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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English (en)
Inventor
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/ko
Priority to CN200880104518A priority patent/CN101790806A/zh
Priority to EP12157983.3A priority patent/EP2463940B1/de
Priority to GB1000554.4A priority patent/GB2463217B/en
Priority to PCT/US2008/010152 priority patent/WO2009029270A1/en
Priority to DE112008002212T priority patent/DE112008002212T5/de
Priority to CA2696771A priority patent/CA2696771C/en
Priority to CN201610044145.0A priority patent/CN105618735A/zh
Priority to EP08828815.4A priority patent/EP2186151B1/de
Priority to RU2010112410/02A priority patent/RU2010112410A/ru
Priority to JP2010522937A priority patent/JP5548126B2/ja
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/ja
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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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/05—Light metals
    • B22F2301/054—Alkali metals, i.e. Li, Na, K, Rb, Cs, Fr
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/45—Others, including non-metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • 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 .)

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EP08828815.4A EP2186151B1 (de) 2007-08-31 2008-08-27 Verfahren zur herstellung einer lithium-dispersion and stabilisiertes lithiummetallpulver
RU2010112410/02A RU2010112410A (ru) 2007-08-31 2008-08-27 Стабилизированный порошок металлического лития для литий-ионных применений, композиций и способ получения
EP12157983.3A EP2463940B1 (de) 2007-08-31 2008-08-27 Stabilisiertes Lithiummetallpulver und Anode dasselbe umfassend
GB1000554.4A GB2463217B (en) 2007-08-31 2008-08-27 Method of forming lithium dispersion, and stabilized lithium metal powder
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DE112008002212T DE112008002212T5 (de) 2007-08-31 2008-08-27 Stabilisiertes Lithiummetallpulver für Li-Ionen-Anwendungen, Zusammensetzung und Herstellungsverfahren
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CN201610044145.0A CN105618735A (zh) 2007-08-31 2008-08-27 用于锂离子应用的稳定锂金属粉末、组合物和制备方法
KR1020107006808A KR20100081304A (ko) 2007-08-31 2008-08-27 리튬 이온 응용을 위한 안정화된 리튬 금속 분말, 조성물 및 제조방법
CN200880104518A CN101790806A (zh) 2007-08-31 2008-08-27 用于锂离子应用的稳定锂金属粉末、组合物和制备方法
JP2010522937A JP5548126B2 (ja) 2007-08-31 2008-08-27 安定化リチウム金属粉末の分散体の形成方法
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