US20090061321A1 - 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

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US20090061321A1
US20090061321A1 US12/198,313 US19831308A US2009061321A1 US 20090061321 A1 US20090061321 A1 US 20090061321A1 US 19831308 A US19831308 A US 19831308A US 2009061321 A1 US2009061321 A1 US 2009061321A1
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Prior art keywords
lithium metal
lithium
polymer
stabilized
metal powder
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US12/198,313
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Marina Yakovleva
Yuan Gao
Kenneth Brian Fitch
Prakash Thyaga Palepu
Yangxing Li
Christopher Jay Woltermann
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FMC Corp
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FMC Corp
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Priority to US12/198,313 priority Critical patent/US20090061321A1/en
Priority to KR1020107006808A priority patent/KR20100081304A/en
Priority to CA2696771A priority patent/CA2696771C/en
Priority to RU2010112410/02A priority patent/RU2010112410A/en
Priority to EP12157983.3A priority patent/EP2463940B1/en
Priority to CN201610044145.0A priority patent/CN105618735A/en
Priority to JP2010522937A priority patent/JP5548126B2/en
Priority to CN200880104518A priority patent/CN101790806A/en
Priority to PCT/US2008/010152 priority patent/WO2009029270A1/en
Priority to EP08828815.4A priority patent/EP2186151B1/en
Priority to GB1000554.4A priority patent/GB2463217B/en
Priority to DE112008002212T priority patent/DE112008002212T5/en
Assigned to FMC CORPORATION, LITHIUM DIVISION reassignment FMC CORPORATION, LITHIUM DIVISION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GAO, YUAN, YAKOVLEVA, MARINA, FITCH, KENNETH BRIAN, LI, YANGXING, PALEPU, PRAKASH THYAGA, WOLTERMANN, CHRISTOPHER JAY
Publication of US20090061321A1 publication Critical patent/US20090061321A1/en
Priority to GB1211010.2A priority patent/GB2490433B/en
Priority to JP2014101264A priority patent/JP6001596B2/en
Priority to US15/422,059 priority patent/US20170149052A1/en
Priority to US15/975,470 priority patent/US11171323B2/en
Assigned to FMC CORPORATION reassignment FMC CORPORATION CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE NAME AND ADDRESS PREVIOUSLY RECORDED ON REEL 021591 FRAME 0743. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Assignors: GAO, YUAN, YAKOVLEVA, MARINA, FITCH, KENNETH BRIAN, LI, YANGXING, PALEPU, PRAKASH THYAGA, WOLTERMANN, CHRISTOPHER JAY
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102Metallic powder coated with organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16Metallic particles coated with a non-metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY 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
    • H01M4/381Alkaline or alkaline earth metals elements
    • H01M4/382Lithium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00Metallic composition of the powder or its coating
    • B22F2301/05Light metals
    • B22F2301/054Alkali metals, i.e. Li, Na, K, Rb, Cs, Fr
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/45Others, including non-metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY 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
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY 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
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the present invention relates to stabilized lithium metal powder (“SLMP”) having improved air and solvent stability and having a longer storage life.
  • SLMP stabilized lithium metal powder
  • Such improved SLMP can be used in a wide variety of applications including organo-metal and polymer synthesis, primary lithium batteries, rechargeable lithium batteries, and rechargeable lithium ion batteries.
  • Lithium and lithium-ion secondary or rechargeable batteries have recently found use in certain applications such as in cellular phones, cameorders, and laptop computers, and even more recently, in larger power applications such as in electric vehicles and hybrid electric vehicles. It is preferred in these applications that the secondary batteries have the highest specific capacity possible but still provide safe operating conditions and good cycleability so that the high specific capacity is maintained in subsequent recharging and discharging cycles.
  • each construction includes a positive electrode (or cathode), a negative electrode (or anode), a separator that separates the cathode and anode, and an electrolyte in electrochemical communication with the cathode and anode.
  • a positive electrode or cathode
  • a negative electrode or anode
  • a separator that separates the cathode and anode
  • an electrolyte in electrochemical communication with the cathode and anode.
  • lithium ions are transferred from the anode to the cathode through the electrolyte when the secondary battery is being discharged, i.e., used for its specific application. During this process, electrons are collected from the anode and pass to the cathode through an external circuit.
  • the lithium ions are transferred from the cathode to the anode through the electrolyte.
  • secondary lithium batteries were produced using non-lithiated compounds having high specific capacities such as TiS 2 , MoS 2 , MnO 2 and V 2 O 5 , as the cathode active materials. These cathode active materials were often coupled with a lithium metal anode. When the secondary battery was discharged, lithium ions were transferred from the lithium metal anode to the cathode through the electrolyte. Unfortunately, upon cycling, the lithium metal developed dendrites that ultimately caused unsafe conditions in the battery. As a result, the production of these types of secondary batteries was stopped in the early 1990's in favor of lithium-ion batteries.
  • Lithium-ion batteries typically use lithium metal oxides such as LiCoO 2 and LiNiO 2 as cathode active materials coupled with a carbon-based anode. In these batteries, the lithium dendrite formation on the anode is avoided thereby making the battery safer. However, the lithium, the amount of which determines the battery capacity, is totally supplied from the cathode. This limits the choice of cathode active materials because the active materials must contain removable lithium. Furthermore, the delithiated products corresponding to LiCoO 2 and LiNiO 2 that are formed during charging (e.g. Li x CoO 2 and Li x NiO 2 where 0.4 ⁇ x ⁇ 1.0) and overcharging (i.e. Li x CoO 2 and Li x NiO 2 where x ⁇ 0.4) are not stable. In particular, these delithiated products tend to react with the electrolyte and generate heat, which raises safety concerns.
  • LiCoO 2 and LiNiO 2 the lithium dendrite formation on the anode is avoided thereby making the battery
  • lithium metal is lithium metal.
  • Lithium metal particularly lithium metal powder; however, because of its high surface area, 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 CO 2 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 CO 2 -passivated lithium metal powder 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.
  • the present invention provides a lithium metal powder protected by a substantially continuous layer of a polymer.
  • a substantially continuous polymer layer provides improved protection such as compared to typical CO 2 -passivation.
  • the resulting lithium metal powder has improved air and solvent stability and improved storage life.
  • the polymer-protected lithium metal powder exhibits significantly better stability in N-methyl-2-pyrrolidone (NMP), which is commonly used as a slurry solvent in the electrode fabrication process, and reacts with unprotected lithium.
  • NMP N-methyl-2-pyrrolidone
  • FIG. 1 is an ARSST stability test of CO 2 -coated SLMP (comparative example 2) with NMP as received ( ⁇ 100 ppm moisture) and 0.6% water doped NMP.
  • FIG. 2 is an ARSST stability test of PEO-coated SLMP (example 2) with 0.6% water doped NMP.
  • FIG. 3 is an ARSST stability test of EVA-coated SLMP with 0.6% water doped NMP, example 10.
  • FIG. 4 is an ARSST stability test of SBR-coated SLMP with 0.6% water doped NMP, example 7.
  • FIG. 5 is an ARSST stability test of BYK P 104-coated (low molecular weight polycarboxylic acid polymer) SLMP with 0.6% water doped NMP, example 3.
  • FIG. 6 demonstrates the effect of a polymer-coated lithium on the electrochemical performance
  • FIG. 7 is an ARSST stability test of CO 2 -coated SLMP and Example 11.
  • FIGS. 8A , 8 B, and 8 C are SEM images for samples prepared using different process parameters.
  • FIG. 9A is a comparison of metallic lithium concentration in anhydrous NMP as a function of time.
  • FIG. 9B is a comparison of metallic lithium concentration in 0.6% water doped NMP as a function of time.
  • the term “about,” as used herein when referring to a measurable value such as an amount of a compound or agent of this invention, dose, time, temperature, and the like, is meant to encompass variations of 20%, 10%, 5%, 1%, 0.5%, or even 0.1% of the specified amount.
  • lithium dispersions are prepared by heating the lithium metal powder in a hydrocarbon oil to a temperature above its melting point, subjecting to conditions sufficient to disperse the molten lithium, agitating or stirring vigorously, and contacting the lithium metal powder with a polymer at a temperature that is between this temperature and at or above the melting point of the lithium to provide a substantially continuous layer of the polymer.
  • the substantially continuous layer of polymer has a thickness of 25 to 200 nm, and often has a thickness of 80 to 120 nm.
  • Other alkali metals such as sodium and potassium can be coated according to the present invention.
  • Suitable polymers can be polymers that are water resistant and that are lithium-ion conducting or non-lithium ion conducting, for example if they are soluble in the common electrolyte solvents.
  • the polymers may be reactive with lithium or non-reactive with lithium.
  • polystyrene-butadiene-styrene block polymers examples include: polyurethanes, polytetrafluoroethylene, polyvinyl fluoride, polyvinyl chloride, polystyrenes, polyethylenes, polypropylene, polyformaldehyde (Delrin), styrene-butadiene-styrene block polymers, ethylene vinyl acetate, ethylene acrylic acid copolymers, polyethylene oxide, polyimides, polythiophenes, poly(para-phenylene), polyanilines, poly(p-phenylenevinylene), silica titania copolymers, unsaturated polycarboxylic acid polymer and polysiloxane copolymers, etc.
  • the polymer 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 polymers 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 “transfer release paper” concept, where certain degree of stickiness is required. It is also understood that the monomers could be used to create an in-situ polymer coating on the surface of the lithium particles.
  • polymer or polymer mixtures with some inorganic coating, for example, Li 2 CO 3 , LiF, Li 3 PO 4 , SiO 2 , Li 4 SiO 4 , LiAlO 2 , Li 2 TiO 3 , LiNbO 3 , Al 2 O 3 , SiO 2 , SnO 2 , ZrO 2 , 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.
  • most polymers are soluble in non-polar solvents at elevated temperatures and solubility at room temperature could be significant (see, Table 2) and washing solvents used to remove oil from the particles should be selected appropriately.
  • dry non-stabilized or stabilized powders could be transferred into non-polar solvents that are compatible with lithium and polymer coatings could be deposited using for example, rotovap techniques, thus avoiding solubility issue.
  • Suitable polymers described above could produce two types of coatings on lithium particles: first type representing physical or adhesive type and second, representing chemically bonded coatings where polymers with functional groups, are used.
  • first type representing physical or adhesive type
  • second representing chemically bonded coatings where polymers with functional groups
  • polymers with functional groups are used.
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • This type of polymer is valuable as a coating reagent for lithium particles in that the physical Van der Waals interaction allows carbon-hydrogen molecules to adhere onto the surface of lithium particles.
  • polymers such as, for example, poly(acrylic acid) and ethylene vinyl acetate do react with lithium since they contain the acid functional groups, thus forming a chemically bonded coating.
  • polymers or polymer mixtures could be introduced above the melting point of lithium before or after other dispersants (e.g., wax) and coating reagents additions to enhance the chemical bonding and uniformity of protecting layer by changing the reaction interfaces.
  • the cooling profile, the temperature at which the polymer is introduced during the dispersion process could be used to control degree of crystallinity and obtain samples with pre-determined degree of stickiness.
  • Battery grade lithium metal (405 g) 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 Penetek 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 throughout 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 CO 2 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.
  • PenetelTM mineral oil (4449 g) and 1724 g of battery grade lithium metal were added to a 15 liter jacketed dispersion reactor under an argon atmosphere at room temperature.
  • the reactor was then heated from room temperature to 200° C. by pumping hot heat transfer fluid through the jacket.
  • the dispersion agitator was kept at low speed to facilitate heat transfer.
  • the dispersion agitator speed was increased to 5000 rpm.
  • 36 g of oleic acid was charged into the reactor and high speed stirring continued for another 4.5 minutes followed by addition of 22 g of CO2 gas.
  • the high speed agitator was turned off and the reactor contents were brought down to room temperature. During the cooling process, the dispersion was kept in suspension using low speed agitation. Lithium dispersion was transferred under argon pressure to a batch filter and the mineral oil was allowed to drain out. The dispersion in the filter was washed four times with hexane; then dry argon was blown through the filter to remove any remaining volatile organics. The dry stabilized polymer coated lithium dispersion was removed from the filter as a final product.
  • a lithium dispersion (47.30 g) passivated with CO 2 gas in oil (27.5%) containing 13.01 g of lithium with a medium particle size of 45 micron was charged into 120 ml hastelloy can equipped with a 1′′ Teflon coated stir bar.
  • 1.3 g of PEO (Polyox WSRN80) dry powder was also added to the can.
  • the solution was heated from ambient to 75° C. at a rate of 5° C./min and held for 10 minutes.
  • the sample was further heated from 75° C. to 175° C. at 5° C./min and held for one hour. This mixture was continuously stirred at 200 rpm during the heating phase. Sample was allowed to cool to room temperature and transferred to the storage bottle.
  • 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 tightly capped storage bottles.
  • a lithium dispersion (45.00 g) passivated with CO 2 gas in oil (27.5.%) containing 12.37 g of lithium with a medium particle size of 45 micron was charged into 120 ml hastelloy can equipped with a 1′′ Teflon coated stir bar.
  • 1.2 g of PEO (Polyox WSRN80) dry powder was also added to the can.
  • the solution was heated from ambient to 75° C. at a rate of 5° C./min and held for 10 minutes.
  • the sample was further heated from 75° C. to 175° C. at 5° C./min and held for one hour.
  • Finally the sample was heated from 175° C. to 200° C. at 20° C./min. This mixture was continuously stirred at 200 rpm during the heating phase.
  • a lithium dispersion (44.00 g) passivated with CO 2 gas in oil (27.5%) containing 12.10 g of lithium with a medium particle size of 45 micron was charged into 120 ml hastelloy can equipped with a 1′′ Teflon coated stir bar.
  • the solution was heated to 75° C. and 1.2 ml of BYK-P 104 S (BYK Chemie) was added to the lithium dispersion. This mixture was continuously stirred at 200 rpm for one hour. Sample was allowed to cool to room temperature and transferred to a storage bottle. Further, lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • a stabilized lithium dispersion (54.99 g) in oil (11.275%) containing 6.20 g 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.
  • 0.62 g of SBR in a form of 10% solution in p-xylene (Aldrich) was added to the lithium dispersion. This mixture was continuously stirred at 200 rpm for 19 hours.
  • Sample was transferred to a storage bottle. Further, lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • a stabilized lithium dispersion (54.68 g) in oil (11.275%) containing 6.17 g 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.
  • EVA Aldrich
  • p-xylene Aldrich
  • Sample was transferred to a storage bottle. Further, lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • a stabilized lithium dispersion (54.00 g) in oil (11.275%) containing 6.09 g 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.
  • 0.5 ml of butadiene (Aldrich) and 0.5 ml of styrene (Aldrich) were added to the lithium dispersion. This mixture was continuously stirred at 200 rpm for 1 hour. Sample was transferred to a storage bottle. Further, lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • SLMP stabilized lithium metal powder
  • 32.1 g of p-xylene (Aldrich) and 0.28 g SBR in a form of 10% solution in p-xylene (Aldrich) pre-dissolved were added to the flask.
  • the flask containing the mixture was attached to a rotavap vacuum extractor and heated with rotation to 70° C.. After holding the temperature at 70° C. for 15 minutes vacuum was applied to strip the solvent. The sample was then transferred to a storage bottle.
  • a stabilized lithium dispersion (2149.8 g) in oil (11.0%) containing 236.5 g of lithium with a medium particle size of 58 micron was charged into 3 liter round bottom flask equipped with a propeller type variable speed mixer.
  • EVA Aldrich
  • p-xylene Aldrich
  • Sample was transferred to a storage bottle.
  • lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • a stabilized lithium dispersion (1127.0 g) in oil (11.2%) containing 126.6 g of lithium with a medium particle size of 63 micron was charged into 5 liter round bottom flask equipped with a propeller type variable speed mixer. The temperature was raised to 41.3° C. and 12.5 g EVA (Aldrich) in a form of 5% solution in p-xylene (Aldrich) was added to the lithium dispersion. This mixture was continuously stirred at 500 rpm for about 6 hours at 40° C. and then for another ⁇ 18 hours at the ambient temperature. Sample was transferred to a storage bottle.
  • lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • PenetekTM mineral oil 15390 g of and 4415 g of battery grade lithium metal were added to a 57 liter jacketed dispersion reactor under an argon atmosphere at room temperature.
  • the reactor was then heated from room temperature to 190° C. by pumping hot heat transfer fluid through the jacket.
  • the dispersion agitator was kept at low speed to facilitate heat transfer to the reactor contents.
  • the dispersion agitator speed was increased to 4800 rpm.
  • 90 g of oleic acid was charged into the reactor and high speed stirring continued for another four minutes followed by addition of 56 grams of CO 2 gas.
  • FIGS. 1-5 and 7 below demonstrate stability of the polymer-coated samples in NMP, which is widely used as a solvent in the electrode fabrication process in the rechargeable lithium-ion battery industry.
  • the following procedure is used to conduct this test: SLMP and solvent are loaded into the test cell under Argon, then the test cell is brought up to 25° C. and isothermal hold continues for 72 hours, then the temperature is ramped up to 55° C. and isothermal hold continues for 48 hours; the mixture is continuously stirred.
  • the metallic lithium content of samples is measured upon completion of the test: the higher the content the better protecting properties of the coating are. As could be seen in Table 1 below, the lithium concentration is 17.3% and higher for the samples in the presented examples.
  • FIGS. 8A , 8 B, and 8 C show the different surface properties of Examples 5, 8, and 9 due to process parameter changes. A separate test was conducted to determine lithium content as a function of time with water doped NMP and significant improvement was observed. (See, FIGS. 9A and 9B .)

Abstract

The present invention provides a lithium metal powder protected by a substantially continuous layer of a polymer. Such a substantially continuous polymer layer provides improved protection such as compared to typical CO2-passivation.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application claims the benefit of, and incorporates herein by reference in its entirety, the following U.S. Provisional Application: U.S. Provisional Application No. 60/969,267, filed Aug. 31, 2007.
  • FIELD AND BACKGROUND OF THE INVENTION
  • The present invention relates to stabilized lithium metal powder (“SLMP”) having improved air and solvent stability and having a longer storage life. Such improved SLMP can be used in a wide variety of applications including organo-metal and polymer synthesis, primary lithium batteries, rechargeable lithium batteries, and rechargeable lithium ion batteries.
  • Lithium and lithium-ion secondary or rechargeable batteries have recently found use in certain applications such as in cellular phones, cameorders, and laptop computers, and even more recently, in larger power applications such as in electric vehicles and hybrid electric vehicles. It is preferred in these applications that the secondary batteries have the highest specific capacity possible but still provide safe operating conditions and good cycleability so that the high specific capacity is maintained in subsequent recharging and discharging cycles.
  • Although there are various constructions for secondary batteries, each construction includes a positive electrode (or cathode), a negative electrode (or anode), a separator that separates the cathode and anode, and an electrolyte in electrochemical communication with the cathode and anode. For secondary lithium batteries, lithium ions are transferred from the anode to the cathode through the electrolyte when the secondary battery is being discharged, i.e., used for its specific application. During this process, electrons are collected from the anode and pass to the cathode through an external circuit. When the secondary battery is being charged or recharged, the lithium ions are transferred from the cathode to the anode through the electrolyte.
  • Historically, secondary lithium batteries were produced using non-lithiated compounds having high specific capacities such as TiS2, MoS2, MnO2 and V2O5, as the cathode active materials. These cathode active materials were often coupled with a lithium metal anode. When the secondary battery was discharged, lithium ions were transferred from the lithium metal anode to the cathode through the electrolyte. Unfortunately, upon cycling, the lithium metal developed dendrites that ultimately caused unsafe conditions in the battery. As a result, the production of these types of secondary batteries was stopped in the early 1990's in favor of lithium-ion batteries.
  • Lithium-ion batteries typically use lithium metal oxides such as LiCoO2 and LiNiO2 as cathode active materials coupled with a carbon-based anode. In these batteries, the lithium dendrite formation on the anode is avoided thereby making the battery safer. However, the lithium, the amount of which determines the battery capacity, is totally supplied from the cathode. This limits the choice of cathode active materials because the active materials must contain removable lithium. Furthermore, the delithiated products corresponding to LiCoO2 and LiNiO2 that are formed during charging (e.g. Lix CoO2 and Lix NiO2 where 0.4<x<1.0) and overcharging (i.e. Lix CoO2 and Lix NiO2 where x<0.4) are not stable. In particular, these delithiated products tend to react with the electrolyte and generate heat, which raises safety concerns.
  • Another option is lithium metal. Lithium metal, particularly lithium metal powder; however, because of its high surface area, 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 stabilized lithium metal powder that has improved stability and storage life.
  • SUMMARY OF THE INVENTION
  • The present invention provides a lithium metal powder protected by a substantially continuous layer of a polymer. Such a substantially continuous polymer layer provides improved protection such as compared to typical CO2-passivation. The resulting lithium metal powder has improved air and solvent stability and improved storage life. Furthermore, the polymer-protected lithium metal powder exhibits significantly better stability in N-methyl-2-pyrrolidone (NMP), which is commonly used as a slurry solvent in the electrode fabrication process, and reacts with unprotected lithium.
  • Objects and advantages of the present invention will become more apparent by describing various embodiments of the present invention with reference to the attached drawings.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is an ARSST stability test of CO2-coated SLMP (comparative example 2) with NMP as received (<100 ppm moisture) and 0.6% water doped NMP.
  • FIG. 2 is an ARSST stability test of PEO-coated SLMP (example 2) with 0.6% water doped NMP.
  • FIG. 3 is an ARSST stability test of EVA-coated SLMP with 0.6% water doped NMP, example 10.
  • FIG. 4 is an ARSST stability test of SBR-coated SLMP with 0.6% water doped NMP, example 7.
  • FIG. 5 is an ARSST stability test of BYK P 104-coated (low molecular weight polycarboxylic acid polymer) SLMP with 0.6% water doped NMP, example 3.
  • FIG. 6 demonstrates the effect of a polymer-coated lithium on the electrochemical performance
  • FIG. 7 is an ARSST stability test of CO2-coated SLMP and Example 11.
  • FIGS. 8A, 8B, and 8C are SEM images for samples prepared using different process parameters.
  • FIG. 9A is a comparison of metallic lithium concentration in anhydrous NMP as a function of time.
  • FIG. 9B is a comparison of metallic lithium concentration in 0.6% water doped NMP as a function of time.
  • DETAILED DESCRIPTION OF THE INVENTION
  • In the drawings and the following detailed description, various 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.
  • 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. Furthermore, the term “about,” as used herein when referring to a measurable value such as an amount of a compound or agent of this invention, dose, time, temperature, and the like, is meant to encompass variations of 20%, 10%, 5%, 1%, 0.5%, or even 0.1% of the specified amount.
  • Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinarv 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.
  • All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. However, the citation of a reference herein should not be construed as an acknowledgement that such reference is prior art to the present invention described herein.
  • 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 to conditions sufficient to disperse the molten lithium, agitating or stirring vigorously, and contacting the lithium metal powder with a polymer at a temperature that is between this temperature and at or above the melting point of the lithium to provide a substantially continuous layer of the polymer. The substantially continuous layer of polymer has a thickness of 25 to 200 nm, and often has a thickness of 80 to 120 nm. Other alkali metals such as sodium and potassium can be coated according to the present invention.
  • Suitable polymers can be polymers that are water resistant and that are lithium-ion conducting or non-lithium ion conducting, for example if they are soluble in the common electrolyte solvents. The polymers may be reactive with lithium or non-reactive with lithium. The following are merely examples of the polymer compounds and include: polyurethanes, polytetrafluoroethylene, polyvinyl fluoride, polyvinyl chloride, polystyrenes, polyethylenes, polypropylene, polyformaldehyde (Delrin), styrene-butadiene-styrene block polymers, ethylene vinyl acetate, ethylene acrylic acid copolymers, polyethylene oxide, polyimides, polythiophenes, poly(para-phenylene), polyanilines, poly(p-phenylenevinylene), silica titania copolymers, unsaturated polycarboxylic acid polymer and polysiloxane copolymers, etc.
  • The polymer 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 polymers 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 “transfer release paper” concept, where certain degree of stickiness is required. It is also understood that the monomers could be used to create an in-situ polymer coating on the surface of the lithium particles.
  • Furthermore, it is beneficial to combine polymer or polymer mixtures with some inorganic coating, for example, Li2CO3, LiF, Li3PO4, SiO2, Li4SiO4, LiAlO2, Li2TiO3, LiNbO3, Al2O3, SiO2, SnO2, ZrO2, 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 polymers are soluble in non-polar solvents at elevated temperatures and solubility at room temperature could be significant (see, Table 2) and washing solvents used to remove oil from the particles should be selected appropriately. Sometimes, dry non-stabilized or stabilized powders could be transferred into non-polar solvents that are compatible with lithium and polymer coatings could be deposited using for example, rotovap techniques, thus avoiding solubility issue.
  • Suitable polymers described above, could produce two types of coatings on lithium particles: first type representing physical or adhesive type and second, representing chemically bonded coatings where polymers with functional groups, are used. For example, polyethylene (PE), polypropylene (PP), and polystyrene (PS) contain carbon-hydrogen groups that do not react with Li. This type of polymer is valuable as a coating reagent for lithium particles in that the physical Van der Waals interaction allows carbon-hydrogen molecules to adhere onto the surface of lithium particles. On the other hand, polymers such as, for example, poly(acrylic acid) and ethylene vinyl acetate do react with lithium since they contain the acid functional groups, thus forming a chemically bonded coating.
  • By altering the processes and process parameters and the order of the reagents addition in polymer-coated lithium particles can result with distinct surface properties. Different process parameters can result in samples with different surface properties (see, FIG. 7). Polymers or polymer mixtures could be introduced above the melting point of lithium before or after other dispersants (e.g., wax) and coating reagents additions to enhance the chemical bonding and uniformity of protecting layer by changing the reaction interfaces. The cooling profile, the temperature at which the polymer is introduced during the dispersion process could be used to control degree of crystallinity and obtain samples with pre-determined degree of stickiness.
  • The following examples are merely illustrative of the invention, and are not limiting thereon.
  • EXAMPLES Comparative Example 1
  • Battery grade lithium metal (405 g) 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 Penetek 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 throughout 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.
  • Comparative Example 2
  • Penetel™ mineral oil (4449 g) and 1724 g of battery grade lithium metal were added to a 15 liter jacketed dispersion reactor under an argon atmosphere at room temperature. The reactor was then heated from room temperature to 200° C. by pumping hot heat transfer fluid through the jacket. During heating the dispersion agitator was kept at low speed to facilitate heat transfer. Once the temperature inside the reactor reached 200° C., the dispersion agitator speed was increased to 5000 rpm. After 3.5 minutes of high speed stirring, 36 g of oleic acid was charged into the reactor and high speed stirring continued for another 4.5 minutes followed by addition of 22 g of CO2 gas. After an additional 4 minutes of high speed stirring, the high speed agitator was turned off and the reactor contents were brought down to room temperature. During the cooling process, the dispersion was kept in suspension using low speed agitation. Lithium dispersion was transferred under argon pressure to a batch filter and the mineral oil was allowed to drain out. The dispersion in the filter was washed four times with hexane; then dry argon was blown through the filter to remove any remaining volatile organics. The dry stabilized polymer coated lithium dispersion was removed from the filter as a final product.
  • Example 1
  • A lithium dispersion (47.30 g) passivated with CO2 gas in oil (27.5%) containing 13.01 g of lithium with a medium particle size of 45 micron was charged into 120 ml hastelloy can equipped with a 1″ Teflon coated stir bar. 1.3 g of PEO (Polyox WSRN80) dry powder was also added to the can. The solution was heated from ambient to 75° C. at a rate of 5° C./min and held for 10 minutes. The sample was further heated from 75° C. to 175° C. at 5° C./min and held for one hour. This mixture was continuously stirred at 200 rpm during the heating phase. Sample was allowed to cool to 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 tightly capped storage bottles.
  • Example 2
  • A lithium dispersion (45.00 g) passivated with CO2 gas in oil (27.5.%) containing 12.37 g of lithium with a medium particle size of 45 micron was charged into 120 ml hastelloy can equipped with a 1″ Teflon coated stir bar. 1.2 g of PEO (Polyox WSRN80) dry powder was also added to the can. The solution was heated from ambient to 75° C. at a rate of 5° C./min and held for 10 minutes. The sample was further heated from 75° C. to 175° C. at 5° C./min and held for one hour. Finally the sample was heated from 175° C. to 200° C. at 20° C./min. This mixture was continuously stirred at 200 rpm during the heating phase. Sample was allowed to cool to room temperature and transferred to a storage bottle. Further, lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • Example 3
  • A lithium dispersion (44.00 g) passivated with CO2 gas in oil (27.5%) containing 12.10 g of lithium with a medium particle size of 45 micron was charged into 120 ml hastelloy can equipped with a 1″ Teflon coated stir bar. The solution was heated to 75° C. and 1.2 ml of BYK-P 104 S (BYK Chemie) was added to the lithium dispersion. This mixture was continuously stirred at 200 rpm for one hour. Sample was allowed to cool to room temperature and transferred to a storage bottle. Further, lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • Example 4
  • A stabilized lithium dispersion (54.99 g) in oil (11.275%) containing 6.20 g 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. At ambient temperature 0.62 g of SBR in a form of 10% solution in p-xylene (Aldrich) was added to the lithium dispersion. This mixture was continuously stirred at 200 rpm for 19 hours. Sample was transferred to a storage bottle. Further, lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • Example 5
  • A stabilized lithium dispersion (54.68 g) in oil (11.275%) containing 6.17 g 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. At ambient temperature 0.62 g of EVA (Aldrich) in a form of 5% solution in p-xylene (Aldrich) pre-dissolved was added to the lithium dispersion. This mixture was continuously stirred at 200 rpm for 2.5 hours. Sample was transferred to a storage bottle. Further, lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • Example 6
  • A stabilized lithium dispersion (54.00 g) in oil (11.275%) containing 6.09 g 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. At ambient temperature 0.5 ml of butadiene (Aldrich) and 0.5 ml of styrene (Aldrich) were added to the lithium dispersion. This mixture was continuously stirred at 200 rpm for 1 hour. Sample was transferred to a storage bottle. Further, lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • Example 7
  • 10.0 g of SLMP (stabilized lithium metal powder) was weighed into a 1 liter round bottom flask. 32.1 g of p-xylene (Aldrich) and 0.28 g SBR in a form of 10% solution in p-xylene (Aldrich) pre-dissolved were added to the flask. The flask containing the mixture was attached to a rotavap vacuum extractor and heated with rotation to 70° C.. After holding the temperature at 70° C. for 15 minutes vacuum was applied to strip the solvent. The sample was then transferred to a storage bottle.
  • Example 8
  • 4.0 g of non-stabilized lithium powder with a medium particle size of 58 micron and 36 g p-xylene (Aldrich) were charged into 120 ml hastelloy can equipped with a 1″ Teflon coated stir bar. This mixture was heated to 40° C. while mixing at 200 rpm. At 40° C., 0.40 g of EVA in a form of 10% solution in p-xylene (Aldrich) pre-dissolved was added to the lithium, p-xylene mixture. This mixture was continuously stirred at 200 rpm for 20 hours. Sample was transferred to a 200 ml round bottom flask. Further, the p-xylene was evaporated away by passing dry argon over the sample. The resulting free-flowing powder was transferred to a tightly capped storage bottle.
  • Example 9
  • A stabilized lithium dispersion (2149.8 g) in oil (11.0%) containing 236.5 g of lithium with a medium particle size of 58 micron was charged into 3 liter round bottom flask equipped with a propeller type variable speed mixer. At ambient temperature 23.8 g EVA (Aldrich) in a form of 10% solution in p-xylene (Aldrich) was added to the lithium dispersion. This mixture was continuously stirred at 500 rpm for 4 hours. Sample was transferred to a storage bottle. Further, lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • Example 10
  • A stabilized lithium dispersion (1127.0 g) in oil (11.2%) containing 126.6 g of lithium with a medium particle size of 63 micron was charged into 5 liter round bottom flask equipped with a propeller type variable speed mixer. The temperature was raised to 41.3° C. and 12.5 g EVA (Aldrich) in a form of 5% solution in p-xylene (Aldrich) was added to the lithium dispersion. This mixture was continuously stirred at 500 rpm for about 6 hours at 40° C. and then for another ˜18 hours at the ambient temperature. Sample was transferred to a storage bottle. Further, lithium dispersion was filtered and washed three times with hexane and twice with n-pentane in an enclosed, sintered glass filter funnel 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 tightly capped storage bottles.
  • Example 11
  • Penetek™ mineral oil 15390 g of and 4415 g of battery grade lithium metal were added to a 57 liter jacketed dispersion reactor under an argon atmosphere at room temperature. The reactor was then heated from room temperature to 190° C. by pumping hot heat transfer fluid through the jacket. During heating the dispersion agitator was kept at low speed to facilitate heat transfer to the reactor contents. Once the temperature inside the reactor reached 190° C., the dispersion agitator speed was increased to 4800 rpm. After three minutes of high speed stirring, 90 g of oleic acid was charged into the reactor and high speed stirring continued for another four minutes followed by addition of 56 grams of CO2 gas. After an additional six minutes of high speed stirring, 154 g of polyethylene oxide (PEO) granules were added to the reactor and high speed stirring continued for three more minutes. Then the high speed agitator was turned off and the reactor contents were brought down to room temperature. During the cooling process, the dispersion was kept in suspension using low speed agitation. The lithium dispersion was transferred under argon pressure to a batch filter and the mineral oil was allowed to drain out under argon pressure. The dispersion was washed four times with hexane; then dry argon was blown through the filter to remove any remaining volatile organics. The dry stabilized polymer coated lithium dispersion was removed from the filter as a final product.
  • FIGS. 1-5 and 7 below demonstrate stability of the polymer-coated samples in NMP, which is widely used as a solvent in the electrode fabrication process in the rechargeable lithium-ion battery industry. The following procedure is used to conduct this test: SLMP and solvent are loaded into the test cell under Argon, then the test cell is brought up to 25° C. and isothermal hold continues for 72 hours, then the temperature is ramped up to 55° C. and isothermal hold continues for 48 hours; the mixture is continuously stirred. The metallic lithium content of samples is measured upon completion of the test: the higher the content the better protecting properties of the coating are. As could be seen in Table 1 below, the lithium concentration is 17.3% and higher for the samples in the presented examples. No adverse effects on electrochemical properties of polymer additive to graphite electrode were observed. (See FIG. 6.) FIGS. 8A, 8B, and 8C show the different surface properties of Examples 5, 8, and 9 due to process parameter changes. A separate test was conducted to determine lithium content as a function of time with water doped NMP and significant improvement was observed. (See, FIGS. 9A and 9B.)
  • TABLE 1
    Examples of the residual metallic lithium concentration measured
    using standard ARSST test with the 0.6% water doped NMP
    Coating Residual metallic
    agent Example Lithium concentration
    EVA Example 10 (785-106) 24.3%
    SBR Example 7 (767-200) 17.3%
    PEO Example 1 38.2%
    (PEOR043007)
    PEO Example 2 30.9%
    (PEOR050807)
  • TABLE 2
    Examples of polymer's solubility in selected solvents
    LuWax A SBR EVA PEO
    Hexane 0.46% 3.92% 1.21% 0.03%
    Pentane 0.48%  4.1% 0.46% 0.03%
    Xylene 0.81%  >10%  >10%  >10%
  • 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 (9)

1. A stabilized lithium metal powder coated with a substantially continuous polymer layer, the polymer selected from the group consisting of polyurethanes, polytetrafluoroethylene, polyvinyl fluoride, polyvinyl chloride, polystyrenes, polyethylenes, polypropylenes, polyformaldehyde, styrene-butadiene-styrene block polymers, ethylene vinyl acetate, ethylene acrylic acid copolymers, polyethylene oxide, polyimides, polythiophenes, poly(para-phenylene), polyaniline, poly(p-phenylenevinylene), silica titania-based copolymers, unsaturated polycarboxylic acids and polysiloxanes.
2. The stabilized lithium metal powder of claim 1, wherein the substantially continuous polymer layer has a thickness of 25 to 200 nm.
3. The stabilized lithium metal powder of claim 2 further including an inorganic coating layer.
4. An anode comprising a host material capable of absorbing or desorbing lithium in an electrochemical system wherein stabilized polymer-coated lithium metal powder of claim 3 is dispersed in the host material.
5. The anode of claim 4, 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.
6. The anode of claim 5, wherein the substantially continuous polymer layer has a thickness of 25 to 200 nm.
7. A stabilized lithium metal powder coated with a substantially continuous polymer layer having a thickness of 25 to 200 nm.
8. An anode comprising a host material capable of absorbing or desorbing lithium in an electrochemical system wherein stabilized polymer-coated lithium metal powder of claim 7 is dispersed in the host material.
9. A method of forming a lithium dispersion comprising the steps of:
a) contacting lithium metal with a hydrocarbon oil;
b) heating the lithium metal and hydrocarbon oil to a temperature higher than the melting point of the lithium metal;
c) subjecting the heated lithium metal and hydrocarbon oil to conditions sufficient to disperse the lithium metal in the oil; and
d) contacting the lithium metal with a polymer selected from the group consisting of polyurethanes, polytetrafluoroethylene, polyvinyl fluoride, polyvinyl chloride, polystyrenes, polyethylenes, polypropylenes, (polyformaldehyde), styrene-butadiene-styrene block polymers, ethylene vinyl acetate, ethylene acrylic acid copolymers, polyethylene oxide, polyimides, polythiophenes, poly(para-phenylene), polyaniline, poly(p-phenylenevinylene), silica titania-based copolymers, unsaturated polycarboxylic acids and polysiloxanes at a temperature between the melting point of the lithium metal and the melting point of the polymer to provide a substantially continuous layer of polymer on the lithium metal.
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GB1000554.4A GB2463217B (en) 2007-08-31 2008-08-27 Method of forming lithium dispersion, and stabilized lithium metal powder
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JP2010522937A JP5548126B2 (en) 2007-08-31 2008-08-27 Method for forming a dispersion of stabilized lithium metal powder
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Cited By (17)

* 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
US20110104571A1 (en) * 2009-11-02 2011-05-05 Aruna Zhamu Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries
DE102010063233A1 (en) 2009-12-18 2011-06-22 Chemetall GmbH, 60487 Surface passivated lithium metal and process for its preparation
WO2012052265A2 (en) 2010-09-28 2012-04-26 Chemetall Gmbh Stabilized, pure lithium metal powder and method for producing the same
CN102642024A (en) * 2012-03-06 2012-08-22 宁德新能源科技有限公司 Lithium ion battery and anode strip thereof and stabilization lithium metal powder
DE102013200416A1 (en) 2012-01-13 2013-07-18 Chemetall Gmbh Stabilized alloy-forming elements coated lithium metal impressions and methods of making the same
WO2013104788A1 (en) 2012-01-13 2013-07-18 Chemetall Gmbh Phosphorous-coated lithium metal products, method for production and use thereof
DE102014207396A1 (en) 2013-04-19 2014-10-23 Rockwood Lithium GmbH Stabilized nitrogen-containing shell-coated lithium metal impressions and methods of making the same
US9029013B2 (en) 2013-03-13 2015-05-12 Uchicago Argonne, Llc Electroactive compositions with poly(arylene oxide) and stabilized lithium metal particles
WO2017123443A1 (en) * 2016-01-13 2017-07-20 Applied Materials, Inc. Anode structure with binders for silicon and stabilized lithium metal powder
US9843043B2 (en) 2014-02-11 2017-12-12 Corning Incorporated Lithium ion batteries including stabilized lithium composite particles
CN109837561A (en) * 2017-11-27 2019-06-04 中国科学院大连化学物理研究所 A kind of metallic lithium powder and its electrochemical preparation method
CN111066178A (en) * 2017-08-31 2020-04-24 雅宝公司 Method for prelithiation of electrodes using lithium silicon alloys
CN111430674A (en) * 2020-01-19 2020-07-17 蜂巢能源科技有限公司 Electrode pole piece, manufacturing method thereof and semi-solid battery
US20210020927A1 (en) * 2019-01-11 2021-01-21 Lg Chem, Ltd. Lithium electrode and lithium secondary battery comprising same
CN114122368A (en) * 2020-08-28 2022-03-01 比亚迪股份有限公司 Lithium supplement material, manufacturing method thereof, negative pole piece and battery
US11394055B2 (en) 2015-04-03 2022-07-19 Samsung Electronics Co., Ltd. Electrolyte for lithium second battery, and lithium second battery comprising the electrolyte

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8231810B2 (en) * 2004-04-15 2012-07-31 Fmc Corporation Composite materials of nano-dispersed silicon and tin and methods of making the same
US20090035663A1 (en) 2006-10-13 2009-02-05 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
CN105206793B (en) 2009-08-24 2017-12-22 赛昂能源有限公司 Stripping system for electrochemical cell
US20110135810A1 (en) * 2009-12-03 2011-06-09 Marina Yakovleva Finely deposited lithium metal powder
DE102010044008A1 (en) 2010-11-16 2012-05-16 Varta Micro Innovation Gmbh Lithium-ion cell with 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 manufacture
KR101336943B1 (en) * 2011-05-20 2013-12-04 고려대학교 산학협력단 Lithium secondary battery using Li-powder, lithium vanadium oxide, and gel-polymer electrolyte and methods of manufacturing the electrodes thereof
JP2012248478A (en) * 2011-05-30 2012-12-13 Denso Corp Lithium ion secondary battery
KR101598650B1 (en) * 2012-08-23 2016-03-03 주식회사 엘지화학 Negative-electrode and lithium secondary battery with high capacity comprising the same
CN103779572B (en) * 2012-10-26 2016-02-24 华为技术有限公司 A kind of lithium ion battery negative additive and preparation method thereof, anode plate for lithium ionic cell and lithium ion battery
US8920925B2 (en) * 2012-11-09 2014-12-30 Corning Incorporated Stabilized lithium composite particles
US9183994B2 (en) * 2012-11-28 2015-11-10 Corning Incorporated Lithium ion capacitors and methods of production
EP2973789B1 (en) 2013-03-15 2019-05-08 Sion Power Corporation Protected electrode structures and methods
JP2016511517A (en) 2013-03-15 2016-04-14 ビーエイエスエフ・ソシエタス・エウロパエアBasf Se Protective electrode structure
US10490796B2 (en) 2014-02-19 2019-11-26 Sion Power Corporation Electrode protection using electrolyte-inhibiting ion conductor
US9653750B2 (en) 2014-02-19 2017-05-16 Sion Power Corporation Electrode protection using a composite comprising an electrolyte-inhibiting ion conductor
CN105098188B (en) * 2014-04-28 2017-09-01 比亚迪股份有限公司 A kind of anode material for lithium-ion batteries additive and preparation method thereof, positive electrode and lithium ion battery containing the additive
JP6375843B2 (en) * 2014-10-03 2018-08-22 Tdk株式会社 Stabilized lithium powder and lithium ion secondary battery using the same
JP6657671B2 (en) * 2014-10-03 2020-03-04 Tdk株式会社 Stabilized lithium powder, negative electrode for lithium ion secondary battery and lithium ion secondary battery using the same
JP6460400B2 (en) * 2015-03-31 2019-01-30 Tdk株式会社 Stabilized lithium powder and lithium ion secondary battery using the same
JP6596877B2 (en) * 2015-03-31 2019-10-30 Tdk株式会社 Stabilized lithium powder and lithium ion secondary battery using the same
JP6668642B2 (en) * 2015-08-27 2020-03-18 Tdk株式会社 Stabilized lithium powder, negative electrode and lithium ion secondary battery using the same
CN107195867A (en) * 2016-03-15 2017-09-22 宁德新能源科技有限公司 Negative active core-shell material and preparation method thereof and secondary cell
CN107644990B (en) * 2016-07-21 2020-04-21 万向一二三股份公司 Metallic lithium negative electrode material with positive temperature coefficient effect
CN107665977B (en) * 2016-07-28 2020-05-19 万向一二三股份公司 High-safety lithium metal negative electrode battery
CN107749489B (en) * 2016-08-15 2020-03-24 万向一二三股份公司 High-safety high-energy-density lithium ion battery
KR20190077553A (en) * 2016-11-22 2019-07-03 캠엑스 파워 엘엘씨 Stable low-voltage electrochemical cell
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WO2023239686A1 (en) 2022-06-07 2023-12-14 Livent Lithium Llc Solid-state battery

Citations (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5567474A (en) * 1993-02-18 1996-10-22 Fmc Corporation Process for producing alkali metal dispersions
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
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
US5976403A (en) * 1993-02-18 1999-11-02 Fmc Corporation Organoalkali compounds and their preparation
US6156457A (en) * 1997-03-11 2000-12-05 Kabushiki Kaisha Toshiba Lithium secondary battery and method for manufacturing a negative electrode
US6168885B1 (en) * 1998-08-21 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
US6373123B1 (en) * 1998-05-08 2002-04-16 Micron Technology, Inc. Semiconductor structure having more usable substrate area and method for forming same
US6387564B1 (en) * 1997-02-28 2002-05-14 Asahi Kasei Kabushiki Kaisha Non-aqueous secondary battery having an aggregation layer
US6398125B1 (en) * 2001-02-10 2002-06-04 Nanotek Instruments, Inc. Process and apparatus for the production of nanometer-sized powders
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
US20030099884A1 (en) * 2001-07-27 2003-05-29 A123Systems, Inc. Battery structures, self-organizing structures and related methods
US20030124422A1 (en) * 2001-12-27 2003-07-03 George Cintra Battery electrode and method of making the same
US20040002005A1 (en) * 2000-12-22 2004-01-01 Yuan Gao Lithium metal dispersion in secondary battery anodes
US20040018430A1 (en) * 2002-07-26 2004-01-29 A123 Systems, Inc. Electrodes and related devices
US20040146784A1 (en) * 2000-12-22 2004-07-29 Yuan Gao Lithium metal dispersion in secondary battery anodes
US20050079420A1 (en) * 2003-08-19 2005-04-14 Cho Chung-Kun Method of preparing a lithium metal anode
US20050095504A1 (en) * 2003-10-31 2005-05-05 Hee-Tak Kim Negative electrode for lithium metal battery and lithium metal battery comprising the same
US20050130043A1 (en) * 2003-07-29 2005-06-16 Yuan Gao Lithium metal dispersion in electrodes
US20050239917A1 (en) * 2004-02-18 2005-10-27 Solicore, Inc. Lithium inks and electrodes and batteries made therefrom
US20050244715A1 (en) * 2004-04-29 2005-11-03 Cho Chung-Kun Lithium secondary battery
US20080057385A1 (en) * 2006-08-30 2008-03-06 Shin-Etsu Chemical Co., Ltd. Separator for non-aqueous secondary battery, making method, and non-aqueous electrolyte secondary battery
US20090035663A1 (en) * 2006-10-13 2009-02-05 Fmc Corporation, Lithium Division Stabilized lithium metal powder for li-ion application, composition and process

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3176172B2 (en) * 1993-04-28 2001-06-11 キヤノン株式会社 Lithium secondary battery and method of manufacturing the same
JP3566509B2 (en) * 1997-08-13 2004-09-15 株式会社リコー Electrode plate for secondary battery and method of manufacturing the same
JPH11135153A (en) * 1997-10-31 1999-05-21 Denso Corp Nonaqueous electrolyte secondary battery
DE19946066A1 (en) * 1999-09-25 2001-03-29 Merck Patent Gmbh Coated lithium mixed oxide particles and their use II
JP4751502B2 (en) * 1999-11-19 2011-08-17 第一工業製薬株式会社 Polymer battery
JP2002313324A (en) * 2000-12-22 2002-10-25 Fmc Corp Anode for use in lithium metal dispersed system secondary battery
CN1918727A (en) * 2004-02-07 2007-02-21 株式会社Lg化学 Organic/inorganic composite porous layer-coated electrode and electrochemical device comprising the same
GB0414161D0 (en) * 2004-06-24 2004-07-28 Aea Technology Battery Systems Anode for lithium ion cell
US7588623B2 (en) * 2005-07-05 2009-09-15 Fmc Corporation Lithium Division Stabilized lithium metal powder for li-ion application, composition and process
JP5256660B2 (en) * 2006-08-30 2013-08-07 信越化学工業株式会社 Non-aqueous secondary battery separator, method for producing the same, and non-aqueous electrolyte secondary battery
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

Patent Citations (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5567474A (en) * 1993-02-18 1996-10-22 Fmc Corporation Process for producing alkali metal dispersions
US5976403A (en) * 1993-02-18 1999-11-02 Fmc Corporation Organoalkali compounds and their preparation
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
US6373123B1 (en) * 1998-05-08 2002-04-16 Micron Technology, Inc. Semiconductor structure having more usable substrate area and method for forming same
US6168885B1 (en) * 1998-08-21 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
US6706447B2 (en) * 2000-12-22 2004-03-16 Fmc Corporation, Lithium Division Lithium metal dispersion in secondary battery anodes
US7276314B2 (en) * 2000-12-22 2007-10-02 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
US20040146784A1 (en) * 2000-12-22 2004-07-29 Yuan Gao Lithium metal dispersion in secondary battery anodes
US6398125B1 (en) * 2001-02-10 2002-06-04 Nanotek Instruments, Inc. Process and apparatus for the production of nanometer-sized powders
US20030099884A1 (en) * 2001-07-27 2003-05-29 A123Systems, Inc. Battery structures, self-organizing structures and related methods
US20030124422A1 (en) * 2001-12-27 2003-07-03 George Cintra Battery electrode and method of making the same
US20040018430A1 (en) * 2002-07-26 2004-01-29 A123 Systems, Inc. Electrodes and related devices
US20050130043A1 (en) * 2003-07-29 2005-06-16 Yuan Gao Lithium metal dispersion in electrodes
US20050079420A1 (en) * 2003-08-19 2005-04-14 Cho Chung-Kun Method of preparing a lithium metal anode
US20050095504A1 (en) * 2003-10-31 2005-05-05 Hee-Tak Kim Negative electrode for lithium metal battery and lithium metal battery comprising the same
US20050239917A1 (en) * 2004-02-18 2005-10-27 Solicore, Inc. Lithium inks and electrodes and batteries made therefrom
US20050244715A1 (en) * 2004-04-29 2005-11-03 Cho Chung-Kun Lithium secondary battery
US20080057385A1 (en) * 2006-08-30 2008-03-06 Shin-Etsu Chemical Co., Ltd. Separator for non-aqueous secondary battery, making method, and non-aqueous electrolyte secondary battery
US20090035663A1 (en) * 2006-10-13 2009-02-05 Fmc Corporation, Lithium Division Stabilized lithium metal powder for li-ion application, composition and process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Surface characterization of emulsified lithium powder electrode, Hong et al, Electrochimica Acta, 50 (2004) 535- 539. *

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9925813B2 (en) 2004-02-18 2018-03-27 Brightvolt, 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
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
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
WO2011073324A1 (en) 2009-12-18 2011-06-23 Chemetall Gmbh Surface-passivated lithium metal and method for the production thereof
DE102010063233A1 (en) 2009-12-18 2011-06-22 Chemetall GmbH, 60487 Surface passivated lithium metal and process for its preparation
US9073120B2 (en) 2009-12-18 2015-07-07 Chemetall Gmbh Surface-passivated lithium metal and method for the production thereof
US11021797B2 (en) 2010-09-28 2021-06-01 Albemarle Germany Gmbh Stabilized, pure lithium metal powder and method for producing the same
WO2012052265A2 (en) 2010-09-28 2012-04-26 Chemetall Gmbh Stabilized, pure lithium metal powder and method for producing the same
US20130181160A1 (en) * 2010-09-28 2013-07-18 Chemetall Gmbh Stabilized, pure lithium metal powder and method for producing the same
US10655229B2 (en) 2010-09-28 2020-05-19 Albemarle Germany Gmbh Stabilized, pure lithium metal powder and method for producing the same
CN103379972A (en) * 2010-09-28 2013-10-30 罗克伍德锂有限责任公司 Stabilized, pure lithium metal powder and method for producing the same
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
US9601762B2 (en) 2012-01-13 2017-03-21 Rockwood Lithium GmbH Phosphorous-coated lithium metal products, method for production and use thereof
US11018334B2 (en) 2012-01-13 2021-05-25 Albemarle Germany Gmbh Stabilized lithium metal impressions coated with alloy-forming elements and method for production thereof
CN104185522A (en) * 2012-01-13 2014-12-03 罗克伍德锂有限责任公司 Stabilized lithium metal impressions coated with alloy-forming elements and method for production thereof
DE102013200414A1 (en) 2012-01-13 2014-01-09 Chemetall Gmbh Phosphorus-coated lithium metal products, process for their preparation and use
WO2013104787A1 (en) 2012-01-13 2013-07-18 Chemetall Gmbh Stabilized lithium metal impressions coated with alloy-forming elements and method for production thereof
WO2013104788A1 (en) 2012-01-13 2013-07-18 Chemetall Gmbh Phosphorous-coated lithium metal products, method for production and use thereof
DE102013200416A1 (en) 2012-01-13 2013-07-18 Chemetall Gmbh Stabilized alloy-forming elements coated lithium metal impressions and methods of making the same
CN102642024A (en) * 2012-03-06 2012-08-22 宁德新能源科技有限公司 Lithium ion battery and anode strip thereof and stabilization lithium metal powder
US9029013B2 (en) 2013-03-13 2015-05-12 Uchicago Argonne, Llc Electroactive compositions with poly(arylene oxide) and stabilized lithium metal particles
DE102014207396A1 (en) 2013-04-19 2014-10-23 Rockwood Lithium GmbH Stabilized nitrogen-containing shell-coated lithium metal impressions and methods of making the same
WO2014170429A1 (en) 2013-04-19 2014-10-23 Rockwood Lithium GmbH Stabilised lithium metal formations coated with a shell containing nitrogen, and a method for the production of same
US9843043B2 (en) 2014-02-11 2017-12-12 Corning Incorporated Lithium ion batteries including stabilized lithium composite particles
US11394055B2 (en) 2015-04-03 2022-07-19 Samsung Electronics Co., Ltd. Electrolyte for lithium second battery, and lithium second battery comprising the electrolyte
US20190013513A1 (en) * 2016-01-13 2019-01-10 Applied Materials, Inc. Anode structure with binders for silicon and stabilized lithium metal powder
US11069888B2 (en) * 2016-01-13 2021-07-20 Applied Materials, Inc. Anode structure with binders for silicon and stabilized lithium metal powder
WO2017123443A1 (en) * 2016-01-13 2017-07-20 Applied Materials, Inc. Anode structure with binders for silicon and stabilized lithium metal powder
CN111066178A (en) * 2017-08-31 2020-04-24 雅宝公司 Method for prelithiation of electrodes using lithium silicon alloys
CN109837561A (en) * 2017-11-27 2019-06-04 中国科学院大连化学物理研究所 A kind of metallic lithium powder and its electrochemical preparation method
US20210020927A1 (en) * 2019-01-11 2021-01-21 Lg Chem, Ltd. Lithium electrode and lithium secondary battery comprising same
US11942629B2 (en) * 2019-01-11 2024-03-26 Lg Energy Solution, Ltd. Lithium electrode and lithium secondary battery comprising same
CN111430674A (en) * 2020-01-19 2020-07-17 蜂巢能源科技有限公司 Electrode pole piece, manufacturing method thereof and semi-solid battery
CN114122368A (en) * 2020-08-28 2022-03-01 比亚迪股份有限公司 Lithium supplement material, manufacturing method thereof, negative pole piece and battery

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