of lithium and had medium particle size of 63 microns was charged under constant flow of dry argon at room temperature to a 125 ml glass flask reactor with a magnetic stirrer bar controlled by super magnetic stirrer. Gentle stirring was maintained at ˜30 rpm to ensure uniform distribution and heat transfer before temperature was increased to 90° C. The reactor was equipped with bottom heating mantle. After the reactor was heated to the temperature of 90° C., 6.55 g (10%) pre-dissolved Luwax A solution in mineral oil was charged into the reactor and the stirring increased to 200 rpm. Then the mixture was kept under stirring for about 15 minutes followed by natural cooling.
  • Example 6
  • [0040]
    Lithium dispersion in mineral oil, stabilized with the CO2-gas, 22.30 grams, (27.5%) that contained 6.13 g of lithium with medium particle size of 45 microns was charged under constant flow of dry argon at room temperature to a 125 ml glass flask reactor with a magnetic stirrer bar controlled by super magnetic stirrer. Gentle stirring was maintained ˜30 rpm to ensure uniform distribution and heat transfer before temperature increased to 90° C. The reactor was equipped with bottom heating mantle. After the reactor was heated to the temperature of 90° C., 6.52 g pre-dissolved 10% Luwax A solution in mineral oil was charged into the reactor and the stirring increased to ˜200 rpm. Then the mixture was kept under stirring for about 15 minutes followed by the natural cooling.
  • Example 7
  • [0041]
    5 g of dry stabilized lithium metal powder (LectroMax Powder 150, FMC), 75 g p-xylene (Aldrich) and 0.1 g Luwax A powder (BASF) were charged under constant flow of dry argon at room temperature to a 200 ml three neck glass flask reactor fitted with a stirring shaft connected to a fixed high speed stirrer motor. The reactor was equipped with bottom heating mantles. The reactor was then heated to about 75° C. and gentle stirring was maintained to ensure uniform distribution and heat transfer. The mixture was stirred for 20 minutes at 75° C. and the heating mantle was then removed to allow the sample to cool rapidly. Further, mixture was filtered in an enclosed, sintered glass filter funnel. The sample was dried by passing dry argon through the filter. The resulting free-flowing powder was transferred to a tightly capped storage bottles.
  • Example 8
  • [0042]
    Dry stabilized lithium metal powder, 10 g, (LectroMax Powder 150, FMC), 50 g p-xylene (Aldrich) and 0.5 g Luwax A powder (BASF) were charged in an argon filled glove box at room temperature to a 250 ml round bottom flask. The flask was then attached to a rotary vacuum solvent extractor (Buchi Rotavapor R110) and partially submerged in a mineral oil bath at room temperature. The flask was turned while the mineral oil bath was heated to 80° C. The temperature of the mixture was maintained at 80° C. with no vacuum applied for 30 minutes. A vacuum of 25 inches of Hg was then applied to strip the p-xylene. After 50% of the solvent was removed, the flask was raised out of the oil bath and allowed to cool rapidly. The remaining solvent was filtered in an enclosed, sintered glass filter funnel. The sample was dried by passing dry argon through the filter. The resulting free-flowing powder was transferred to a tightly capped storage bottles.
  • Example 9
  • [0043]
    4924 g of mineral oil and 1364 g of battery grade lithium metal rods were added to an argon inerted 5 gallon dispersion apparatus. The mixture was heated to temperature above lithium melting point under an argon atmosphere with stirring to ensure that all lithium has melted. The high speed disperser blade was then started and a mixture of 27 g of oleic acid and 29 g of mineral oil was introduced into the dispersion pot. After an additional several minutes of high speed stirring, 18 g of CO2 carbon dioxide gas was introduced. After this, the high speed stirring was brought down to minimum speed and reaction mixture cooled down to 105° C. with external cooling. 136 g of Luwax A powder (BASF) was introduced and the temperature was maintained above 95° C. for the next 15 minutes followed by cooling to ambient temperature. The wax coated SLMP dispersion was then transferred out of the pot. A sample of the dispersion was washed with hexane and pentane to remove the mineral oil. The material was then dried under argon.
  • Example 10
  • [0044]
    Dry stabilized lithium metal powder, 10 g, (LectroMax Powder 150, FMC), 50 g p-xylene (Aldrich) and 0.5 g Luwax A powder (BASF) were charged in an argon filled glove box at room temperature to a 250 ml round bottom flask. The flask was then attached to a rotary vacuum solvent extractor (Buchi Rotavapor R110) and partially submerged in a mineral oil bath at room temperature. The flask was turned while the mineral oil bath was heated to 80° C. The temperature of the mixture was maintained at 80° C. with no vacuum applied for 30 minutes. A vacuum of 25 inches of Hg was then applied to strip the p-xylene. As the sample began to dry the vacuum was lowered to 30 inches of Hg to remove the remaining solvent. The flask was removed from the rotary evaporator and the sample was further dried by passing dry argon through the flask. The resulting powder was transferred to a tightly capped storage bottles.
  • Example 11
  • [0045]
    Battery grade lithium metal 4427 g and 15345 g of mineral oil were added to a 15 gallon dispersion pot. The mixture was heated to the temperature above the melting point of lithium metal while stirring. Then the high speed disperser blade was set into motion at 4800 rpm and a mixture of 90 gm of oleic acid and 90 g of mineral oil was introduced in to the dispersion pot. After several minutes of high speed dispersion, 58 g of carbon dioxide gas was introduced in to the pot and allowed to react with the metal particles. The high speed disperser was shut off shortly after CO2 addition and cold mineral oil was added to the mix to bring the temperature of the dispersion below the melting point of lithium metal. Anchor agitator was used to continue stirring the dispersion mixture until the material was cooled down to the room temperature to promote uniformity of the suspension. External cooling was applied to the system. The material was discharged and analyzed. The mean diameter of the stabilized lithium dispersion was 52 micron.
  • Example 12
  • [0046]
    Battery grade lithium metal 44137 g and 15436 g of mineral oil were added to a 15 gallon dispersion pot. The mixture was heated to the temperature above the melting point of lithium metal under continuous stirring. Then the high speed disperser blade was set into motion at 4800 rpm and a mixture of 89 gm of oleic acid and 87 g of mineral oil was introduced into the dispersion pot. After several minutes of high speed dispersion, 57 g of carbon dioxide gas was charged into the pot and allowed to react with the metal particles. Upon completion of the reaction, 118 g of Luwax S was introduced into the pot. After additional high speed mixing the high speed disperser was shut off and cold mineral oil was added to the mix to bring the temperature below the melting point of lithium metal. Anchor agitator was used to continue stirring the dispersion mixture until the material was cooled down to the room temperature to promote uniformity of the suspension. External cooling was applied to the system. The material was discharged and analyzed. The mean diameter of the stabilized lithium dispersion was 40 micron.
  • [0047]
    These two examples and figures demonstrate that wax could be used both as a coating reagent and as a dispersant reagent. This is a very important property that could be used in designing products with reduced particle size/increased surface area for specific applications, for example spraying SLMP powder in the solvent solution onto the electrode surfaces or continuously introducing dry SLMP powder into the Tokamak edge using the “gun”-like devices to increase plasma stability and electron temperatures and reduce the impurity levels (lithium is a getter). Table 1 below summarizes specific process conditions and particle size results.
  • [0000]
    TABLE 1
    Process conditions and experimental results for examples 11 and 12
    Oleic Dispersing Stabilizing D50
    acid, % Speed RPM Additives micron
    Example 11 2% 4800 1.25% CO2 52
    Example 12 2% 4800 1.25% CO2 & 2.5% 40
    Luwax S
  • [0048]
    Having thus described certain embodiments of the present invention, it is to be understood that the invention defined by the appended claims is not to be limited by particular details set forth in the above description as many apparent variations thereof are possible without departing from the spirit or scope thereof as hereinafter claimed. The following claims are provided to ensure that the present application meets all statutory requirements as a priority application in all jurisdictions and shall not be construed as setting forth the full scope of the present invention.

Claims (17)

  1. 1. A stabilized lithium metal powder coated with a wax.
  2. 2. The stabilized lithium metal powder of claim 1, wherein the wax has a thickness of 20 μm to 200 μm.
  3. 3. The stabilized lithium metal powder of claim 2, wherein the wax is selected from the group consisting of natural waxes, synthetic waxes, petroleum waxes, and microcrystalline waxes.
  4. 4. The stabilized lithium metal powder of claim 3, further comprising an inorganic coating.
  5. 5. The stabilized lithium metal powder of claim 4, wherein the inorganic coating is selected from the group consisting of Li2CO3, LiF, Li3PO4, SiO2, Li4SiO4, LiAlO2, Li2TiO3, and LiNbO3.
  6. 6. An anode comprising a host material capable of absorbing or desorbing lithium in an electrochemical system wherein the stabilized lithium metal of claim 1 is dispersed in the host material.
  7. 7. An anode comprising a host material capable of absorbing or desorbing lithium in an electrochemical system wherein the stabilized lithium metal of claim 3 is dispersed in the host material.
  8. 8. The anode of claim 6, wherein said host material comprises at least one material selected from the group consisting of carbonaceous materials, silicon, tin, tin oxides, composite tin alloys, transition metal oxides, lithium metal nitrides, graphite, carbon black, and lithium metal oxides.
  9. 9. The anode of claim 7, wherein said host material comprises at least one material selected from the group consisting of carbonaceous materials, silicon, tin, tin oxides, composite tin alloys, transition metal oxides, lithium metal nitrides, graphite, carbon black, and lithium metal oxides.
  10. 10. The stabilized lithium metal powder according to claim 1, wherein said powder has a mean diameter of from 10 μm to 200 μm in N-methyl-2-pyrrolidone.
  11. 11. The stabilized lithium metal powder according to claim 1, wherein said powder has a mean diameter of from 10 μm to 200 μm in gamma-butyrolactone.
  12. 12. A method of forming a lithium dispersion comprising the steps of:
    a) contacting lithium metal powder with a hydrocarbon oil;
    b) heating the lithium metal powder and hydrocarbon oil to a temperature higher than the melting point of the lithium metal powder;
    c) subjecting the heated lithium metal powder and hydrocarbon oil to conditions sufficient to disperse the lithium metal powder in the oil; and
    d) contacting the lithium metal powder with a wax at a temperature between the melting point of the lithium metal powder and the melting point of the wax.
  13. 13. The method of claim 12, wherein the wax has a thickness of 20 nm to 200 nm.
  14. 14. The method of claim 12, wherein the hydrocarbon oil is selected from the group consisting of petroleum oils, shale oils, and paraffin oils.
  15. 15. A method of forming a lithium dispersion comprising the steps of:
    a) contacting lithium metal powder with a hydrocarbon oil;
    b) heating the lithium metal powder and hydrocarbon oil to a temperature higher than the melting point of the lithium metal powder;
    c) adding a dispersant and a coating reagent;
    d) subjecting the heated lithium metal powder and hydrocarbon oil to conditions sufficient to disperse the lithium metal powder in the oil; and
    e) contacting the lithium metal powder with a wax at a temperature between the melting point of the lithium metal powder and the melting point of the wax.
  16. 16. The method of claim 15, wherein the wax has a thickness of 20 nm to 200 nm.
  17. 17. The method of claim 15, further comprising an inorganic coating.
US11870544 2006-10-13 2007-10-11 Stabilized lithium metal powder for li-ion application, composition and process Abandoned US20090035663A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US82937806 true 2006-10-13 2006-10-13
US11870544 US20090035663A1 (en) 2006-10-13 2007-10-11 Stabilized lithium metal powder for li-ion application, composition and process

Applications Claiming Priority (15)

Application Number Priority Date Filing Date Title
US11870544 US20090035663A1 (en) 2006-10-13 2007-10-11 Stabilized lithium metal powder for li-ion application, composition and process
CN 201110154403 CN102255080B (en) 2006-10-13 2007-10-12 Stabilized lithium metal powder for li-ion application, composition and process
EP20100192630 EP2338622B1 (en) 2006-10-13 2007-10-12 Stabilized lithium metal powder for li-ion application, composition and process.
CA 2660789 CA2660789C (en) 2006-10-13 2007-10-12 Stabilized lithium metal powder for li-ion application, composition and process
PCT/US2007/021894 WO2008045557A1 (en) 2006-10-13 2007-10-12 Stabilized lithium metal powder for li-ion application, composition and process
GB0901850A GB2453095B (en) 2006-10-13 2007-10-12 Anode and method of forming anode
GB201109888A GB2478239B (en) 2006-10-13 2007-10-12 Stabilized lithium metal powder for Li-ion application, composition and process
CN 200780037907 CN101522343B (en) 2006-10-13 2007-10-12 Stabilized lithium metal powder for li-ion application, composition and process
KR20097005901A KR101458078B1 (en) 2006-10-13 2007-10-12 Stabilized lithium metal powder for Li-ion application, composition and process
DE200711002375 DE112007002375T5 (en) 2006-10-13 2007-10-12 Stabilized lithium metal powder for Li-ion application, composition and method
EP20070839528 EP2073946B1 (en) 2006-10-13 2007-10-12 Anode and method of forming lithium dispersion
JP2009532448A JP5351033B2 (en) 2006-10-13 2007-10-12 Stabilized lithium metal powder
US13151371 US20110226987A1 (en) 2006-10-13 2011-06-02 Anode for electrochemical system
US14604036 US20150132641A1 (en) 2006-10-13 2015-01-23 Stabilized lithium metal powder for li-ion application, composition and process
US15830707 US20180083273A1 (en) 2006-10-13 2017-12-04 Stabilized lithium metal powder for li-ion application, composition and process

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US13151371 Division US20110226987A1 (en) 2006-10-13 2011-06-02 Anode for electrochemical system
US14604036 Continuation US20150132641A1 (en) 2006-10-13 2015-01-23 Stabilized lithium metal powder for li-ion application, composition and process

Publications (1)

Publication Number Publication Date
US20090035663A1 true true US20090035663A1 (en) 2009-02-05

Family

ID=39091992

Family Applications (4)

Application Number Title Priority Date Filing Date
US11870544 Abandoned US20090035663A1 (en) 2006-10-13 2007-10-11 Stabilized lithium metal powder for li-ion application, composition and process
US13151371 Abandoned US20110226987A1 (en) 2006-10-13 2011-06-02 Anode for electrochemical system
US14604036 Abandoned US20150132641A1 (en) 2006-10-13 2015-01-23 Stabilized lithium metal powder for li-ion application, composition and process
US15830707 Pending US20180083273A1 (en) 2006-10-13 2017-12-04 Stabilized lithium metal powder for li-ion application, composition and process

Family Applications After (3)

Application Number Title Priority Date Filing Date
US13151371 Abandoned US20110226987A1 (en) 2006-10-13 2011-06-02 Anode for electrochemical system
US14604036 Abandoned US20150132641A1 (en) 2006-10-13 2015-01-23 Stabilized lithium metal powder for li-ion application, composition and process
US15830707 Pending US20180083273A1 (en) 2006-10-13 2017-12-04 Stabilized lithium metal powder for li-ion application, composition and process

Country Status (9)

Country Link
US (4) US20090035663A1 (en)
EP (2) EP2073946B1 (en)
JP (1) JP5351033B2 (en)
KR (1) KR101458078B1 (en)
CN (2) CN102255080B (en)
CA (1) CA2660789C (en)
DE (1) DE112007002375T5 (en)
GB (2) GB2478239B (en)
WO (1) WO2008045557A1 (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050239917A1 (en) * 2004-02-18 2005-10-27 Solicore, Inc. Lithium inks and electrodes and batteries made therefrom
US20080283155A1 (en) * 2007-05-16 2008-11-20 Fmc Corporation, Lithium Division Stabilized lithium metal powder for Li-ion application, composition and process
US20090061321A1 (en) * 2007-08-31 2009-03-05 Fmc Corporation, Lithium Division Stabilized lithium metal powder for li-ion application, composition and process
US20110104571A1 (en) * 2009-11-02 2011-05-05 Aruna Zhamu Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries
WO2011068767A1 (en) 2009-12-03 2011-06-09 Fmc Corporation Finely deposited lithium metal powder
JP2013514459A (en) * 2009-12-18 2013-04-25 ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツングChemetall GmbH Lithium metal and a manufacturing method thereof that surface passivation
US20130181160A1 (en) * 2010-09-28 2013-07-18 Chemetall Gmbh Stabilized, pure lithium metal powder and method for producing the same
US20150037682A1 (en) * 2012-01-13 2015-02-05 Rockwood Lithium GmbH Phosphorous-coated lithium metal products, method for production and use thereof
US9029013B2 (en) 2013-03-13 2015-05-12 Uchicago Argonne, Llc Electroactive compositions with poly(arylene oxide) and stabilized lithium metal particles
US20160087263A1 (en) * 2012-11-09 2016-03-24 Corning Incorporated Encapsulated lithium particles and methods of making and use thereof
US20160164073A1 (en) * 2014-06-16 2016-06-09 The Regents Of The University Of California Porous Silicon Oxide (SiO) Anode Enabled by a Conductive Polymer Binder and Performance Enhancement by Stabilized Lithium Metal Power (SLMP)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010044008A1 (en) 2010-11-16 2012-05-16 Varta Micro Innovation Gmbh Lithium-ion cell with an improved aging behavior
CN102064316A (en) * 2010-12-24 2011-05-18 上海中兴派能能源科技有限公司 Method for making negative electrode of lithium ion battery and lithium ion battery
DE102011003016A1 (en) 2011-01-24 2012-07-26 Varta Micro Innovation Gmbh Electrode for lithium-ion batteries and their preparation
CN102130359A (en) * 2011-01-25 2011-07-20 天津中能锂业有限公司 Lithium sulfur battery and preparation method thereof
CA2857491A1 (en) * 2011-12-01 2013-06-06 Nanoscale Components, Inc. Method for alkaliating anodes
US20150010826A1 (en) * 2012-01-13 2015-01-08 Rockwood Lithium GmbH Stabilized lithium metal impressions coated with alloy-forming elements and method for production thereof
US8871385B2 (en) 2012-01-27 2014-10-28 Battelle Energy Alliance, Llc Electrodes including a polyphosphazene cyclomatrix, methods of forming the electrodes, and related electrochemical cells
CN102642024B (en) * 2012-03-06 2014-07-23 宁德新能源科技有限公司 Lithium ion battery and anode strip thereof and stabilization lithium metal powder
CN103779572B (en) * 2012-10-26 2016-02-24 华为技术有限公司 A lithium ion battery negative electrode additive and preparation method, a lithium ion battery and a lithium ion battery negative electrode sheet
EP3198671A1 (en) * 2014-09-23 2017-08-02 Corning Incorporated Encapsulated lithium particles and methods of making and use thereof
US9183994B2 (en) * 2012-11-28 2015-11-10 Corning Incorporated Lithium ion capacitors and methods of production
KR20150110797A (en) 2013-01-30 2015-10-02 나노스캐일 컴포넌츠, 인코포레이티드 Phased introduction of lithium into the pre-lithiated anode of a lithium ion electrochemical cell
CA2909681A1 (en) 2013-04-19 2014-10-23 Rockwood Lithium GmbH Stabilized lithium metal formations coated with a shell containing nitrogen, and method for producing same
CN105098189B (en) * 2014-05-21 2018-02-16 微宏动力系统(湖州)有限公司 The method of preparing a negative electrode material and additives
KR20170126480A (en) * 2015-03-02 2017-11-17 이오셀 리미티드 Silicon: silicon lithium silicate composite silicon having a silicon nano-particles embedded in a substrate-silicon oxide-lithium composite material and its preparation method

Citations (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6168885A (en) *
US3271196A (en) * 1961-11-08 1966-09-06 Leesona Corp Fuel cell electrodes
US3508967A (en) * 1967-09-22 1970-04-28 Gulton Ind Inc Negative lithium electrode and electrochemical battery containing the same
US4615959A (en) * 1984-05-07 1986-10-07 Sanyo Chemical Industries, Ltd. Secondary battery or cell with improved rechargeability
US4668595A (en) * 1985-05-10 1987-05-26 Asahi Kasei Kogyo Kabushiki Kaisha Secondary battery
US4945014A (en) * 1988-02-10 1990-07-31 Mitsubishi Petrochemical Co., Ltd. Secondary battery
US5028500A (en) * 1989-05-11 1991-07-02 Moli Energy Limited Carbonaceous electrodes for lithium cells
US5153082A (en) * 1990-09-04 1992-10-06 Bridgestone Corporation Nonaqueous electrolyte secondary battery
US5162176A (en) * 1991-01-19 1992-11-10 Varta Batterie Aktiengesellschaft Electrochemical secondary element
US5286582A (en) * 1990-11-02 1994-02-15 Seiko Electronic Components Ltd. Monaqueous electrolyte secondary battery and process for producing positive active materials
US5312623A (en) * 1993-06-18 1994-05-17 The United States Of America As Represented By The Secretary Of The Army High temperature, rechargeable, solid electrolyte electrochemical cell
US5312611A (en) * 1991-01-14 1994-05-17 Kabushiki Kaisha Toshiba Lithium secondary battery process for making carbonaceous material for a negative electrode of lithium secondary battery
US5543021A (en) * 1994-09-01 1996-08-06 Le Carbone Lorraine Negative electrode based on pre-lithiated carbonaceous material for a rechargeable electrochemical lithium generator
US5587256A (en) * 1994-07-08 1996-12-24 Moli Energy (1990) Limited Carbonaceous insertion compounds and use as anodes in rechargeable batteries
US5643665A (en) * 1993-06-14 1997-07-01 Valence Technology, Inc. Lithium containing solid electrochemical cells
US5672446A (en) * 1996-01-29 1997-09-30 Valence Technology, Inc. Lithium ion electrochemical cell
US5707756A (en) * 1994-11-29 1998-01-13 Fuji Photo Film Co., Ltd. Non-aqueous secondary battery
US5725968A (en) * 1992-12-07 1998-03-10 Honda Giken Kogyo Kabushiki Kaisha Alkaline ion-absorbing/desorbing carbon material electrode material for secondary battery using the carbon material and lithium secondary battery using the electron material
US5753387A (en) * 1995-11-24 1998-05-19 Kabushiki Kaisha Toshiba Lithium secondary battery
US5753388A (en) * 1995-04-12 1998-05-19 Valence Technology, Inc. Process for prelithiation of carbon based anodes for lithium ion electrochemical cells
US5776369A (en) * 1993-02-18 1998-07-07 Fmc Corporation Alkali metal dispersions
US5807645A (en) * 1997-06-18 1998-09-15 Wilson Greatbatch Ltd. Discharge promoter mixture for reducing cell swelling in alkali metal electrochemical cells
US5948569A (en) * 1997-07-21 1999-09-07 Duracell Inc. Lithium ion electrochemical cell
US5951919A (en) * 1997-12-30 1999-09-14 Korea Kumho Petro Chemical Co., Ltd. Method of preparing cathode material for lithium ion cell
US5958622A (en) * 1996-03-28 1999-09-28 Kabushiki Kaisha Toyota Chuo Kenkyusho Negative electrode material for lithium secondary batteries
US6156457A (en) * 1997-03-11 2000-12-05 Kabushiki Kaisha Toshiba Lithium secondary battery and method for manufacturing a negative electrode
US6168885B1 (en) * 1998-09-08 2001-01-02 Sri International Fabrication of electrodes and devices containing electrodes
US6183911B1 (en) * 1999-03-10 2001-02-06 Samsung Display Devices Co., Ltd. Positive active material for rechargeable lithium battery and method of preparing same
US6265110B1 (en) * 1996-12-20 2001-07-24 Danionics A/S Lithium secondary battery with flake graphite negative electrode
US6270926B1 (en) * 1996-07-16 2001-08-07 Murata Manufacturing Co., Ltd. Lithium secondary battery
US6387564B1 (en) * 1997-02-28 2002-05-14 Asahi Kasei Kabushiki Kaisha Non-aqueous secondary battery having an aggregation layer
US20020119373A1 (en) * 2000-12-22 2002-08-29 Fmc Corporation Lithium metal dispersion in secondary battery anodes
US6465126B1 (en) * 1999-06-14 2002-10-15 Telefonaktiebolaget L M Ericsson (Publ) Binder and/or electrolyte material
US6541156B1 (en) * 1999-11-16 2003-04-01 Mitsubishi Chemical Corporation Negative electrode material for non-aqueous lithium secondary battery, method for manufacturing the same, and non-aqueous lithium secondary battery using the same
US20040002005A1 (en) * 2000-12-22 2004-01-01 Yuan Gao Lithium metal dispersion in secondary battery anodes
US20040146784A1 (en) * 2000-12-22 2004-07-29 Yuan Gao Lithium metal dispersion in secondary battery anodes
US20050130043A1 (en) * 2003-07-29 2005-06-16 Yuan Gao Lithium metal dispersion in electrodes

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58199806A (en) * 1982-05-17 1983-11-21 Toshiba Corp Production of metallic lithium powder
WO1994019100A1 (en) 1993-02-18 1994-09-01 Fmc Corporation Alkali metal dispersions
JP2004508687A (en) * 2000-08-19 2004-03-18 ゼノ エナジー カンパニー、リミテッド Lithium powder cathode, a lithium battery and a process for their preparation using the same
DE10150610A1 (en) * 2001-10-12 2003-04-30 Clariant Gmbh A process for the preparation of organic organometallic intermediates through amide bases
GB0414161D0 (en) * 2004-06-24 2004-07-28 Aea Technology Battery Systems Anode for lithium ion cell
WO2008014354A3 (en) * 2006-07-25 2008-11-27 Cqgt Llc Charting with depth of market volume flow
US8021496B2 (en) * 2007-05-16 2011-09-20 Fmc Corporation Stabilized lithium metal powder for Li-ion application, composition and process

Patent Citations (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6168885A (en) *
US3271196A (en) * 1961-11-08 1966-09-06 Leesona Corp Fuel cell electrodes
US3508967A (en) * 1967-09-22 1970-04-28 Gulton Ind Inc Negative lithium electrode and electrochemical battery containing the same
US4615959A (en) * 1984-05-07 1986-10-07 Sanyo Chemical Industries, Ltd. Secondary battery or cell with improved rechargeability
US4668595A (en) * 1985-05-10 1987-05-26 Asahi Kasei Kogyo Kabushiki Kaisha Secondary battery
US4945014A (en) * 1988-02-10 1990-07-31 Mitsubishi Petrochemical Co., Ltd. Secondary battery
US5028500A (en) * 1989-05-11 1991-07-02 Moli Energy Limited Carbonaceous electrodes for lithium cells
US5153082A (en) * 1990-09-04 1992-10-06 Bridgestone Corporation Nonaqueous electrolyte secondary battery
US5286582A (en) * 1990-11-02 1994-02-15 Seiko Electronic Components Ltd. Monaqueous electrolyte secondary battery and process for producing positive active materials
US5312611A (en) * 1991-01-14 1994-05-17 Kabushiki Kaisha Toshiba Lithium secondary battery process for making carbonaceous material for a negative electrode of lithium secondary battery
US5162176A (en) * 1991-01-19 1992-11-10 Varta Batterie Aktiengesellschaft Electrochemical secondary element
US5725968A (en) * 1992-12-07 1998-03-10 Honda Giken Kogyo Kabushiki Kaisha Alkaline ion-absorbing/desorbing carbon material electrode material for secondary battery using the carbon material and lithium secondary battery using the electron material
US5976403A (en) * 1993-02-18 1999-11-02 Fmc Corporation Organoalkali compounds and their preparation
US5776369A (en) * 1993-02-18 1998-07-07 Fmc Corporation Alkali metal dispersions
US5643665A (en) * 1993-06-14 1997-07-01 Valence Technology, Inc. Lithium containing solid electrochemical cells
US5312623A (en) * 1993-06-18 1994-05-17 The United States Of America As Represented By The Secretary Of The Army High temperature, rechargeable, solid electrolyte electrochemical cell
US5587256A (en) * 1994-07-08 1996-12-24 Moli Energy (1990) Limited Carbonaceous insertion compounds and use as anodes in rechargeable batteries
US5543021A (en) * 1994-09-01 1996-08-06 Le Carbone Lorraine Negative electrode based on pre-lithiated carbonaceous material for a rechargeable electrochemical lithium generator
US5707756A (en) * 1994-11-29 1998-01-13 Fuji Photo Film Co., Ltd. Non-aqueous secondary battery
US5753388A (en) * 1995-04-12 1998-05-19 Valence Technology, Inc. Process for prelithiation of carbon based anodes for lithium ion electrochemical cells
US5753387A (en) * 1995-11-24 1998-05-19 Kabushiki Kaisha Toshiba Lithium secondary battery
US5672446A (en) * 1996-01-29 1997-09-30 Valence Technology, Inc. Lithium ion electrochemical cell
US5958622A (en) * 1996-03-28 1999-09-28 Kabushiki Kaisha Toyota Chuo Kenkyusho Negative electrode material for lithium secondary batteries
US6270926B1 (en) * 1996-07-16 2001-08-07 Murata Manufacturing Co., Ltd. Lithium secondary battery
US6265110B1 (en) * 1996-12-20 2001-07-24 Danionics A/S Lithium secondary battery with flake graphite negative electrode
US6387564B1 (en) * 1997-02-28 2002-05-14 Asahi Kasei Kabushiki Kaisha Non-aqueous secondary battery having an aggregation layer
US6156457A (en) * 1997-03-11 2000-12-05 Kabushiki Kaisha Toshiba Lithium secondary battery and method for manufacturing a negative electrode
US5807645A (en) * 1997-06-18 1998-09-15 Wilson Greatbatch Ltd. Discharge promoter mixture for reducing cell swelling in alkali metal electrochemical cells
US5948569A (en) * 1997-07-21 1999-09-07 Duracell Inc. Lithium ion electrochemical cell
US5951919A (en) * 1997-12-30 1999-09-14 Korea Kumho Petro Chemical Co., Ltd. Method of preparing cathode material for lithium ion cell
US6168885B1 (en) * 1998-09-08 2001-01-02 Sri International Fabrication of electrodes and devices containing electrodes
US6183911B1 (en) * 1999-03-10 2001-02-06 Samsung Display Devices Co., Ltd. Positive active material for rechargeable lithium battery and method of preparing same
US6465126B1 (en) * 1999-06-14 2002-10-15 Telefonaktiebolaget L M Ericsson (Publ) Binder and/or electrolyte material
US6541156B1 (en) * 1999-11-16 2003-04-01 Mitsubishi Chemical Corporation Negative electrode material for non-aqueous lithium secondary battery, method for manufacturing the same, and non-aqueous lithium secondary battery using the same
US20020119373A1 (en) * 2000-12-22 2002-08-29 Fmc Corporation Lithium metal dispersion in secondary battery anodes
US20040002005A1 (en) * 2000-12-22 2004-01-01 Yuan Gao Lithium metal dispersion in secondary battery anodes
US6706447B2 (en) * 2000-12-22 2004-03-16 Fmc Corporation, Lithium Division Lithium metal dispersion in secondary battery anodes
US20040146784A1 (en) * 2000-12-22 2004-07-29 Yuan Gao Lithium metal dispersion in secondary battery anodes
US7276314B2 (en) * 2000-12-22 2007-10-02 Fmc Corporation Lithium metal dispersion in secondary battery anodes
US20050130043A1 (en) * 2003-07-29 2005-06-16 Yuan Gao Lithium metal dispersion in electrodes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Mujumdar et al. (Improvement of humidity resistance of magnesium powder using dry particle coating, Powder Technology 140 (2004) 86-97). *
Zhang et al. (Formation of organic coating on ultrafine silver particles using a gas-phase process, Aerosol Science 35 (2004) 457-471) *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7968233B2 (en) 2004-02-18 2011-06-28 Solicore, Inc. Lithium inks and electrodes and batteries made therefrom
US8318358B2 (en) 2004-02-18 2012-11-27 Solicore, Inc. Lithium inks and electrodes and batteries made therefrom
US20050239917A1 (en) * 2004-02-18 2005-10-27 Solicore, Inc. Lithium inks and electrodes and batteries made therefrom
US9925813B2 (en) 2004-02-18 2018-03-27 Brightvolt, Inc. Lithium inks and electrodes and batteries made therefrom
US20080283155A1 (en) * 2007-05-16 2008-11-20 Fmc Corporation, Lithium Division Stabilized lithium metal powder for Li-ion application, composition and process
US8377236B2 (en) 2007-05-16 2013-02-19 Fmc Corporation Stabilized lithium metal powder for Li-ion application, composition and process
US8021496B2 (en) * 2007-05-16 2011-09-20 Fmc Corporation Stabilized lithium metal powder for Li-ion application, composition and process
US20090061321A1 (en) * 2007-08-31 2009-03-05 Fmc Corporation, Lithium Division Stabilized lithium metal powder for li-ion application, composition and process
US8236452B2 (en) 2009-11-02 2012-08-07 Nanotek Instruments, Inc. Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries
US20110104571A1 (en) * 2009-11-02 2011-05-05 Aruna Zhamu Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries
US20110135810A1 (en) * 2009-12-03 2011-06-09 Marina Yakovleva Finely deposited lithium metal powder
WO2011068767A1 (en) 2009-12-03 2011-06-09 Fmc Corporation Finely deposited lithium metal powder
JP2013514459A (en) * 2009-12-18 2013-04-25 ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツングChemetall GmbH Lithium metal and a manufacturing method thereof that surface passivation
US20130181160A1 (en) * 2010-09-28 2013-07-18 Chemetall Gmbh Stabilized, pure lithium metal powder and method for producing the same
US20150037682A1 (en) * 2012-01-13 2015-02-05 Rockwood Lithium GmbH Phosphorous-coated lithium metal products, method for production and use thereof
US9601762B2 (en) * 2012-01-13 2017-03-21 Rockwood Lithium GmbH Phosphorous-coated lithium metal products, method for production and use thereof
US20160087263A1 (en) * 2012-11-09 2016-03-24 Corning Incorporated Encapsulated lithium particles and methods of making and use thereof
US9029013B2 (en) 2013-03-13 2015-05-12 Uchicago Argonne, Llc Electroactive compositions with poly(arylene oxide) and stabilized lithium metal particles
US20160164073A1 (en) * 2014-06-16 2016-06-09 The Regents Of The University Of California Porous Silicon Oxide (SiO) Anode Enabled by a Conductive Polymer Binder and Performance Enhancement by Stabilized Lithium Metal Power (SLMP)

Also Published As

Publication number Publication date Type
EP2338622A2 (en) 2011-06-29 application
CN102255080A (en) 2011-11-23 application
US20180083273A1 (en) 2018-03-22 application
EP2073946A1 (en) 2009-07-01 application
GB201109888D0 (en) 2011-07-27 grant
CN101522343B (en) 2013-07-24 grant
CN101522343A (en) 2009-09-02 application
EP2073946B1 (en) 2010-12-08 grant
GB2453095B (en) 2012-01-18 grant
EP2338622A3 (en) 2011-11-30 application
GB2478239A (en) 2011-08-31 application
US20150132641A1 (en) 2015-05-14 application
US20110226987A1 (en) 2011-09-22 application
KR101458078B1 (en) 2014-11-04 grant
GB2478239B (en) 2012-01-18 grant
JP5351033B2 (en) 2013-11-27 grant
CA2660789C (en) 2014-08-19 grant
GB0901850D0 (en) 2009-03-11 grant
GB2453095A (en) 2009-03-25 application
EP2338622B1 (en) 2016-10-19 grant
CN102255080B (en) 2015-06-24 grant
KR20090069167A (en) 2009-06-29 application
DE112007002375T5 (en) 2009-08-27 application
JP2010507197A (en) 2010-03-04 application
CA2660789A1 (en) 2008-04-17 application
WO2008045557A1 (en) 2008-04-17 application

Similar Documents

Publication Publication Date Title
US7169328B2 (en) Multiphase nanocomposite material and method for its manufacture
US20050136330A1 (en) Carbon-coated silicon particle power as the anode material for lithium batteries and the method of making the same
US20050031957A1 (en) Multi-phase, silicon-containing electrode for a lithium-ion battery
US20040002005A1 (en) Lithium metal dispersion in secondary battery anodes
US5472808A (en) Solid electrolyte and batteries
US20050130043A1 (en) Lithium metal dispersion in electrodes
US5512214A (en) Lithium battery electrode compositions
US20030175589A1 (en) Process for manufacture of negative electrode material for a non-aqueous electrolyte secondary battery
JP2007294423A (en) Silicon-silicon oxide-lithium based composite and its manufacturing method as well as negative electrode material for nonaqueous electrolyte secondary battery
US20120270107A1 (en) Nickel-cobalt-manganese complex hydroxide particles and method for producing same, positive electrode active material for nonaqueous electrolyte secondary battery and method for producing same, and nonaqueous electrolyte secondary battery
JP2000340257A (en) Lithium secondary battery
JP2004214054A (en) Negative electrode active material for lithium secondary battery, its manufacturing method, and lithium secondary battery
JP2006100255A (en) Metal silicon powder for non-aqueous electrolyte secondary battery negative electrode material, and non-aqueous electrolyte secondary battery negative electrode
JP2000149937A (en) Negative electrode material for nonaqueous electrolyte secondary battery, and its manufacture
US7323120B2 (en) Coated carbonaceous particles particulary useful as electrode materials in electrical storage cells, and methods of making the same
JP2002075351A (en) Alloy powder for negative electrode of nonaqueous electrolyte secondary battery and method for manufacturing the alloy powder
JP2007294461A (en) Cathode material for manufacturing rechargeable battery
JP2009211950A (en) Solid electrolyte and its manufacturing method
JP2004247249A (en) Manufacturing method of electrode for secondary battery
JP2005071771A (en) Negative electrode active material for lithium secondary battery,its manufacturing method, and lithium secondary battery
JP2004095469A (en) Negative electrode material for nonaqueous electrolyte secondary battery and manufacturing method of same
US20080283155A1 (en) Stabilized lithium metal powder for Li-ion application, composition and process
US20090061321A1 (en) Stabilized lithium metal powder for li-ion application, composition and process
JP2004235057A (en) Negative electrode for lithium secondary battery, and the battery
US20050053718A1 (en) Positive active material for rechargeable lithium-sulfur batteries and method of preparing same

Legal Events

Date Code Title Description
AS Assignment

Owner name: FMC CORPORATION, LITHIUM DIVISION, PENNSYLVANIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YAKOVLEVA, MARINA;GAO, YUAN;FITCH, KENNETH BRIAN;AND OTHERS;REEL/FRAME:020173/0370;SIGNING DATES FROM 20071030 TO 20071127