WO2001039290A2 - Method and apparatus for producing lithium based cathodes - Google Patents
Method and apparatus for producing lithium based cathodes Download PDFInfo
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- WO2001039290A2 WO2001039290A2 PCT/US2000/031889 US0031889W WO0139290A2 WO 2001039290 A2 WO2001039290 A2 WO 2001039290A2 US 0031889 W US0031889 W US 0031889W WO 0139290 A2 WO0139290 A2 WO 0139290A2
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- mist
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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
- H01M4/139—Processes of manufacture
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0027—Mixed oxides or hydroxides containing one alkali metal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
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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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/08—Intercalated structures, i.e. with atoms or molecules intercalated in their structure
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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
- This invention relates generally to thin film batteries, and more particularly to the production of lithium cathodes of thin film, rechargeable lithium ion batteries .
- canister type batteries today include toxic materials such as cadmium, mercury, lead and acid electrolytes. These chemicals are presently facing governmental regulations or bans as manufacturing materials, thus limiting their use as battery components. Another problem associated with these battery materials is that the amount of energy stored and delivered by these batteries is directly related to the size and weight of the active components used therein. Large batteries, such as those found in automobiles, produce large amounts of current but have very low energy densities (Watts hours per liter) and specific energies (Watt hours per gram) . As such, they require lengthy recharge times which render them impractical for many uses.
- Thin film lithium batteries have been produced which have a stacked configuration of films commencing with an inert ceramic substrate upon which a cathode current collector and cathode are mounted. A solid state electrolyte is deposited upon the cathode, an anode in turn deposited upon the electrolyte, and an anode current collector mounted upon the anode. Typically, a protective coating is applied over the entire cell.
- Lithium batteries of this type are describe in detail in U.S. Patent Nos . 5,569,520 and 5,597,660, the disclosures of which are specifically incorporated herein. However, the lithiated cathode material of these batteries have a (003) alignment of the lithium cells, as shown in Fig. 1, which creates a high internal cell resistance resulting in large capacity losses .
- Thin film batteries have also been produced by forming active cathode materials through chemical vapor deposition techniques.
- chemical vapor deposition cathodes have been manufactured in extremely low pressure environments, within a range of 1-100 torr .
- the requirements of this extremely low pressure environment greatly increases the cost of production and greatly reduces the feasibility of producing commercially viable products as a result of the difficulty in controlling such.
- this type of chemical vapor deposition is typically carried out by heating a precursor solution to cause evaporation of the solution to a gas phase so that it may be carried off to a deposition location through a stream of non-reactive gas, such as argon.
- the heating of the precursor for an extended time period can cause the solution to decompose and therefor become unworkable.
- the high temperature and low pressure of the system requires extensive heating of the transport lines conveying the solution to prevent the evaporated solution from condensing between the heating location and the deposition location, thus further increasing the cost and the complications involved in production.
- a method of producing a layer of LiCo0 2 comprises the steps of providing a lithium based solution, atomizing the lithium based solution to form a mist, heating a stream of gas, entraining the atomized lithium based solution into the heated gas stream so as to heat the lithium based solution mist to a vapor state, and depositing the vapor upon a substrate .
- BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an illustration of a lithium intercalation compound oriented along the (003) plane.
- Fig. 2 is an illustration of a lithium intercalation compound oriented along the preferred (101) plane.
- Fig. 3 is a plan view of a thin film lithium battery illustrating principles of the invention in a preferred embodiment .
- Fig. 4 is a cross-sectional view of the thin film lithium battery of Fig. 3 taken along plane 4-4.
- Fig. 5 is a schematic diagram of the apparatus utilized to deposit the cathode of the thin film lithium battery of Fig. 3.
- Fig. 6 is a photocopy of a photograph showing the first region of the cathode layer deposited in accordance with the method of the preferred embodiment.
- Fig. 7 is a photocopy of a photograph showing the second region of the cathode layer deposited in accordance with the method of the preferred embodiment.
- Fig. 8 is a photocopy of a photograph showing the third region of the cathode layer deposited in accordance with the method of the preferred embodiment .
- Fig. 9 is a photocopy of a photograph showing the first region of the cathode layer deposited in accordance with the method of the preferred embodiment after being annealed.
- Fig. 10 is a photocopy of a photograph showing the second region of the cathode layer deposited in accordance with the method of the preferred embodiment after being annealed.
- Fig. 11 is a photocopy of a photograph showing the third region of the cathode layer deposited in accordance with the method of the preferred embodiment after being annealed.
- Fig. 12 is a graph of an x-ray diffraction pattern of a cathode layer deposited in accordance with the method of the preferred embodiment .
- Fig. 13 is a graph of an x-ray diffraction pattern of a cathode layer deposited in accordance with the method of the preferred embodiment after being annealed.
- Fig. 14 is a schematic diagram of the apparatus utilized to deposit the cathode of the thin film lithium battery of Fig. 3.
- Fig. 15 is a cross-section of the nozzle of the apparatus shown in Fig. 14.
- Fig. 16 is a photocopy of a photograph showing the cathode layer deposited in accordance with the alternative embodiment .
- Fig. 17 is a schematic diagram of an apparatus utilized to deposit cathodes in another preferred embodiment .
- the battery cell 10 has an aluminum cathode current collector 11 sandwiched between two cathodes 12.
- the cathodes 12 are made of a lithium intercalation compound, or lithium metal oxide, such as LiCo0 2 , LiMg0 2 , LiNi0 2 or LiFe0 2 .
- Each cathode 12 has a solid state electrolyte 13 formed thereon.
- the electrolyte 13 is preferably made of lithium phosphorus oxynitride, Li x PO y N z .
- each electrolyte 13 has an anode 14 deposited thereon.
- the anode 14 is preferably made of silicon-tin oxynitride, SiTON, when used in lithium ion batteries, or other suitable materials such as lithium metal, zinc nitride or tin nitride.
- an anode current collector 16 preferably made of copper or nickel, contacts both anodes 14 to substantially encase the cathode collector 11, cathode 12, electrolyte 13 and anode 14.
- the inventive method will utilize a vapor deposition apparatus shown in Fig. 5.
- the apparatus includes a holding tank 20 coupled to an ultrasonic generator 21.
- the holding tank 20 has an air inlet 22 coupled to an air pump 23 and an outlet conduit 24 extending to an injection tube 25 having a nozzle 27 at one end.
- the injection tube 25 is coupled to a heating element 28.
- the nozzle 27 is directed towards a heater block 29 positioned adjacent the nozzle 27.
- the battery cell 10 is preferably manufactured in the following manner.
- a mixture of Li (TMHD) commonly referred to as lithium (2 , 2 , 6 , 6-tetramethyl-3 , 5-heptadionate or Li(C 11 H 19 0 2 ) and commonly referred to as cobalt (III) acety lacetonate Co(C 5 H 7 0 2 ) 3 or Co(acac) 3 is dissolved in an organic solvent, such as a mixture of diglyme, toluene and HTMHD, to produce a solution which is held within holding tank 20.
- an organic solvent such as a mixture of diglyme, toluene and HTMHD
- the ultrasonic generator 21, or any other type of conventional atomizer creates a stream of solution mist, having a liquid droplet size distribution of between 5 to 20 micrometers with a preferred droplet size of approximately 5 micrometers .
- the mist droplets are carried through the outlet conduit 24 to the injection tube 25 due to the force of the pressurized air from air pump 23 introduced into the holding tank through air inlet 22, the air inlet airstream is pressurized to between 1-2 p.s.i.
- the injection tube 25 is heated to approximately 200°C so that the mist droplets passing therethrough are vaporized.
- This vapor is then directed onto a substrate positioned approximately 1.5 to 2 inches from the end of nozzle.
- the substrate is heated by the underlying heating block 29 to approximately 400°C.
- the Li (TMHD) and Co(acac) 3 reacts with the 0 2 within the ambient air resulting in the formation of a layer of LiCo0 2 on the substrate surface and the production of volatile organic gases which are vented away. It has been discovered that the resulting layer LiCo0 2 forms as crystals having a preferred orientation along the (101) plane, as shown in Fig. 2.
- the substrate may then be inverted m order to deposit a layer upon its opposite side.
- TMHD TMHD
- Co (acac) 3 0.5 grams of Co (acac) 3 in an organic solvent comprising a mixture of diglyme, toluene and HTMHD having a volume of 53 ml.
- the mixture contained 40 ml of diglyme, 10 ml toluene and 3 ml of HTMHD.
- This solution provides a critical advantage as it is capable of being handled in air without any adverse effects.
- the misted solution was passed through a 1/4 inch ID outlet conduit 24 at a rate of 2 liters per minute and through an approximately 2 inch long injection tube heated to 200°C in order to achieve complete vaporization of the mist.
- the resulting vapor was directed onto a Si0 2 substrate positioned approximately 1.5 inches from the nozzle 27.
- the resulting layer of LiCo0 2 appeared to have three concentric, distinct regions: a central first region Rl having a dark green, shiny appearance, a second region R2 surrounding the first region Rl having a dark green appearance, and a third region R3 surrounding the second region R2 having a light green appearance. It is believed that this non-uniformity is due to the injection scheme utilized in the experiment.
- FIGs. 6-8 there are shown SEM photographs of the first, second and third regions, respectively.
- Figs. 6 and 8 show that the first and third regions of the layer to be extremely smooth with very uniform grain sizes of approximately lOOnm. This smoothness and grain size provides an exceptional cathode structure not previously achieved with conventional vapor deposition methods. The layer exhibited no evidence of cracking or peeling.
- an x-ray diffraction pattern of all three regions shows a high degree of texturing in the (101) plane. It should be noted that the peaks associated with the LiCo0 2 phase are sharp which indicates that this phase has good crystallinity . This also shows a broad peak at approximately 22° which is assumed to be associated with the amorphous Si0 2 substrate.
- the sample layer of LiCo0 2 was then annealed at 650°C for a period of 30 minutes. A comparison of the pre- annealed sample to the post -annealed sample showed little differences.
- Figs. 9-11 show the first, second and third regions, respectively, of the post-annealed sample. It should be noted that the crystalline structure within the
- the present invention results in the formation of a LiCo0 2 layer with the proper (101) plane crystalline growth. Moreover, this process achieves this result without the need of annealing the LiCo0 2 layer to achieve the proper (101) plane crystalline growth. Lastly, this was achieved utilizing chemical vapor deposition in ambient conditions.
- the cathode layer is complete the remaining portions of the battery, such as the electrolyte 13, anode 14, anode collector 16 may be applied.
- the electrolyte and anode may be applied through any conventional means, such as by sputtering, chemical vapor deposition, spray pyrolysis, laser ablation, ion beam evaporation or the like .
- the length of the injection tube 25, flow rate through the injection tube and heating of the injection tube are all variables that must be adjusted in order to achieve the proper vaporization of the mist droplets passing through the injection tube, i.e. the heat input must be matched to the boiling point of the solvent.
- the injection tube may be heated by any convention means, such as with microwave radiation, heat lamps, resistive coils, etc. Also, any conventional device may be utilized to mist or atomize the solution.
- the inventive method also includes the method of spraying the solution into a mist form that is then passed through a heated zone so as to vaporize the mist prior to reaching the substrate, as illustrated in Fig. 5 by heating elements 28.
- lithium and cobalt compounds or chelates compounds may be utilized in the inventive method preferably those which can be volatilized below 300°C. However, it is believed that the recited compounds provide the critical advantage of the capability of being handled in air.
- the first region Rl is utilized as the cathode of a battery. It is believed that through a proper arrangement of multiple nozzles the first region Rl may be optimized in size while the second and third regions R2 and R3 minimized or altogether eliminated.
- the inventive method utilizes a chemical vapor deposition apparatus 40 shown in Fig. 14.
- the apparatus 40 includes a copper heating chamber 42 having a heating element 43 therein, preferably made of nichrome or other suitable resistance heating wire such a platinum, and a temperature probe 44 for monitoring the temperature within the heating chamber 42.
- the heating element 43 is coupled to a variable transformer 46 which controls the power to the resistive heating element 43 and thereby the heat within the heating chamber.
- the heating chamber 42 is in fluid communication with a pressure tank 47 through a conduit 48.
- the pressure tank 47 contains a supply of compressed inert gas such as nitrogen or argon.
- the heating chamber 42 is also in fluid communication with a supply of precursor solution contained within a non-reactive storage container 50, such as that made of polyethylene, via a conduit 51.
- the storage container 50 contains an ultrasonic generator 52 which atomizes the solution as previously described.
- the storage container 50 is also in fluid communication with the supply of compressed inert gas within pressure tank 47 through a conduit 55.
- Conduits 48 and 53 have metering valves 54 which control the flow of gas through the respective conduits.
- a nozzle 55 is coupled to the heating chamber 42 so as to direct the flow of the precursor entrained heated gas stream onto an adjacent substrate 56.
- the nozzle is preferably made of ceramic having an approximately 1mm opening therethrough. As best shown in Fig.
- the nozzle 55 is coupled to conduit 51 and has an interior passage shaped to create a venturi effect which aids in drawing the precursor from the conduit and causing a uniform mixing of the precursor with the heated gas stream.
- the substrate may also include a temperature probe for monitoring the temperature of the substrate during deposition.
- the battery cell is preferably manufactured with the just described apparatus 40 in the following manner.
- the metering valve 54 coupled to conduit 48 is opened to allow the flow of inert gas from within the pressure tank 47 into the heating chamber 42 wherein the heating element 43 raises the temperature of the gas stream passing through the heating chamber to approximately 600 degrees Celsius.
- the metering valve 54 of conduit 53 is opened to cause the pressurized inert gas to flow through conduit 53 into the storage container 50.
- the precursor mist droplets produced by the ultrasonic generator 52 are delivered into the pre-heated inert gas stream at rates ranging from 5 to 50 ml/hr.
- the precursor mist droplets are carried though conduit 51 to the heating chamber nozzle 55 due to the force of the pressurized inert gas entering the storage container 50.
- the precursor droplets Upon entering the heating chamber 42 downstream of the heating element 43, the precursor droplets are flash vaporized wherein the vapor is entrained into the heated gas stream. The precursor droplets are additionally reacted from contact with the heated gas stream. This serves to chemically activate the precursor and allows for subsequent deposition onto a substrate. This stream is then directed by nozzle 55 onto a substrate, positioned approximately 0.28 inch from the nozzle 55, wherein the vaporized precursor arrives at the substrate 56 and decomposes into a mixed oxide. The substrate 56 is heated to approximately 350 degrees Celsius. In this case, the mixed oxide is lithium cobalt oxide and the deposition rate of the lithium cobalt oxide is believed to be approximately 0.5 microns/hr .
- Fig. 15 there is shown a photocopy of a photograph of the resulting lithium cobalt oxide layer produced in the previously described manner upon an alumina ceramic substrate.
- the layer was produced utilizing a solution comprised of 150 ml of de-ionized water, 0.09 grams of lithium (acac) and 0.3 grams of cobalt
- FIG. 17 there is shown an apparatus similar to that shown in Fig. 14 except that the pressure tank 47 is not in fluid communication with the storage container 50. Here, the precursor is drawn through the conduit 51 through the force of the venturi alone. It should be understood that similar apparatuses may be devised which do not utilize a venturi nozzle or may utilize spray nozzles which deliver droplets into the heating chamber downstream of heating element 43.
- aqueous solvent as used herein, is intended in include solvents which are largely water based and therefore may also include other additional materials such as organic solvents. It should also be understood that the just described method may be accomplished without the external heating of the substrate. It thus is seen that a high rate capability battery cathode is now provided which is manufacture without an extremely low pressure environment and without a non- reactive gas environment, yet still includes a good crystal alignment without the need of post annealing. It should of course be understood that many modifications may be made to the specific preferred embodiment described herein without departure from the spirit and scope of the invention as set forth in the following claims.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00982172A EP1252664A2 (en) | 1999-11-23 | 2000-11-20 | Method and apparatus for producing lithium based cathodes |
JP2001540859A JP2003515888A (en) | 1999-11-23 | 2000-11-20 | Method and apparatus for producing a lithium-based cathode |
IL14979500A IL149795A0 (en) | 1999-11-23 | 2000-11-20 | Method and apparatus for producing lithium based cathodes |
AU19237/01A AU1923701A (en) | 1999-11-23 | 2000-11-20 | Method and apparatus for producing lithium based cathodes |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/447,250 US6582481B1 (en) | 1999-11-23 | 1999-11-23 | Method of producing lithium base cathodes |
US09/447,250 | 1999-11-23 | ||
US09/511,275 | 2000-02-23 | ||
US09/511,275 US6511516B1 (en) | 2000-02-23 | 2000-02-23 | Method and apparatus for producing lithium based cathodes |
Publications (2)
Publication Number | Publication Date |
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WO2001039290A2 true WO2001039290A2 (en) | 2001-05-31 |
WO2001039290A3 WO2001039290A3 (en) | 2001-11-22 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2000/031889 WO2001039290A2 (en) | 1999-11-23 | 2000-11-20 | Method and apparatus for producing lithium based cathodes |
Country Status (7)
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EP (1) | EP1252664A2 (en) |
JP (1) | JP2003515888A (en) |
KR (1) | KR20030014346A (en) |
CN (1) | CN1195681C (en) |
AU (1) | AU1923701A (en) |
IL (1) | IL149795A0 (en) |
WO (1) | WO2001039290A2 (en) |
Families Citing this family (6)
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US8354294B2 (en) * | 2006-01-24 | 2013-01-15 | De Rochemont L Pierre | Liquid chemical deposition apparatus and process and products therefrom |
JP2008300190A (en) * | 2007-05-31 | 2008-12-11 | Fuji Heavy Ind Ltd | Manufacturing method of electrode |
CN100511777C (en) * | 2007-07-13 | 2009-07-08 | 张家港市国泰华荣化工新材料有限公司 | A making method of cathode material for lithium ion battery |
JP2010083700A (en) * | 2008-09-30 | 2010-04-15 | Dainippon Printing Co Ltd | Layered body having cobalt oxide film |
CA2770906A1 (en) * | 2009-08-14 | 2011-02-17 | The Regents Of The University Of Michigan | Direct thermal spray synthesis of li ion battery components |
CN113913787A (en) * | 2021-10-15 | 2022-01-11 | 浙江生波智能装备有限公司 | Novel film preparation process and vacuum coating equipment |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5589300A (en) * | 1993-09-27 | 1996-12-31 | Arthur D. Little, Inc. | Small particle electrodes by aerosol process |
US5770018A (en) * | 1996-04-10 | 1998-06-23 | Valence Technology, Inc. | Method for preparing lithium manganese oxide compounds |
US5976489A (en) * | 1996-04-10 | 1999-11-02 | Valence Technology, Inc. | Method for preparing lithium manganese oxide compounds |
Family Cites Families (1)
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JPH08975B2 (en) * | 1991-10-17 | 1996-01-10 | 東ソー・アクゾ株式会社 | Metal acetylacetonato complex for oxide thin film formation |
-
2000
- 2000-11-20 KR KR1020027006563A patent/KR20030014346A/en not_active Application Discontinuation
- 2000-11-20 WO PCT/US2000/031889 patent/WO2001039290A2/en not_active Application Discontinuation
- 2000-11-20 CN CNB008178372A patent/CN1195681C/en not_active Expired - Fee Related
- 2000-11-20 JP JP2001540859A patent/JP2003515888A/en active Pending
- 2000-11-20 AU AU19237/01A patent/AU1923701A/en not_active Abandoned
- 2000-11-20 EP EP00982172A patent/EP1252664A2/en not_active Withdrawn
- 2000-11-20 IL IL14979500A patent/IL149795A0/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5589300A (en) * | 1993-09-27 | 1996-12-31 | Arthur D. Little, Inc. | Small particle electrodes by aerosol process |
US5770018A (en) * | 1996-04-10 | 1998-06-23 | Valence Technology, Inc. | Method for preparing lithium manganese oxide compounds |
US5976489A (en) * | 1996-04-10 | 1999-11-02 | Valence Technology, Inc. | Method for preparing lithium manganese oxide compounds |
Also Published As
Publication number | Publication date |
---|---|
CN1414924A (en) | 2003-04-30 |
JP2003515888A (en) | 2003-05-07 |
AU1923701A (en) | 2001-06-04 |
EP1252664A2 (en) | 2002-10-30 |
WO2001039290A3 (en) | 2001-11-22 |
KR20030014346A (en) | 2003-02-17 |
CN1195681C (en) | 2005-04-06 |
IL149795A0 (en) | 2002-11-10 |
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