US20050169833A1 - Process for making nano-sized and sub-micron-sized lithium-transition metal oxides - Google Patents
Process for making nano-sized and sub-micron-sized lithium-transition metal oxides Download PDFInfo
- Publication number
- US20050169833A1 US20050169833A1 US11/088,529 US8852905A US2005169833A1 US 20050169833 A1 US20050169833 A1 US 20050169833A1 US 8852905 A US8852905 A US 8852905A US 2005169833 A1 US2005169833 A1 US 2005169833A1
- Authority
- US
- United States
- Prior art keywords
- lithium
- transition
- sized
- metal oxide
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- 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
-
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- C01P2006/12—Surface area
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- the present invention relates to a process for producing nano-sized and sub-micron-sized lithium titanate, lithium manganate, lithium cobalt oxide and other oxides of lithium and transition metals. It covers parts of the process and the product of the process.
- the starting material is a coarse oxide with low surface area.
- the product made according to the process of the present invention has a high surface area and a narrow particle size distribution.
- Lithium-transition metal oxides are materials presently used or under development for the electrodes of lithium ion batteries.
- the transition metals Co, Mn, Ni, Ti, and V have received particular attention for this application. Recently, it has become apparent that a smaller particle size and a narrower particle size distribution are beneficial for producing electrodes, which retain their charging capacity at high charging and discharging rates.
- a method to prepare lithium titanate from inorganic solutions or suspensions is described in U.S. Pat. Appln. Pub. 2003/0017104 A1, the relevant portions of which are incorporated herein by reference. That application describes a process to produce lithium titanate crystallites. The process achieves good phase and size control in the range of 5 to 2000 nm. In general, the process includes providing a source of lithium titanate with a particle size smaller than the desired particle size and re-firing the lithium titanate under conditions to produce a final lithium titanate having a desired particle size with a narrow size distribution and controlled surface area.
- a source of lithium titanate is from a process that includes forming a blend that comprises titanium and lithium.
- the blend is evaporated to form homogeneous particles containing a lithium salt and titanium dioxide.
- the evaporation is conducted at a temperature above the boiling point of the solution in the blend but below the temperature where reaction of the lithium salt and the titanium dioxide occurs.
- the homogeneous particles are calcined to form lithium titanate.
- the lithium titanate is milled or crushed to a size smaller than the desired size of the final product. Finally, the milled lithium titanate is re-fired under conditions to produce lithium titanate having a desired surface area and size distribution.
- the blend of titanium and lithium can be provided from a variety of suitable sources.
- the blend of titanium and lithium is provided as aqueous chloride solutions of titanium and lithium.
- the blend of titanium and lithium is provided as a suspension of amorphous titanium dioxide in a lithium solution.
- the lithium solution can be formed from a source of lithium selected from the group consisting of lithium chloride, lithium nitrate, lithium hydroxide, lithium sulfate, lithium oxide, lithium fluoride, lithium bromide, and mixtures thereof.
- lithium titanate made by any known means and having a particle size smaller than the particle size of the desired product, can be used as the source of lithium and titanium for the re-firing step, where crystals are grown to the desired size.
- Materials commercially available for the manufacture of battery electrodes generally have a wide particle size distribution and include large particles of several microns in size as well as very fine dust. Therefore, there is a need for materials having a narrow size distribution and having a controlled surface area for such applications as electrodes for batteries.
- the present invention provides a process to produce lithium-transition metal oxides in the range 10 to 1000 nm, and preferably 10 to 100 nm with a narrow particle size distribution.
- the phrase narrow particle size distribution means that the particle size of the lithium-transition metal oxide is within 10 nm to 1,000 nm with a standard deviation of no more than 20%.
- the process starts from a coarse oxide of lithium and a transition metal.
- the coarse oxide of lithium and a transition metal can be provided by any suitable method including using commercially available coarse oxides.
- the process produces nano-sized crystals through a combination of milling, dispersion and calcining (re-firing) steps.
- the transition metal may be any metal commonly defined as transition metal, including but not limited to Ti, Co, Mn, V, Fe, and Ni.
- FIG. 1 is a flow sheet of the general aspect of the process.
- FIG. 2 is a flow sheet of the process according to one embodiment of the present invention, where the starting material is lithium titanate spinel and the final product is a slurry containing nano-sized particles.
- FIG. 3 is a flow sheet of the process according to the invention, where the starting material is lithium manganate LiMn 2 O 4 or lithium cobalt oxide LiCoO 2 and the final product is a nano-sized dispersed lithium manganate or lithium cobalt oxide powder.
- FIG. 4 is a scanning electron micrograph of lithium titanate spinel of about 1 to 2 ⁇ m in size, serving as starting material for the process of the present invention.
- FIG. 5 is a scanning electron micrograph showing lithium titanate spinel products of different particles sizes, produced following the process of the present invention.
- FIG. 6 is a scanning electron micrograph showing commercial lithium manganate used as starting material for the process of the present invention.
- FIG. 7 is a scanning electron micrograph showing lithium manganate products of different particle sizes produced following the process of the present invention.
- a process for making lithium-transition-metal oxides is provided.
- a lithium transition-metal oxide is milled or crushed to a size smaller than the desired size of the final product.
- the milled or crushed lithium-metal oxide is re-fired under controlled conditions to produce lithium-transition-metal oxide (e.g., lithium titanate) having a desired surface area and size distribution.
- Further processing may include dispersion, remilling, slurrying and spray drying and the final product may be a slurry, a spry dried powder consisting of agglomerates of nano-particles, or a fully dispersed powder.
- FIG. 1 a flow sheet according to the general process is shown.
- Coarse lithium-transition-metal oxide particles are milled 40 to a desired median size.
- the lithium-transition-metal oxide e.g., lithium titanate
- the controlled temperature furnace 50 to produce particles having a desired size and size distribution.
- the particles produced from the re-firing can be dispersed 60 or can be milled 90 . If the particles are dispersed, they may be further processed or may be left as is. Further processing may include forming a lithium transition-metal oxide slurry 70 , which can be further processed by spray drying 80 to produce spray-dried powder agglomerates that consist of primary particles. The spray-dried powder agglomerates may be sold or may be further processed by milling 90 to produce a fully dispersed powder.
- the starting material of coarse particles can be made by any method.
- commercially available coarse lithium-transition-metal oxide particles can be used as the starting material.
- one suitable method is described in U.S. Pat. Appln. Publication 2003/0017104 A1, the relevant portions of which are incorporated herein by reference. While the process described in U.S. Pat. Appln. Publication 2003/0017104 is directed to lithium titanate; it has now been found that the described process can be used to make the lithium transition-metal oxides described in the present application.
- a related method is described in U.S. Pat. Appln. Publication 2002/0071806, the relevant portions of which are incorporated herein by reference.
- a blend of a transition metal and lithium is provided by providing a source of lithium and a source of a transition metal.
- This blend may be referred to herein as the lithium-transition-metal blend or the transition-metal-lithium blend.
- the blend is evaporated.
- the evaporation process is conducted above the boiling point of the liquid in the blend and below the temperature where significant reaction of the lithium and the transition-metal compounds occurs or where there is significant crystallization of lithium-transition-metal.
- the evaporation is conducted under conditions to achieve substantially total evaporation and to form an intermediate.
- the evaporation is conducted at a temperature higher than the boiling point of the blend but lower than the temperature where significant crystal growth of an oxide phase occurs.
- the evaporation may be conducted at a temperature higher than the boiling point of the blend but lower than the calcination temperature of the intermediate.
- substantially total evaporation or “substantially complete evaporation” refers to evaporation of greater than 85% of the free water content, preferably greater than 90% of the free water and more preferably greater than 95% of the free water present in the feed solution.
- free water is understood and means water that is not chemically bound and can be removed by heating at a temperature below 150° C. After substantially total evaporation or substantially complete evaporation, the intermediate product will have no visible moisture present.
- the evaporation process is performed in a manner to control the physical form of the product.
- the evaporation process is accomplished by spraying the blend while it is heated at a temperature in the range from about 120° C. to about 350° C., and desirably in the range from about 200° C. to about 250° C. This process may be conducted in a spray dryer.
- the evaporation process may be conducted in such a manner as to form a film of a mixture of a lithium compound and an amorphous oxidized transition-metal compound.
- the evaporation process may be conducted in such a way as to form a thin film of lithium salt on the preexisting particles of amorphous oxidized transition-metal compound.
- the characteristics of the solid intermediate product can be reliably controlled within a fairly narrow range.
- the product resulting from injection in a spray dryer will generally be composed of hollow spheres or parts of spheres.
- the dimensions of the spheres may vary from less than 0.1 ⁇ m to 100 ⁇ m or more in diameter and a shell thickness in the range from about 30 nanometer to about 1000 nanometer or more.
- the structure of the shell consists of an intimate mixture of transition-metal and lithium compounds.
- Evaporation by spraying also has the advantage of direct processing of the solution so that a homogeneous intermediate product is formed and so that evaporation of water and acid is simultaneously accomplished. Preferably, from about 90% to about 99% of any aqueous material is evaporated.
- the product resulting from the evaporation step is calcined at a temperature and for a length of time sufficient to convert the mixture of transition-metal and lithium compounds to lithium transition metal oxide of the desired structure and particle size.
- Calcination temperatures can range between about 600° C. to 950° C. Desirably, the calcination is conducted at temperatures ranging from about 700° C. to about 900° C.
- the calcination time varies over a wide range, from about 1 hour to as long as 36 hours. Desirably, the calcination time is in the range from about 6 hours to about 12 hours. Lower temperatures will require longer calcination times.
- the product of calcination shows a structure of individual units that can be broken up by milling into particles of the desired median size and size distribution.
- the lithium salt reacts with oxygen and water in the furnace atmosphere to release, for example, HCl gas or nitrous and nitric oxides or other gases formed by decomposition of the salt present in the original solution. These gases may be recovered.
- the calcination conditions are chosen such that contact with oxygen is sufficient to substantially convert the mixture to a lithium transition-metal oxide with low impurity level.
- the product of calcination may contain traces of the original lithium salt used as feed.
- the particles may be subject to one or several wash cycles. In each cycle, the particles are mixed with water and are separated by settling or filtration. The washing step is particularly useful if the lithium salt used is lithium chloride.
- the lithium-transition metal oxide is suspended in water and milled in a horizontal or vertical pressure media mill to crush the crystals to a size smaller than the size desired in the final product.
- wet-milled particles are dried by any known means.
- wet-milled particles may be dried in a spray drier at a temperature from about 120° to about 350° C., desirably from about 200° to about 250° C. Drying may also be part of the re-firing process.
- the product is re-fired in a controlled-temperature furnace to make a product with a well-controlled specific surface area, consisting of regular-shaped crystals with a narrow size distribution.
- the refiring temperature is chosen to achieve the desired particle size and surface area of the product.
- the re-firing temperature is between about 250° and 900° C.
- the BET surface area of the re-fired product is in the range 5 to 100 m 2 /g, with the higher re-firing temperature corresponding to the lower specific surface area.
- the product may be dispersed 60 to separate the agglomerates formed during re-firing into distinct nano-sized particles. This step is generally accomplished after slurrying the product in water.
- the product of the re-firing step may be milled 90 , i.e., dry-milled, preferably in a jet-mill.
- the product from the dispersing step can be kept as a slurry, or spray-dried, or spray-dried and jet-milled as indicated in FIG. 1 .
- Lithium titanate made by spray drying according to U.S. Pat. Appln. Publication 2003/0017104 A1 and described above was further calcined in an oxidizing atmosphere at a temperature of 800° C. for 12 hours.
- the product after calcination consisted of crystals of Li 4 Ti 5 O 12 of about 400 to about 1000 nm in size.
- FIG. 4 is a scanning electron micrograph of the product serving as starting material for the process of the present invention.
- FIG. 5 shows electron micrographs of the product obtained after refiring at 900°, 650°, 500°, and 400° C. respectively.
- the particle size was about 100 nm at 400° C., and increased to about 200, 500 and 1000 nm respectively at the higher temperatures.
- the micrographs show well-formed crystals with a narrow size distribution.
- Electron micrographs of each of the samples are shown in FIG. 7 . All calcined crystals are well formed and show narrow size distributions.
Abstract
A process is provided for making nano-sized or sub-micron sized oxides of lithium and a transition metal. The desired size is generally in the range 10 nm to 1000 nm and preferably in the range 10 nm to 100 nm. The particles have a narrow size distribution. The process includes milling and re-firing under controlled conditions so that crystallites of the desired particle size are grown.
Description
- The present application claims priority to U.S. Ser. No. 60/362,723 filed Mar. 8, 2002, the entire contents of which is hereby incorporated by reference.
- The present invention relates to a process for producing nano-sized and sub-micron-sized lithium titanate, lithium manganate, lithium cobalt oxide and other oxides of lithium and transition metals. It covers parts of the process and the product of the process. The starting material is a coarse oxide with low surface area. The product made according to the process of the present invention has a high surface area and a narrow particle size distribution.
- Lithium-transition metal oxides are materials presently used or under development for the electrodes of lithium ion batteries. The transition metals Co, Mn, Ni, Ti, and V have received particular attention for this application. Recently, it has become apparent that a smaller particle size and a narrower particle size distribution are beneficial for producing electrodes, which retain their charging capacity at high charging and discharging rates.
- A method to prepare lithium titanate from inorganic solutions or suspensions is described in U.S. Pat. Appln. Pub. 2003/0017104 A1, the relevant portions of which are incorporated herein by reference. That application describes a process to produce lithium titanate crystallites. The process achieves good phase and size control in the range of 5 to 2000 nm. In general, the process includes providing a source of lithium titanate with a particle size smaller than the desired particle size and re-firing the lithium titanate under conditions to produce a final lithium titanate having a desired particle size with a narrow size distribution and controlled surface area.
- That application describes that a source of lithium titanate is from a process that includes forming a blend that comprises titanium and lithium. The blend is evaporated to form homogeneous particles containing a lithium salt and titanium dioxide. The evaporation is conducted at a temperature above the boiling point of the solution in the blend but below the temperature where reaction of the lithium salt and the titanium dioxide occurs. The homogeneous particles are calcined to form lithium titanate.
- The lithium titanate is milled or crushed to a size smaller than the desired size of the final product. Finally, the milled lithium titanate is re-fired under conditions to produce lithium titanate having a desired surface area and size distribution.
- The blend of titanium and lithium can be provided from a variety of suitable sources. For example, the blend of titanium and lithium is provided as aqueous chloride solutions of titanium and lithium. Alternatively, the blend of titanium and lithium is provided as a suspension of amorphous titanium dioxide in a lithium solution. In this instance, the lithium solution can be formed from a source of lithium selected from the group consisting of lithium chloride, lithium nitrate, lithium hydroxide, lithium sulfate, lithium oxide, lithium fluoride, lithium bromide, and mixtures thereof. In yet another alternative, lithium titanate, made by any known means and having a particle size smaller than the particle size of the desired product, can be used as the source of lithium and titanium for the re-firing step, where crystals are grown to the desired size.
- A method to prepare mixed metal oxides and metal oxide compounds is also described in U.S. Pat. Appln. Publication U.S. 2002/0071806 A1 the relevant portions of which are incorporated herein by reference. This method applies to mixed oxides of lithium and transition metals. Products made according to this patent application can be used as starting materials for the process of the present invention.
- Materials commercially available for the manufacture of battery electrodes generally have a wide particle size distribution and include large particles of several microns in size as well as very fine dust. Therefore, there is a need for materials having a narrow size distribution and having a controlled surface area for such applications as electrodes for batteries.
- The present invention provides a process to produce lithium-transition metal oxides in the range 10 to 1000 nm, and preferably 10 to 100 nm with a narrow particle size distribution. The phrase narrow particle size distribution means that the particle size of the lithium-transition metal oxide is within 10 nm to 1,000 nm with a standard deviation of no more than 20%.
- In general, the process starts from a coarse oxide of lithium and a transition metal. The coarse oxide of lithium and a transition metal can be provided by any suitable method including using commercially available coarse oxides. The process produces nano-sized crystals through a combination of milling, dispersion and calcining (re-firing) steps. The transition metal may be any metal commonly defined as transition metal, including but not limited to Ti, Co, Mn, V, Fe, and Ni.
-
FIG. 1 is a flow sheet of the general aspect of the process. -
FIG. 2 is a flow sheet of the process according to one embodiment of the present invention, where the starting material is lithium titanate spinel and the final product is a slurry containing nano-sized particles. -
FIG. 3 is a flow sheet of the process according to the invention, where the starting material is lithium manganate LiMn2O4 or lithium cobalt oxide LiCoO2 and the final product is a nano-sized dispersed lithium manganate or lithium cobalt oxide powder. -
FIG. 4 is a scanning electron micrograph of lithium titanate spinel of about 1 to 2 μm in size, serving as starting material for the process of the present invention. -
FIG. 5 is a scanning electron micrograph showing lithium titanate spinel products of different particles sizes, produced following the process of the present invention. -
FIG. 6 is a scanning electron micrograph showing commercial lithium manganate used as starting material for the process of the present invention. -
FIG. 7 is a scanning electron micrograph showing lithium manganate products of different particle sizes produced following the process of the present invention. - According to the present invention, a process for making lithium-transition-metal oxides is provided. In this process, a lithium transition-metal oxide is milled or crushed to a size smaller than the desired size of the final product. The milled or crushed lithium-metal oxide is re-fired under controlled conditions to produce lithium-transition-metal oxide (e.g., lithium titanate) having a desired surface area and size distribution. Further processing may include dispersion, remilling, slurrying and spray drying and the final product may be a slurry, a spry dried powder consisting of agglomerates of nano-particles, or a fully dispersed powder.
- Turning now to
FIG. 1 , a flow sheet according to the general process is shown. Coarse lithium-transition-metal oxide particles are milled 40 to a desired median size. After milling, the lithium-transition-metal oxide (e.g., lithium titanate) is dried 45 and re-fired in a controlledtemperature furnace 50 to produce particles having a desired size and size distribution. - Thereafter, the particles produced from the re-firing can be dispersed 60 or can be milled 90. If the particles are dispersed, they may be further processed or may be left as is. Further processing may include forming a lithium transition-
metal oxide slurry 70, which can be further processed by spray drying 80 to produce spray-dried powder agglomerates that consist of primary particles. The spray-dried powder agglomerates may be sold or may be further processed bymilling 90 to produce a fully dispersed powder. - The specific steps of the process will be explained in more detail below.
- Starting Material
- The starting material of coarse particles can be made by any method. For example, commercially available coarse lithium-transition-metal oxide particles can be used as the starting material. Alternatively, as noted above, one suitable method is described in U.S. Pat. Appln. Publication 2003/0017104 A1, the relevant portions of which are incorporated herein by reference. While the process described in U.S. Pat. Appln. Publication 2003/0017104 is directed to lithium titanate; it has now been found that the described process can be used to make the lithium transition-metal oxides described in the present application. In addition, a related method is described in U.S. Pat. Appln. Publication 2002/0071806, the relevant portions of which are incorporated herein by reference.
- According to those processes, a blend of a transition metal and lithium is provided by providing a source of lithium and a source of a transition metal. This blend may be referred to herein as the lithium-transition-metal blend or the transition-metal-lithium blend.
- After the lithium-transition-metal blend is created, the blend is evaporated. The evaporation process is conducted above the boiling point of the liquid in the blend and below the temperature where significant reaction of the lithium and the transition-metal compounds occurs or where there is significant crystallization of lithium-transition-metal.
- The evaporation is conducted under conditions to achieve substantially total evaporation and to form an intermediate. In particular, the evaporation is conducted at a temperature higher than the boiling point of the blend but lower than the temperature where significant crystal growth of an oxide phase occurs. The evaporation may be conducted at a temperature higher than the boiling point of the blend but lower than the calcination temperature of the intermediate.
- The term “substantially total evaporation” or “substantially complete evaporation” refers to evaporation of greater than 85% of the free water content, preferably greater than 90% of the free water and more preferably greater than 95% of the free water present in the feed solution. The term “free water” is understood and means water that is not chemically bound and can be removed by heating at a temperature below 150° C. After substantially total evaporation or substantially complete evaporation, the intermediate product will have no visible moisture present.
- The evaporation process is performed in a manner to control the physical form of the product. Preferably, the evaporation process is accomplished by spraying the blend while it is heated at a temperature in the range from about 120° C. to about 350° C., and desirably in the range from about 200° C. to about 250° C. This process may be conducted in a spray dryer.
- As noted in U.S. Pat. Appln. Pub. 2003/0017104 A1, the evaporation process may be conducted in such a manner as to form a film of a mixture of a lithium compound and an amorphous oxidized transition-metal compound. In this regard, the evaporation process may be conducted in such a way as to form a thin film of lithium salt on the preexisting particles of amorphous oxidized transition-metal compound.
- In both cases, through control of the operating parameters, including temperature and concentration of transition-metal and lithium, the characteristics of the solid intermediate product can be reliably controlled within a fairly narrow range. For example, the product resulting from injection in a spray dryer, will generally be composed of hollow spheres or parts of spheres. The dimensions of the spheres may vary from less than 0.1 μm to 100 μm or more in diameter and a shell thickness in the range from about 30 nanometer to about 1000 nanometer or more. The structure of the shell consists of an intimate mixture of transition-metal and lithium compounds.
- Evaporation by spraying also has the advantage of direct processing of the solution so that a homogeneous intermediate product is formed and so that evaporation of water and acid is simultaneously accomplished. Preferably, from about 90% to about 99% of any aqueous material is evaporated.
- The product resulting from the evaporation step is calcined at a temperature and for a length of time sufficient to convert the mixture of transition-metal and lithium compounds to lithium transition metal oxide of the desired structure and particle size. Calcination temperatures can range between about 600° C. to 950° C. Desirably, the calcination is conducted at temperatures ranging from about 700° C. to about 900° C. The calcination time varies over a wide range, from about 1 hour to as long as 36 hours. Desirably, the calcination time is in the range from about 6 hours to about 12 hours. Lower temperatures will require longer calcination times. The product of calcination shows a structure of individual units that can be broken up by milling into particles of the desired median size and size distribution.
- During calcination, the lithium salt reacts with oxygen and water in the furnace atmosphere to release, for example, HCl gas or nitrous and nitric oxides or other gases formed by decomposition of the salt present in the original solution. These gases may be recovered. The calcination conditions are chosen such that contact with oxygen is sufficient to substantially convert the mixture to a lithium transition-metal oxide with low impurity level.
- The product of calcination may contain traces of the original lithium salt used as feed. To remove the traces of salt, the particles may be subject to one or several wash cycles. In each cycle, the particles are mixed with water and are separated by settling or filtration. The washing step is particularly useful if the lithium salt used is lithium chloride.
- Milling
- The lithium-transition metal oxide is suspended in water and milled in a horizontal or vertical pressure media mill to crush the crystals to a size smaller than the size desired in the final product.
- Drying
- The wet-milled particles are dried by any known means. For example, wet-milled particles may be dried in a spray drier at a temperature from about 120° to about 350° C., desirably from about 200° to about 250° C. Drying may also be part of the re-firing process.
- Re-Firing
- After milling or drying, the product is re-fired in a controlled-temperature furnace to make a product with a well-controlled specific surface area, consisting of regular-shaped crystals with a narrow size distribution. The refiring temperature is chosen to achieve the desired particle size and surface area of the product. In general, the re-firing temperature is between about 250° and 900° C., and the BET surface area of the re-fired product is in the
range 5 to 100 m2/g, with the higher re-firing temperature corresponding to the lower specific surface area. - Dispersing
- After the refiring step, the product may be dispersed 60 to separate the agglomerates formed during re-firing into distinct nano-sized particles. This step is generally accomplished after slurrying the product in water. Alternatively, the product of the re-firing step may be milled 90, i.e., dry-milled, preferably in a jet-mill.
- Further Processing
- Depending on the destination of the final product, the product from the dispersing step can be kept as a slurry, or spray-dried, or spray-dried and jet-milled as indicated in
FIG. 1 . - The following examples illustrate, but do not limit, the present invention.
- Lithium titanate made by spray drying according to U.S. Pat. Appln. Publication 2003/0017104 A1 and described above was further calcined in an oxidizing atmosphere at a temperature of 800° C. for 12 hours. The product after calcination consisted of crystals of Li4Ti5O12 of about 400 to about 1000 nm in size.
FIG. 4 is a scanning electron micrograph of the product serving as starting material for the process of the present invention. - The product of the calcination step was further suspended in water and milled with 0.4 to 0.6 mm zirconia grinding media for 8 hours. The BET surface area of this product was 135 m2/g. This product was refired at constant temperature for 3 hours.
FIG. 5 shows electron micrographs of the product obtained after refiring at 900°, 650°, 500°, and 400° C. respectively. The particle size was about 100 nm at 400° C., and increased to about 200, 500 and 1000 nm respectively at the higher temperatures. The micrographs show well-formed crystals with a narrow size distribution. - Commercial lithium manganate, of particle size and shape shown in
FIG. 6 , was slurried as a 40 weight % suspension in water and was milled in a Premier Mill bead mill for 20 h. The product of this operation was dried, and then calcined in ceramic trays placed in a constant temperature furnace for 3 hours. The results of calcinations at different temperatures are given in the Table below:Calcination temperature Particle size (C.) (nm) uncalcined 15 400° 20 450° 30 500° 50 - Electron micrographs of each of the samples are shown in
FIG. 7 . All calcined crystals are well formed and show narrow size distributions. - While the invention has been described in conjunction with specific embodiments, it is to be understood that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, this invention is intended to embrace all such alternatives, modifications, and variations that fall within the spirit and scope of the appended claims.
Claims (11)
1. A process for producing a nano-sized or sub-micron oxide of lithium and a transition metal comprising:
a. milling a coarse lithium transition-metal oxide; and,
b. re-firing the lithium transition-metal oxide
2. The process of claim 1 wherein the lithium transition-metal oxide is tetra lithium titanate spinel
3. The process of claim 1 wherein the lithium transition-metal oxide is LiCoO2.
4. The process of claim 1 wherein the lithium transition-metal oxide is LiMn2O4.
5. The process of claim 1 wherein the milling is accomplished by wet-milling in a bead mill.
6. The process of claim 1 further comprising:
a. dispersing the product resulting from re-firing to liberate crystallites; and,
b. slurrying the crystallites to form a suspension.
7. The process of claim 1 further comprising milling the product resulting from re-firing to form a dispersed powder.
8. The process of claim 6 further comprising spray-drying the suspension.
9. The process of claim 8 further comprising milling the spray-dried product to form a dispersed powder.
10. A lithium-transition metal oxide with a particle size between 10 nm and 1000 nm and a standard deviation of no more than 20%.
11. A lithium-transition metal oxide with a particle size between 10 nm and 1000 nm and a standard deviation of no more than 20% made according to the process of claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/088,529 US20050169833A1 (en) | 2002-03-08 | 2005-03-24 | Process for making nano-sized and sub-micron-sized lithium-transition metal oxides |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US36272302P | 2002-03-08 | 2002-03-08 | |
US10/383,821 US6881393B2 (en) | 2002-03-08 | 2003-03-07 | Process for making nano-sized and sub-micron-sized lithium-transition metal oxides |
US11/088,529 US20050169833A1 (en) | 2002-03-08 | 2005-03-24 | Process for making nano-sized and sub-micron-sized lithium-transition metal oxides |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/383,821 Continuation US6881393B2 (en) | 2002-03-08 | 2003-03-07 | Process for making nano-sized and sub-micron-sized lithium-transition metal oxides |
Publications (1)
Publication Number | Publication Date |
---|---|
US20050169833A1 true US20050169833A1 (en) | 2005-08-04 |
Family
ID=27805218
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/383,821 Expired - Lifetime US6881393B2 (en) | 2002-03-08 | 2003-03-07 | Process for making nano-sized and sub-micron-sized lithium-transition metal oxides |
US11/088,529 Abandoned US20050169833A1 (en) | 2002-03-08 | 2005-03-24 | Process for making nano-sized and sub-micron-sized lithium-transition metal oxides |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/383,821 Expired - Lifetime US6881393B2 (en) | 2002-03-08 | 2003-03-07 | Process for making nano-sized and sub-micron-sized lithium-transition metal oxides |
Country Status (8)
Country | Link |
---|---|
US (2) | US6881393B2 (en) |
EP (1) | EP1483206B1 (en) |
JP (1) | JP4340160B2 (en) |
AT (1) | ATE485241T1 (en) |
AU (1) | AU2003228290A1 (en) |
CA (1) | CA2478698C (en) |
DE (1) | DE60334610D1 (en) |
WO (1) | WO2003076338A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040197657A1 (en) * | 2001-07-31 | 2004-10-07 | Timothy Spitler | High performance lithium titanium spinel li4t15012 for electrode material |
US20070092798A1 (en) * | 2005-10-21 | 2007-04-26 | Spitler Timothy M | Lithium ion batteries |
WO2007078429A2 (en) * | 2005-12-23 | 2007-07-12 | Uchicago Argonne, Llc. | Electrode materials and lithium battery systems |
US20080108529A1 (en) * | 2006-11-08 | 2008-05-08 | The Lubrizol Corporation | Process for Preparing High Concentration Dispersions of Lithium Hydroxide Monohydrate and of Anhydrous Lithium Hydroxide Oils |
US20110052484A1 (en) * | 2009-08-27 | 2011-03-03 | Honeywell International Inc. | Process for the preparation of lithium metal oxides involving fluidized bed techniques |
CN102139929A (en) * | 2011-03-28 | 2011-08-03 | 浙江理工大学 | Method for preparing Co3O4 nanometer sheet |
US8420264B2 (en) | 2007-03-30 | 2013-04-16 | Altairnano, Inc. | Method for preparing a lithium ion cell |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6964828B2 (en) | 2001-04-27 | 2005-11-15 | 3M Innovative Properties Company | Cathode compositions for lithium-ion batteries |
AU2002355544A1 (en) * | 2001-08-07 | 2003-02-24 | 3M Innovative Properties Company | Cathode compositions for lithium ion batteries |
JP4340160B2 (en) * | 2002-03-08 | 2009-10-07 | アルテアナノ インコーポレイテッド | Method for producing nano-sized and sub-micron sized lithium transition metal oxides |
US20040121234A1 (en) * | 2002-12-23 | 2004-06-24 | 3M Innovative Properties Company | Cathode composition for rechargeable lithium battery |
TWM249953U (en) * | 2003-03-19 | 2004-11-11 | Yeu Ming Tai Chemical Ind Co L | Processing device for nano-material |
DE10317067A1 (en) * | 2003-04-14 | 2004-11-11 | Degussa Ag | Domains in a metal oxide matrix |
US7211237B2 (en) * | 2003-11-26 | 2007-05-01 | 3M Innovative Properties Company | Solid state synthesis of lithium ion battery cathode material |
TWI233231B (en) * | 2003-12-25 | 2005-05-21 | Ind Tech Res Inst | Cathode material with nano-oxide layer on the surface and the produce method |
US7608332B2 (en) * | 2004-06-14 | 2009-10-27 | Industrial Technology Research Institute | Cathode material particle comprising of plurality of cores of coated grains |
JP4630021B2 (en) * | 2004-08-26 | 2011-02-09 | 大研化学工業株式会社 | Spinel type lithium manganate powder, method for producing the same, electrode and lithium secondary battery |
JP2007018883A (en) * | 2005-07-07 | 2007-01-25 | Toshiba Corp | Negative electrode active material, nonaqueous electrolyte battery and battery pack |
CA2637618C (en) | 2006-02-16 | 2015-03-31 | Brigham Young University | Preparation of uniform nanoparticles of ultra-high purity metal oxides, mixed metal oxides, metals, and metal alloys |
KR101336566B1 (en) * | 2006-02-28 | 2013-12-03 | 프리메트 프리시젼 머테리알스, 인크. | Lithium-Based Compound Nanoparticle Compositions and Methods of Forming the Same |
US8168330B2 (en) * | 2006-04-11 | 2012-05-01 | Enerdel, Inc. | Lithium titanate cell with reduced gassing |
US7820327B2 (en) * | 2006-04-11 | 2010-10-26 | Enerdel, Inc. | Lithium titanate and lithium cells and batteries including the same |
US8076030B2 (en) | 2006-06-05 | 2011-12-13 | A123 Systems, Inc. | Alkali metal titanates, and electrodes and batteries based on the same |
US7879493B2 (en) * | 2006-06-05 | 2011-02-01 | A123 Systems, Inc. | Alkali metal titanates and methods for their synthesis |
US20100135937A1 (en) * | 2007-03-26 | 2010-06-03 | The Trustees Of Columbia University In The City Of New York | Metal oxide nanocrystals: preparation and uses |
WO2008123558A1 (en) * | 2007-03-29 | 2008-10-16 | Toho Titanium Co., Ltd. | Method for production of alkali titanate, method for production of hollow powder of alkali titanate, alkali titanate and hollow powder thereof produced by the methods, and friction material comprising the alkali titanate or the hollow powder thereof |
CN100453212C (en) * | 2007-07-17 | 2009-01-21 | 南京航空航天大学 | Mechanical process of preparing composite nanometer ceramic and micron metal powder |
EP3017986B1 (en) | 2008-06-27 | 2022-11-09 | Proterra Operating Company, Inc. | Vehicle battery systems and method |
RU2397576C1 (en) * | 2009-03-06 | 2010-08-20 | ООО "Элионт" | Anode material for lithium electrolytic cell and method of preparing said material |
JP5174730B2 (en) * | 2009-03-27 | 2013-04-03 | 日揮触媒化成株式会社 | Method for producing crystalline lithium titanate and crystalline lithium titanate |
EP2564486B1 (en) | 2010-04-26 | 2020-09-16 | Proterra Inc. | Systems and methods for automatic connection and charging of an electric vehicle at a charging station |
WO2012169331A1 (en) * | 2011-06-10 | 2012-12-13 | 東邦チタニウム株式会社 | Lithium titanate primary particles, lithium titanate aggregate, lithium ion secondary battery using lithium titanate primary particles or lithium titanate aggregate, and lithium ion capacitor using lithium titanate primary particles or lithium titanate aggregate |
JP5569980B2 (en) * | 2011-12-26 | 2014-08-13 | 太陽誘電株式会社 | Lithium titanium composite oxide, battery electrode using the same, and lithium ion secondary battery |
JP5597662B2 (en) * | 2012-03-09 | 2014-10-01 | 株式会社東芝 | Negative electrode active material, non-aqueous electrolyte battery and battery pack |
US9114378B2 (en) | 2012-03-26 | 2015-08-25 | Brigham Young University | Iron and cobalt based fischer-tropsch pre-catalysts and catalysts |
US9079164B2 (en) | 2012-03-26 | 2015-07-14 | Brigham Young University | Single reaction synthesis of texturized catalysts |
JP2014001110A (en) * | 2012-06-20 | 2014-01-09 | Taiyo Yuden Co Ltd | Lithium titanium complex oxide, production method thereof and electrode for battery |
WO2014078456A1 (en) | 2012-11-13 | 2014-05-22 | Proterra Inc. | Systems and methods for enabling fast charging of an electric vehicle at a charging station |
US9289750B2 (en) | 2013-03-09 | 2016-03-22 | Brigham Young University | Method of making highly porous, stable aluminum oxides doped with silicon |
US11081731B2 (en) | 2017-10-18 | 2021-08-03 | International Business Machines Corporation | High-capacity rechargeable batteries |
Citations (69)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3765921A (en) * | 1972-03-13 | 1973-10-16 | Engelhard Min & Chem | Production of calcined clay pigment from paper wastes |
US3903239A (en) * | 1973-02-07 | 1975-09-02 | Ontario Research Foundation | Recovery of titanium dioxide from ores |
US4012338A (en) * | 1974-08-10 | 1977-03-15 | Tioxide Group Limited | Process for manufacturing a carrier of titanium dioxide |
US4058592A (en) * | 1976-06-30 | 1977-11-15 | Union Carbide Corporation | Preparation of sub-micron metal oxide powders from chloride-containing compounds |
US4065544A (en) * | 1970-05-11 | 1977-12-27 | Union Carbide Corporation | Finely divided metal oxides and sintered objects therefrom |
US4189102A (en) * | 1978-05-10 | 1980-02-19 | Andrews Norwood H | Comminuting and classifying apparatus and process of the re-entrant circulating stream jet type |
US4219164A (en) * | 1979-03-16 | 1980-08-26 | Microfuels, Inc. | Comminution of pulverulent material by fluid energy |
US4482642A (en) * | 1981-08-19 | 1984-11-13 | Degussa Aktiengesellschaft | Process for the production of slugs of pyrogenically produced oxides |
US4502641A (en) * | 1981-04-29 | 1985-03-05 | E. I. Du Pont De Nemours And Company | Fluid energy mill with differential pressure means |
US4546926A (en) * | 1981-11-27 | 1985-10-15 | Jouko Niemi | Pressure-chamber grinder |
US4649037A (en) * | 1985-03-29 | 1987-03-10 | Allied Corporation | Spray-dried inorganic oxides from non-aqueous gels or solutions |
US4664319A (en) * | 1984-09-24 | 1987-05-12 | Norandy, Incorporated | Re-entrant circulating stream jet comminuting and classifying mill |
US4842832A (en) * | 1985-03-05 | 1989-06-27 | Idemitsu Kosan Company Limited | Ultra-fine spherical particles of metal oxide and a method for the preparation thereof |
US4923682A (en) * | 1989-03-30 | 1990-05-08 | Kemira, Inc. | Preparation of pure titanium dioxide with anatase crystal structure from titanium oxychloride solution |
US4944936A (en) * | 1987-04-10 | 1990-07-31 | Kemira, Inc. | Titanium dioxide with high purity and uniform particle size and method therefore |
US4999182A (en) * | 1987-12-11 | 1991-03-12 | Rhone-Poulenc Chimie | Stabilized zirconia powders |
US5036037A (en) * | 1989-05-09 | 1991-07-30 | Maschinenfabrik Andritz Aktiengesellschaft | Process of making catalysts and catalysts made by the process |
US5068056A (en) * | 1988-12-16 | 1991-11-26 | Tioxide Group Plc | Aqueous dispersions of acicular titanium dioxide |
US5114702A (en) * | 1988-08-30 | 1992-05-19 | Battelle Memorial Institute | Method of making metal oxide ceramic powders by using a combustible amino acid compound |
US5133504A (en) * | 1990-11-27 | 1992-07-28 | Xerox Corporation | Throughput efficiency enhancement of fluidized bed jet mill |
US5160712A (en) * | 1990-04-12 | 1992-11-03 | Technology Finance Corporation (Prop.) Ltd | Lithium transition metal oxide |
US5173455A (en) * | 1986-09-24 | 1992-12-22 | Union Carbide Coatings Service Technology Corporation | Low sintering cordierite powder composition |
US5478671A (en) * | 1992-04-24 | 1995-12-26 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
US5545468A (en) * | 1993-03-17 | 1996-08-13 | Matsushita Electric Industrial Co., Ltd. | Rechargeable lithium cell and process for making an anode for use in the cell |
US5550095A (en) * | 1992-05-08 | 1996-08-27 | Mitsubishi Rayon Co., Ltd. | Process for producing catalyst used for synthesis of methacrylic acid |
US5562763A (en) * | 1992-04-07 | 1996-10-08 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Process for the preparation of composite pigments |
US5654114A (en) * | 1994-03-25 | 1997-08-05 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
US5698177A (en) * | 1994-08-31 | 1997-12-16 | University Of Cincinnati | Process for producing ceramic powders, especially titanium dioxide useful as a photocatalyst |
US5698205A (en) * | 1993-08-30 | 1997-12-16 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Photostabilization of titanium dioxide sols |
US5714260A (en) * | 1993-12-13 | 1998-02-03 | Ishihara Sangyo Kaisha, Ltd. | Ultrafine iron-containing rutile titanium oxide and process for producing the same |
US5766796A (en) * | 1997-05-06 | 1998-06-16 | Eic Laboratories, Inc. | Passivation-free solid state battery |
US5770310A (en) * | 1996-04-02 | 1998-06-23 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Composite fine particles of metal oxides and production thereof |
US5807532A (en) * | 1995-01-26 | 1998-09-15 | Japan Metals And Chemicals Co., Ltd. | Method of producing spinel type limn204 |
US5833892A (en) * | 1996-07-12 | 1998-11-10 | Kemira Pigments, Inc. | Formation of TiO2 pigment by spray calcination |
US5840111A (en) * | 1995-11-20 | 1998-11-24 | Bayer Ag | Nanodisperse titanium dioxide, process for the production thereof and use thereof |
US6001326A (en) * | 1998-07-16 | 1999-12-14 | Korea Atomic Energy Research Institute | Method for production of mono-dispersed and crystalline TiO2 ultrafine powders for aqueous TiOCl2 solution using homogeneous precipitation |
US6037289A (en) * | 1995-09-15 | 2000-03-14 | Rhodia Chimie | Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions |
US6080510A (en) * | 1994-09-30 | 2000-06-27 | Zentrum Fur Sonnenenergie-Und Wasserstoff Forshung Baden Wurttemberg Gemeinnultzige Stiftung | Ternary mixed lithium oxides, process for preparing the same, and secondary lithium battery formed therefrom |
US6099634A (en) * | 1997-02-28 | 2000-08-08 | Titan Kogyo Kabushiki Kaisha | Fan- or disk-shaped titanium oxide particles, processes for production thereof and uses thereof |
US6139815A (en) * | 1997-07-15 | 2000-10-31 | Sony Corporation | Hydrogen lithium titanate and manufacturing method therefor |
US6168884B1 (en) * | 1999-04-02 | 2001-01-02 | Lockheed Martin Energy Research Corporation | Battery with an in-situ activation plated lithium anode |
US6274271B1 (en) * | 1996-08-27 | 2001-08-14 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte lithium secondary battery |
US20010031401A1 (en) * | 1999-02-16 | 2001-10-18 | Tetsuya Yamawaki | Process for producing lithium titanate and lithium ion battery and negative electrode therein |
US6348182B1 (en) * | 1996-06-27 | 2002-02-19 | The Honjo Chemical Corporation | Process for producing lithium manganese oxide with spinel structure |
US6375923B1 (en) * | 1999-06-24 | 2002-04-23 | Altair Nanomaterials Inc. | Processing titaniferous ore to titanium dioxide pigment |
US6409985B1 (en) * | 1998-12-02 | 2002-06-25 | Mitsui Mining And Smelting Company, Ltd. | Method for producing lithium manganate |
US6440383B1 (en) * | 1999-06-24 | 2002-08-27 | Altair Nanomaterials Inc. | Processing aqueous titanium chloride solutions to ultrafine titanium dioxide |
US6447739B1 (en) * | 1997-02-19 | 2002-09-10 | H.C. Starck Gmbh & Co. Kg | Method for producing lithium transition metallates |
US6475673B1 (en) * | 1999-02-16 | 2002-11-05 | Toho Titanium Co., Ltd. | Process for producing lithium titanate and lithium ion battery and negative electrode therein |
US6548039B1 (en) * | 1999-06-24 | 2003-04-15 | Altair Nanomaterials Inc. | Processing aqueous titanium solutions to titanium dioxide pigment |
US6673491B2 (en) * | 2000-01-21 | 2004-01-06 | Showa Denko Kabushiki Kaisha | Cathode electroactive material, production method therefor, and nonaqueous secondary cell using the same |
US6680041B1 (en) * | 1998-11-09 | 2004-01-20 | Nanogram Corporation | Reaction methods for producing metal oxide particles |
US6689716B2 (en) * | 2000-10-17 | 2004-02-10 | Altair Nanomaterials Inc. | Method for producing catalyst structures |
US6719821B2 (en) * | 2001-02-12 | 2004-04-13 | Nanoproducts Corporation | Precursors of engineered powders |
US6737037B2 (en) * | 2002-03-26 | 2004-05-18 | Council Of Scientific And Industrial Research | Solid state thermal synthesis of lithium cobaltate |
US6749648B1 (en) * | 2000-06-19 | 2004-06-15 | Nanagram Corporation | Lithium metal oxides |
US6789756B2 (en) * | 2002-02-20 | 2004-09-14 | Super Fine Ltd. | Vortex mill for controlled milling of particulate solids |
US20040197657A1 (en) * | 2001-07-31 | 2004-10-07 | Timothy Spitler | High performance lithium titanium spinel li4t15012 for electrode material |
US6881393B2 (en) * | 2002-03-08 | 2005-04-19 | Altair Nanomaterials Inc. | Process for making nano-sized and sub-micron-sized lithium-transition metal oxides |
US6890510B2 (en) * | 2001-07-20 | 2005-05-10 | Altair Nanomaterials Inc. | Process for making lithium titanate |
US6908711B2 (en) * | 2002-04-10 | 2005-06-21 | Pacific Lithium New Zealand Limited | Rechargeable high power electrochemical device |
US6974566B2 (en) * | 2000-09-05 | 2005-12-13 | Altair Nanomaterials Inc. | Method for producing mixed metal oxides and metal oxide compounds |
US6982073B2 (en) * | 2001-11-02 | 2006-01-03 | Altair Nanomaterials Inc. | Process for making nano-sized stabilized zirconia |
US7026074B2 (en) * | 2002-02-15 | 2006-04-11 | The University Of Chicago | Lithium ion battery with improved safety |
US7060390B2 (en) * | 2003-01-06 | 2006-06-13 | Hon Hai Precision Ind. Co., Ltd. | Lithium ion battery comprising nanomaterials |
US7087349B2 (en) * | 2001-10-31 | 2006-08-08 | Samsung Sdi Co., Ltd. | Organic electrolytic solution and lithium secondary battery employing the same |
US7101642B2 (en) * | 2000-04-26 | 2006-09-05 | Quallion Llc | Rechargeable lithium battery for tolerating discharge to zero volts |
US7115339B2 (en) * | 2003-02-21 | 2006-10-03 | Matsushita Electric Industrial Co., Ltd. | Lithium ion secondary battery |
US20070092798A1 (en) * | 2005-10-21 | 2007-04-26 | Spitler Timothy M | Lithium ion batteries |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2283942A1 (en) | 1997-03-14 | 1998-09-24 | Eveready Battery Company, Inc. | Lithiated metal oxides |
KR100261120B1 (en) | 1997-08-26 | 2000-07-01 | 김순택 | Lithium manganese oxide, method for manufacturing the same and secondary lithiumion ion battery having same |
JP3652539B2 (en) * | 1999-02-05 | 2005-05-25 | 日本碍子株式会社 | Method for manufacturing lithium secondary battery |
-
2003
- 2003-03-07 JP JP2003574567A patent/JP4340160B2/en not_active Expired - Fee Related
- 2003-03-07 AU AU2003228290A patent/AU2003228290A1/en not_active Abandoned
- 2003-03-07 WO PCT/US2003/006989 patent/WO2003076338A1/en active Application Filing
- 2003-03-07 US US10/383,821 patent/US6881393B2/en not_active Expired - Lifetime
- 2003-03-07 AT AT03726038T patent/ATE485241T1/en not_active IP Right Cessation
- 2003-03-07 CA CA2478698A patent/CA2478698C/en not_active Expired - Fee Related
- 2003-03-07 DE DE60334610T patent/DE60334610D1/en not_active Expired - Lifetime
- 2003-03-07 EP EP03726038A patent/EP1483206B1/en not_active Expired - Lifetime
-
2005
- 2005-03-24 US US11/088,529 patent/US20050169833A1/en not_active Abandoned
Patent Citations (70)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4065544A (en) * | 1970-05-11 | 1977-12-27 | Union Carbide Corporation | Finely divided metal oxides and sintered objects therefrom |
US3765921A (en) * | 1972-03-13 | 1973-10-16 | Engelhard Min & Chem | Production of calcined clay pigment from paper wastes |
US3903239A (en) * | 1973-02-07 | 1975-09-02 | Ontario Research Foundation | Recovery of titanium dioxide from ores |
US4012338A (en) * | 1974-08-10 | 1977-03-15 | Tioxide Group Limited | Process for manufacturing a carrier of titanium dioxide |
US4058592A (en) * | 1976-06-30 | 1977-11-15 | Union Carbide Corporation | Preparation of sub-micron metal oxide powders from chloride-containing compounds |
US4189102A (en) * | 1978-05-10 | 1980-02-19 | Andrews Norwood H | Comminuting and classifying apparatus and process of the re-entrant circulating stream jet type |
US4219164A (en) * | 1979-03-16 | 1980-08-26 | Microfuels, Inc. | Comminution of pulverulent material by fluid energy |
US4502641A (en) * | 1981-04-29 | 1985-03-05 | E. I. Du Pont De Nemours And Company | Fluid energy mill with differential pressure means |
US4482642A (en) * | 1981-08-19 | 1984-11-13 | Degussa Aktiengesellschaft | Process for the production of slugs of pyrogenically produced oxides |
US4546926A (en) * | 1981-11-27 | 1985-10-15 | Jouko Niemi | Pressure-chamber grinder |
US4664319A (en) * | 1984-09-24 | 1987-05-12 | Norandy, Incorporated | Re-entrant circulating stream jet comminuting and classifying mill |
US4842832A (en) * | 1985-03-05 | 1989-06-27 | Idemitsu Kosan Company Limited | Ultra-fine spherical particles of metal oxide and a method for the preparation thereof |
US4649037A (en) * | 1985-03-29 | 1987-03-10 | Allied Corporation | Spray-dried inorganic oxides from non-aqueous gels or solutions |
US5173455A (en) * | 1986-09-24 | 1992-12-22 | Union Carbide Coatings Service Technology Corporation | Low sintering cordierite powder composition |
US4944936A (en) * | 1987-04-10 | 1990-07-31 | Kemira, Inc. | Titanium dioxide with high purity and uniform particle size and method therefore |
US4999182A (en) * | 1987-12-11 | 1991-03-12 | Rhone-Poulenc Chimie | Stabilized zirconia powders |
US5114702A (en) * | 1988-08-30 | 1992-05-19 | Battelle Memorial Institute | Method of making metal oxide ceramic powders by using a combustible amino acid compound |
US5068056A (en) * | 1988-12-16 | 1991-11-26 | Tioxide Group Plc | Aqueous dispersions of acicular titanium dioxide |
US4923682A (en) * | 1989-03-30 | 1990-05-08 | Kemira, Inc. | Preparation of pure titanium dioxide with anatase crystal structure from titanium oxychloride solution |
US5036037A (en) * | 1989-05-09 | 1991-07-30 | Maschinenfabrik Andritz Aktiengesellschaft | Process of making catalysts and catalysts made by the process |
US5160712A (en) * | 1990-04-12 | 1992-11-03 | Technology Finance Corporation (Prop.) Ltd | Lithium transition metal oxide |
US5133504A (en) * | 1990-11-27 | 1992-07-28 | Xerox Corporation | Throughput efficiency enhancement of fluidized bed jet mill |
US5562763A (en) * | 1992-04-07 | 1996-10-08 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Process for the preparation of composite pigments |
US5478671A (en) * | 1992-04-24 | 1995-12-26 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
US5550095A (en) * | 1992-05-08 | 1996-08-27 | Mitsubishi Rayon Co., Ltd. | Process for producing catalyst used for synthesis of methacrylic acid |
US5545468A (en) * | 1993-03-17 | 1996-08-13 | Matsushita Electric Industrial Co., Ltd. | Rechargeable lithium cell and process for making an anode for use in the cell |
US5698205A (en) * | 1993-08-30 | 1997-12-16 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Photostabilization of titanium dioxide sols |
US5714260A (en) * | 1993-12-13 | 1998-02-03 | Ishihara Sangyo Kaisha, Ltd. | Ultrafine iron-containing rutile titanium oxide and process for producing the same |
US5654114A (en) * | 1994-03-25 | 1997-08-05 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
US5698177A (en) * | 1994-08-31 | 1997-12-16 | University Of Cincinnati | Process for producing ceramic powders, especially titanium dioxide useful as a photocatalyst |
US6080510A (en) * | 1994-09-30 | 2000-06-27 | Zentrum Fur Sonnenenergie-Und Wasserstoff Forshung Baden Wurttemberg Gemeinnultzige Stiftung | Ternary mixed lithium oxides, process for preparing the same, and secondary lithium battery formed therefrom |
US5807532A (en) * | 1995-01-26 | 1998-09-15 | Japan Metals And Chemicals Co., Ltd. | Method of producing spinel type limn204 |
US6037289A (en) * | 1995-09-15 | 2000-03-14 | Rhodia Chimie | Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions |
US5840111A (en) * | 1995-11-20 | 1998-11-24 | Bayer Ag | Nanodisperse titanium dioxide, process for the production thereof and use thereof |
US5770310A (en) * | 1996-04-02 | 1998-06-23 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Composite fine particles of metal oxides and production thereof |
US6348182B1 (en) * | 1996-06-27 | 2002-02-19 | The Honjo Chemical Corporation | Process for producing lithium manganese oxide with spinel structure |
US5833892A (en) * | 1996-07-12 | 1998-11-10 | Kemira Pigments, Inc. | Formation of TiO2 pigment by spray calcination |
US6274271B1 (en) * | 1996-08-27 | 2001-08-14 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte lithium secondary battery |
US6447739B1 (en) * | 1997-02-19 | 2002-09-10 | H.C. Starck Gmbh & Co. Kg | Method for producing lithium transition metallates |
US6099634A (en) * | 1997-02-28 | 2000-08-08 | Titan Kogyo Kabushiki Kaisha | Fan- or disk-shaped titanium oxide particles, processes for production thereof and uses thereof |
US5766796A (en) * | 1997-05-06 | 1998-06-16 | Eic Laboratories, Inc. | Passivation-free solid state battery |
US6139815A (en) * | 1997-07-15 | 2000-10-31 | Sony Corporation | Hydrogen lithium titanate and manufacturing method therefor |
US6001326A (en) * | 1998-07-16 | 1999-12-14 | Korea Atomic Energy Research Institute | Method for production of mono-dispersed and crystalline TiO2 ultrafine powders for aqueous TiOCl2 solution using homogeneous precipitation |
US6680041B1 (en) * | 1998-11-09 | 2004-01-20 | Nanogram Corporation | Reaction methods for producing metal oxide particles |
US6409985B1 (en) * | 1998-12-02 | 2002-06-25 | Mitsui Mining And Smelting Company, Ltd. | Method for producing lithium manganate |
US6475673B1 (en) * | 1999-02-16 | 2002-11-05 | Toho Titanium Co., Ltd. | Process for producing lithium titanate and lithium ion battery and negative electrode therein |
US6645673B2 (en) * | 1999-02-16 | 2003-11-11 | Toho Titanium Co., Ltd. | Process for producing lithium titanate and lithium ion battery and negative electrode therein |
US20010031401A1 (en) * | 1999-02-16 | 2001-10-18 | Tetsuya Yamawaki | Process for producing lithium titanate and lithium ion battery and negative electrode therein |
US6168884B1 (en) * | 1999-04-02 | 2001-01-02 | Lockheed Martin Energy Research Corporation | Battery with an in-situ activation plated lithium anode |
US6440383B1 (en) * | 1999-06-24 | 2002-08-27 | Altair Nanomaterials Inc. | Processing aqueous titanium chloride solutions to ultrafine titanium dioxide |
US6375923B1 (en) * | 1999-06-24 | 2002-04-23 | Altair Nanomaterials Inc. | Processing titaniferous ore to titanium dioxide pigment |
US6548039B1 (en) * | 1999-06-24 | 2003-04-15 | Altair Nanomaterials Inc. | Processing aqueous titanium solutions to titanium dioxide pigment |
US6673491B2 (en) * | 2000-01-21 | 2004-01-06 | Showa Denko Kabushiki Kaisha | Cathode electroactive material, production method therefor, and nonaqueous secondary cell using the same |
US7101642B2 (en) * | 2000-04-26 | 2006-09-05 | Quallion Llc | Rechargeable lithium battery for tolerating discharge to zero volts |
US6749648B1 (en) * | 2000-06-19 | 2004-06-15 | Nanagram Corporation | Lithium metal oxides |
US6974566B2 (en) * | 2000-09-05 | 2005-12-13 | Altair Nanomaterials Inc. | Method for producing mixed metal oxides and metal oxide compounds |
US6689716B2 (en) * | 2000-10-17 | 2004-02-10 | Altair Nanomaterials Inc. | Method for producing catalyst structures |
US6719821B2 (en) * | 2001-02-12 | 2004-04-13 | Nanoproducts Corporation | Precursors of engineered powders |
US6890510B2 (en) * | 2001-07-20 | 2005-05-10 | Altair Nanomaterials Inc. | Process for making lithium titanate |
US20040197657A1 (en) * | 2001-07-31 | 2004-10-07 | Timothy Spitler | High performance lithium titanium spinel li4t15012 for electrode material |
US7087349B2 (en) * | 2001-10-31 | 2006-08-08 | Samsung Sdi Co., Ltd. | Organic electrolytic solution and lithium secondary battery employing the same |
US6982073B2 (en) * | 2001-11-02 | 2006-01-03 | Altair Nanomaterials Inc. | Process for making nano-sized stabilized zirconia |
US7026074B2 (en) * | 2002-02-15 | 2006-04-11 | The University Of Chicago | Lithium ion battery with improved safety |
US6789756B2 (en) * | 2002-02-20 | 2004-09-14 | Super Fine Ltd. | Vortex mill for controlled milling of particulate solids |
US6881393B2 (en) * | 2002-03-08 | 2005-04-19 | Altair Nanomaterials Inc. | Process for making nano-sized and sub-micron-sized lithium-transition metal oxides |
US6737037B2 (en) * | 2002-03-26 | 2004-05-18 | Council Of Scientific And Industrial Research | Solid state thermal synthesis of lithium cobaltate |
US6908711B2 (en) * | 2002-04-10 | 2005-06-21 | Pacific Lithium New Zealand Limited | Rechargeable high power electrochemical device |
US7060390B2 (en) * | 2003-01-06 | 2006-06-13 | Hon Hai Precision Ind. Co., Ltd. | Lithium ion battery comprising nanomaterials |
US7115339B2 (en) * | 2003-02-21 | 2006-10-03 | Matsushita Electric Industrial Co., Ltd. | Lithium ion secondary battery |
US20070092798A1 (en) * | 2005-10-21 | 2007-04-26 | Spitler Timothy M | Lithium ion batteries |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040197657A1 (en) * | 2001-07-31 | 2004-10-07 | Timothy Spitler | High performance lithium titanium spinel li4t15012 for electrode material |
US7547490B2 (en) | 2001-07-31 | 2009-06-16 | Altairnano Inc. | High performance lithium titanium spinel Li4Ti5012 for electrode material |
US20070092798A1 (en) * | 2005-10-21 | 2007-04-26 | Spitler Timothy M | Lithium ion batteries |
WO2007078429A2 (en) * | 2005-12-23 | 2007-07-12 | Uchicago Argonne, Llc. | Electrode materials and lithium battery systems |
WO2007078429A3 (en) * | 2005-12-23 | 2007-11-01 | Uchicago Argonne Llc | Electrode materials and lithium battery systems |
US20080108529A1 (en) * | 2006-11-08 | 2008-05-08 | The Lubrizol Corporation | Process for Preparing High Concentration Dispersions of Lithium Hydroxide Monohydrate and of Anhydrous Lithium Hydroxide Oils |
US8168146B2 (en) * | 2006-11-08 | 2012-05-01 | The Lubrizol Corporation | Process for preparing high concentration dispersions of lithium hydroxide monohydrate and of anhydrous lithium hydroxide oils |
US8420264B2 (en) | 2007-03-30 | 2013-04-16 | Altairnano, Inc. | Method for preparing a lithium ion cell |
US20110052484A1 (en) * | 2009-08-27 | 2011-03-03 | Honeywell International Inc. | Process for the preparation of lithium metal oxides involving fluidized bed techniques |
US8333950B2 (en) * | 2009-08-27 | 2012-12-18 | Honeywell International Inc. | Process for the preparation of lithium metal oxides involving fluidized bed techniques |
CN102139929A (en) * | 2011-03-28 | 2011-08-03 | 浙江理工大学 | Method for preparing Co3O4 nanometer sheet |
Also Published As
Publication number | Publication date |
---|---|
JP2005519831A (en) | 2005-07-07 |
EP1483206A1 (en) | 2004-12-08 |
JP4340160B2 (en) | 2009-10-07 |
EP1483206B1 (en) | 2010-10-20 |
WO2003076338A1 (en) | 2003-09-18 |
ATE485241T1 (en) | 2010-11-15 |
CA2478698C (en) | 2012-05-29 |
DE60334610D1 (en) | 2010-12-02 |
US20030228464A1 (en) | 2003-12-11 |
AU2003228290A1 (en) | 2003-09-22 |
CA2478698A1 (en) | 2003-09-18 |
US6881393B2 (en) | 2005-04-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6881393B2 (en) | Process for making nano-sized and sub-micron-sized lithium-transition metal oxides | |
CA2454324C (en) | Process for making lithium titanate | |
AU2002319587A1 (en) | Process for making lithium titanate | |
KR101569782B1 (en) | Manufacturing method of lithium-titanium composite doped by different metal, and lithium-titanium composite doped with different metal made by same | |
TWI517487B (en) | Complexometric precursor formulation methodology for industrial production of fine and ultrafine powders and nanopowders of layered lithium mixed metal oxides for battery applications | |
JP6204576B2 (en) | Method for producing lithium titanium composite oxide doped with different metal, and lithium titanium composite oxide doped with different metal produced thereby | |
JP3894614B2 (en) | Method for producing lithium titanate | |
JP2013503102A (en) | Method for preparing lithium metal oxides using fluidized bed technology | |
KR20140047669A (en) | Production of nanostructured li4ti5o12 with superior high rate performance | |
JP2002060225A (en) | Lithium cobaltate aggregate, cobalt oxide aggregate, method for manufacturing the same and lithium cell using lithium cobaltate aggregate | |
JP4435926B2 (en) | High crystalline lithium titanate | |
JPH111324A (en) | Platy nickel hydroxide particle, its production and production of lithium-nickel complex oxide particle using the nickel hydroxide particle as raw material | |
JP3753754B2 (en) | Method for producing spinel type LiMn2O4 | |
Park et al. | Ultrasonic spray pyrolysis of nano crystalline spinel LiMn2O4 showing good cycling performance in the 3 V range | |
CN111094189A (en) | Method for preparing electrode active material | |
JPH11292548A (en) | Tricobalt tetroxide and its production | |
JP2002274849A (en) | Lithium titanate, production method therefor and its use | |
WO2020153409A1 (en) | Titanium oxide, method for producing titanium oxide, and lithium secondary battery using titanium oxide-containing electrode active material | |
KR100491677B1 (en) | METHOD FOR PREPARING OF CeO2 NANO POWDER | |
EP3543215B1 (en) | Method for manufacturing lithium-titanium composite oxide by controlling particle size of slurry through wet milling | |
JPH10182157A (en) | Production of lithium manganese multiple oxide |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ALTAIR NANOMATERIALS INC., NEVADA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SPITLER, TIMOTHY M.;PROCHAZKA, JAN;REEL/FRAME:021015/0138 Effective date: 20030716 |
|
AS | Assignment |
Owner name: ALTAIRNANO, INC., NEVADA Free format text: CHANGE OF NAME;ASSIGNOR:ALTAIR NANOMATERIALS INC.;REEL/FRAME:021021/0829 Effective date: 20080501 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |