CA2787373C - Producing oxidic compounds - Google Patents
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- CA2787373C CA2787373C CA2787373A CA2787373A CA2787373C CA 2787373 C CA2787373 C CA 2787373C CA 2787373 A CA2787373 A CA 2787373A CA 2787373 A CA2787373 A CA 2787373A CA 2787373 C CA2787373 C CA 2787373C
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Complex oxides containing manganese and at least one other metal element
- C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
- C01G45/1228—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Complex oxides containing cobalt and at least one other metal element
- C01G51/42—Complex oxides containing cobalt and at least one other metal element 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—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D1/00—Casings; Linings; Walls; Roofs
- F27D1/16—Making or repairing linings ; Increasing the durability of linings; Breaking away linings
- F27D1/1694—Breaking away the lining or removing parts thereof
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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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- 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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
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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
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- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A process for producing oxidic compounds of the general formula (?) LizMxOy (?) wherein M is one or more elements from groups 2 to 12 of the periodic table, more particularly selected from Co, Mn, Ni, Fe, Al, Mg, x is 1 to 2, y is 2 to 4, and z is 0.5 to 1.5, comprises heating mixtures selected from oxides, hydroxides, carbonates and nitrates of Li and of M together to temperatures in the range from 600 to 1200? in a reaction vessel performing incomplete rotary motions about one axis.
Description
Producing oxidic compounds The present invention relates to a process for producing oxidic compounds of the general formula (I) LizMx0y (I) where M is one or more elements from groups 2 to 12 of the periodic table and/or aluminum, more particularly selected from Co, Mn, Ni, Fe, Al, Mg, is from 1 to 2, is from 2 to 4, and is from 0.5 to 1.5, which process comprises heating mixtures selected from oxides, hydroxides, carbonates and nitrates of Li and of M together to temperatures in the range from 600 to 1200 C in a reaction vessel performing incomplete rotary motions about one axis.
Another embodiment of the invention relates to a process for producing oxidic compounds of the general formula (I) LizMx0y (I) where is selected from the group consisting of Co, Mn, Ni, Fe, Al and Mg, is from 1 to 2, is from 2 to 4, and is from 0.5 to 1.5, which process comprises heating a mixture comprising at least one first compound and at least one second compound together, - the at least one first compound being selected from the group consisting of oxides of Li, hydroxides of Li, carbonates of Li and nitrates of Li, and
Another embodiment of the invention relates to a process for producing oxidic compounds of the general formula (I) LizMx0y (I) where is selected from the group consisting of Co, Mn, Ni, Fe, Al and Mg, is from 1 to 2, is from 2 to 4, and is from 0.5 to 1.5, which process comprises heating a mixture comprising at least one first compound and at least one second compound together, - the at least one first compound being selected from the group consisting of oxides of Li, hydroxides of Li, carbonates of Li and nitrates of Li, and
2 - the at least one second compound being selected from the group consisting of oxides of M, hydroxides of M, carbonates of M and nitrates of M, M being as defined above, to reaction temperatures in the range from 600 to 1200 C in a reaction vessel performing incomplete rotary motions about one axis.
Another embodiment of the invention relates to the process defined hereinabove, wherein the reaction vessel has an inclination in the range from 1 to 200 .
Another embodiment of the invention relates to the process defined hereinabove, wherein the axis about which incomplete rotary motions are performed has an inclination in the range from 1 to 20 relative to the horizontal plane.
Another embodiment of the invention relates to the process defined hereinabove, wherein the reaction vessel comprises a pendulum kiln.
Another embodiment of the invention relates to the process defined hereinabove, wherein said process is further carried out in an oxygen-containing atmosphere or an oxygen-enriched atmosphere.
Another embodiment of the invention relates to the process defined hereinabove, wherein said mixture is in a pulverulent form or a pasty form.
Another embodiment of the invention relates to the process defined hereinabove, wherein said mixture is in the pasty form, and wherein said pasty form is obtained by adding water or an alcohol to said mixture.
Another embodiment of the invention relates to the process defined hereinabove, wherein the field of traverse of the incomplete rotary motion is in the range from 60 to 250 .
Another embodiment of the invention relates to the process defined hereinabove, wherein the reaction temperatures are at least partially obtained by direct heating.
Various applications today require oxidic compounds comprising lithium, for example for so-called lithium ion batteries. In lithium ion batteries, charge is transported not by protons in a more or less hydrated form but by lithium ions in a nonaqueous solvent or
Another embodiment of the invention relates to the process defined hereinabove, wherein the reaction vessel has an inclination in the range from 1 to 200 .
Another embodiment of the invention relates to the process defined hereinabove, wherein the axis about which incomplete rotary motions are performed has an inclination in the range from 1 to 20 relative to the horizontal plane.
Another embodiment of the invention relates to the process defined hereinabove, wherein the reaction vessel comprises a pendulum kiln.
Another embodiment of the invention relates to the process defined hereinabove, wherein said process is further carried out in an oxygen-containing atmosphere or an oxygen-enriched atmosphere.
Another embodiment of the invention relates to the process defined hereinabove, wherein said mixture is in a pulverulent form or a pasty form.
Another embodiment of the invention relates to the process defined hereinabove, wherein said mixture is in the pasty form, and wherein said pasty form is obtained by adding water or an alcohol to said mixture.
Another embodiment of the invention relates to the process defined hereinabove, wherein the field of traverse of the incomplete rotary motion is in the range from 60 to 250 .
Another embodiment of the invention relates to the process defined hereinabove, wherein the reaction temperatures are at least partially obtained by direct heating.
Various applications today require oxidic compounds comprising lithium, for example for so-called lithium ion batteries. In lithium ion batteries, charge is transported not by protons in a more or less hydrated form but by lithium ions in a nonaqueous solvent or
3 in a nonaqueous solvent system. Lithium ion batteries comprise two or more electrodes, of which at least one, the cathode, may be fabricated from highly corrosive material.
Examples of such materials are mixed oxides and intercalation compounds of lithium oxide.
It is desirable that the electrodes, more particularly the cathodes, are made of a particularly homogeneous material. Existing production processes leave something to be desired in this respect, however.
In existing production processes, suitable powders are mixed with one another and subsequently reacted with one another at high temperatures in the manner of a solid state reaction. However, the search for suitable kilns has hitherto only brought forth solutions that are non optimal.
Tunnel kilns and roller kilns are known as such in various versions and comprise several cars or crucibles on which the reactant material to be fired travels through the heated kiln. Kilns of this type can be used to thermally react powders.
DE 10 2007 024 587 recommends a specific version, a multi-compartment kiln, for producing carbon anodes. However, the powder obtained is in many cases observed to have a nonuniform composition. In addition, the residence times in such kilns tend to be long and therefore the capacity and/or the space-time yield is unsatisfactory.
Rotary kilns are further known to be used for reacting pulverulent materials.
Rotary kilns, which are generally slightly inclined, generally provide a distinctly better homogenization of the product compared with tunnel kilns and roller kilns, and the space-time yield is better owing to the reduced residence time. In the present case, however, other problems are observed when rotary kilns are used. Lithium-containing mixed oxides are often highly corrosive, which greatly limits the choice of material suitable for the rotary kiln.
3a With ceramic rotary kilns, which are sufficiently stable to the action of highly corrosive lithium salts, the heat transfer through the ceramic walls in indirect heating is less than optimal. In addition, owing to the nature of their material of construction, ceramic rotary tubes are only fabricatable and operable in comparatively small sizes, and therefore are only suitable for comparatively small production capacities.
Finally, numerous morphologies are observed to give rise to substantial dusting and thus to a broad particle size distribution having an undesirably high proportion of fine dust.
The present invention accordingly has for its object to provide a process suitable for producing lithium-containing oxidic materials useful as cathode materials for lithium ion batteries. The present invention more particularly has for its object to produce such oxidic materials as have a homogeneous composition and thus are very useful for producing electrode materials. The present invention further has for its object to provide pulverulent materials useful for producing lithium ion batteries.
We have found that this object is achieved by the process defined at the beginning, which herein is also referred to as inventive process.
The inventive process has the purpose of producing oxidic compounds. Oxidic compounds in the context of the present invention may comprise mixed oxides, intercalation compounds, sheet oxides, or spinels. Sheet oxides are preferred.
Oxidic compounds obtained according to the present invention have the general formula (I) LizMx0y (I) where M is one or more transition metals or elements of groups 2 to 12 of the periodic table and/or aluminum, preferably Mg, Al or elements of groups 5 to 10 of the periodic table, more preferably selected from Co, Mn, Ni, Fe, Al, Mg. M can be present in the oxidation states +1 to +4, preference being given to the oxidation states +2 and +3, and it is particularly preferable to have the oxidation state +3 in the case of Al and the oxidation state +2 in the case of Co, Mn, Ni, Fe, and Mg.
3h In oxidic compound of formula (I), M can represent combinations of two or more metals, for example combinations of Co and Mn or combinations of Ni and Mn. Other illustrative combinations are Ni, Co, Al, and Ni, Co, Mn. The metals mentioned can be present therein in identical or different molar fractions. In one embodiment of the present invention, M represents Ni, Co, Mn in respectively identical molar fractions.
In another embodiment of the present invention, M represents Ni0.6Co0.2Mno.2.
In another embodiment of the present invention, M represents Ni0.5Co0.2Mno.3. In another embodiment of the present invention, M represents Ni0.4ComMno4.
In another embodiment of the present invention, M is selected from Ni0.4Co0.3Mno.3, Ni0.45Coo.1Mn0.45, Ni0.4C00.1Mno.5 and Ni0.5C00.1Mn0.4.
X is a number from 1 to 2, can be an average value and is not restricted to integers.
Preferably x is 1.
y is a number from 2 to 4, can be an average value and is not restricted to integers.
Preferably y is 2 + (x-1) + (z-1).
z is a number from 0.5 to 1.5 and preferably from 0.75 to 1.4.
The inventive process proceeds from mixtures of oxides, hydroxides, carbonates and nitrates of lithium and of M, i.e., the transition metal or metals, with at least one lithium compound. The oxide(s), hydroxide(s), carbonate(s) or nitrate(s) of M on the one hand and the lithium compound on the other can have identical or different counter-ions, based on M and lithium.
Examples of such materials are mixed oxides and intercalation compounds of lithium oxide.
It is desirable that the electrodes, more particularly the cathodes, are made of a particularly homogeneous material. Existing production processes leave something to be desired in this respect, however.
In existing production processes, suitable powders are mixed with one another and subsequently reacted with one another at high temperatures in the manner of a solid state reaction. However, the search for suitable kilns has hitherto only brought forth solutions that are non optimal.
Tunnel kilns and roller kilns are known as such in various versions and comprise several cars or crucibles on which the reactant material to be fired travels through the heated kiln. Kilns of this type can be used to thermally react powders.
DE 10 2007 024 587 recommends a specific version, a multi-compartment kiln, for producing carbon anodes. However, the powder obtained is in many cases observed to have a nonuniform composition. In addition, the residence times in such kilns tend to be long and therefore the capacity and/or the space-time yield is unsatisfactory.
Rotary kilns are further known to be used for reacting pulverulent materials.
Rotary kilns, which are generally slightly inclined, generally provide a distinctly better homogenization of the product compared with tunnel kilns and roller kilns, and the space-time yield is better owing to the reduced residence time. In the present case, however, other problems are observed when rotary kilns are used. Lithium-containing mixed oxides are often highly corrosive, which greatly limits the choice of material suitable for the rotary kiln.
3a With ceramic rotary kilns, which are sufficiently stable to the action of highly corrosive lithium salts, the heat transfer through the ceramic walls in indirect heating is less than optimal. In addition, owing to the nature of their material of construction, ceramic rotary tubes are only fabricatable and operable in comparatively small sizes, and therefore are only suitable for comparatively small production capacities.
Finally, numerous morphologies are observed to give rise to substantial dusting and thus to a broad particle size distribution having an undesirably high proportion of fine dust.
The present invention accordingly has for its object to provide a process suitable for producing lithium-containing oxidic materials useful as cathode materials for lithium ion batteries. The present invention more particularly has for its object to produce such oxidic materials as have a homogeneous composition and thus are very useful for producing electrode materials. The present invention further has for its object to provide pulverulent materials useful for producing lithium ion batteries.
We have found that this object is achieved by the process defined at the beginning, which herein is also referred to as inventive process.
The inventive process has the purpose of producing oxidic compounds. Oxidic compounds in the context of the present invention may comprise mixed oxides, intercalation compounds, sheet oxides, or spinels. Sheet oxides are preferred.
Oxidic compounds obtained according to the present invention have the general formula (I) LizMx0y (I) where M is one or more transition metals or elements of groups 2 to 12 of the periodic table and/or aluminum, preferably Mg, Al or elements of groups 5 to 10 of the periodic table, more preferably selected from Co, Mn, Ni, Fe, Al, Mg. M can be present in the oxidation states +1 to +4, preference being given to the oxidation states +2 and +3, and it is particularly preferable to have the oxidation state +3 in the case of Al and the oxidation state +2 in the case of Co, Mn, Ni, Fe, and Mg.
3h In oxidic compound of formula (I), M can represent combinations of two or more metals, for example combinations of Co and Mn or combinations of Ni and Mn. Other illustrative combinations are Ni, Co, Al, and Ni, Co, Mn. The metals mentioned can be present therein in identical or different molar fractions. In one embodiment of the present invention, M represents Ni, Co, Mn in respectively identical molar fractions.
In another embodiment of the present invention, M represents Ni0.6Co0.2Mno.2.
In another embodiment of the present invention, M represents Ni0.5Co0.2Mno.3. In another embodiment of the present invention, M represents Ni0.4ComMno4.
In another embodiment of the present invention, M is selected from Ni0.4Co0.3Mno.3, Ni0.45Coo.1Mn0.45, Ni0.4C00.1Mno.5 and Ni0.5C00.1Mn0.4.
X is a number from 1 to 2, can be an average value and is not restricted to integers.
Preferably x is 1.
y is a number from 2 to 4, can be an average value and is not restricted to integers.
Preferably y is 2 + (x-1) + (z-1).
z is a number from 0.5 to 1.5 and preferably from 0.75 to 1.4.
The inventive process proceeds from mixtures of oxides, hydroxides, carbonates and nitrates of lithium and of M, i.e., the transition metal or metals, with at least one lithium compound. The oxide(s), hydroxide(s), carbonate(s) or nitrate(s) of M on the one hand and the lithium compound on the other can have identical or different counter-ions, based on M and lithium.
4 In one embodiment of the present invention, oxides, carbonates, hydroxides and nitrates of M comprise stoichiometrically unitary compounds.
In another embodiment of the present invention, oxides, carbonates, hydroxides and nitrates of M comprise stoichiometrically nonunitary compounds. Basic carbonates, oxide hydroxides for example of the formula MOOH, basic hydroxides and basic nitrates are suitable for example.
It is further possible for hydroxides, oxides, carbonates and/or nitrates of M
and also of lithium to be present in solvated, more particularly hydrated, form or in nonsolvated or nonhydrated form.
Prior to the actual reaction, oxides, hydroxides, carbonates and/or nitrates of lithium and of M are mixed with one another and the desired stoichiometric ratio of M
and Li is established in the course of mixing.
The inventive process is carried out in a reaction vessel that is preferably essentially tube-shaped although its shape can be chosen within wide limits.
"Essentially tube-shaped" in the context of the present invention is to be understood as meaning that the length of the reaction vessel in question is distinctly greater than the average diameter as measured at the cross section, and that the cross section is essentially the same along the length of the reaction vessel.
In one embodiment of the present invention, the cross section of the reaction vessel used is circle shaped.
In another embodiment of the present invention, the cross section of the reaction vessel used differs from the circle shape and comprises for example a polygon having rounded corners, for example a rectangle or an equilateral or nonequilateral penta- or hexagon having respectively rounded corners in that one or more of the corners can be rounded in each case.
In another embodiment of the present invention, the cross section of the reaction vessel used in the inventive process is elliptical.
In one embodiment of the present invention, the reaction vessel is from 2 to 200 m, preferably from 3 to 100 m and more preferably from 5 to 50 m in length.
In one embodiment of the present invention, the reaction vessel has an average cross-sectional diameter in the range from 200 to 10 000 mm, preferably in the range from 300 to 5000 mm and more preferably in the range from 500 to 4000 mm. The average diameter in the case of noncircular cross sections is the so-called hydraulic diameter of the cross section, which computes as the ratio (4 times cross section)/(circumference of cross section).
In another embodiment of the present invention, oxides, carbonates, hydroxides and nitrates of M comprise stoichiometrically nonunitary compounds. Basic carbonates, oxide hydroxides for example of the formula MOOH, basic hydroxides and basic nitrates are suitable for example.
It is further possible for hydroxides, oxides, carbonates and/or nitrates of M
and also of lithium to be present in solvated, more particularly hydrated, form or in nonsolvated or nonhydrated form.
Prior to the actual reaction, oxides, hydroxides, carbonates and/or nitrates of lithium and of M are mixed with one another and the desired stoichiometric ratio of M
and Li is established in the course of mixing.
The inventive process is carried out in a reaction vessel that is preferably essentially tube-shaped although its shape can be chosen within wide limits.
"Essentially tube-shaped" in the context of the present invention is to be understood as meaning that the length of the reaction vessel in question is distinctly greater than the average diameter as measured at the cross section, and that the cross section is essentially the same along the length of the reaction vessel.
In one embodiment of the present invention, the cross section of the reaction vessel used is circle shaped.
In another embodiment of the present invention, the cross section of the reaction vessel used differs from the circle shape and comprises for example a polygon having rounded corners, for example a rectangle or an equilateral or nonequilateral penta- or hexagon having respectively rounded corners in that one or more of the corners can be rounded in each case.
In another embodiment of the present invention, the cross section of the reaction vessel used in the inventive process is elliptical.
In one embodiment of the present invention, the reaction vessel is from 2 to 200 m, preferably from 3 to 100 m and more preferably from 5 to 50 m in length.
In one embodiment of the present invention, the reaction vessel has an average cross-sectional diameter in the range from 200 to 10 000 mm, preferably in the range from 300 to 5000 mm and more preferably in the range from 500 to 4000 mm. The average diameter in the case of noncircular cross sections is the so-called hydraulic diameter of the cross section, which computes as the ratio (4 times cross section)/(circumference of cross section).
5 In one embodiment of the present invention, the reaction vessel has a ratio of length to average or hydraulic diameter in the range from 50:1 to 2:1, preferably in the range from 30:1 to 4:1 and more preferably in the range from 20:1 to 7:1.
In the practice of the inventive process, the reaction vessel performs incomplete rotary motions about one axis, preferably about the longitudinal axis.
Incomplete rotary motions comprise continuous incomplete rotary motions in one embodiment of the present invention and discontinuous incomplete rotary motions in another embodiment of the present invention.
"Incomplete rotary motions" in the context of the present invention is to be understood as meaning that the rotary motions amount to rotation of less than 360 but not to rotation by 360 . The extent of the rotary motions can be characterized for example by the field of traverse of the incomplete rotary motion. In one embodiment of the present invention, the field of traverse of the incomplete rotary motion is in the range from 40 to 300 , preferably in the range from 60 to 250 and more preferably in the range from 80 to 180 . It is very particularly preferable for the field of traverse of the incomplete rotary motion to be in the range from 90 to 130 . The field of traverse of the incomplete rotary motion may preferably be determined between the two end deflections (points of reversal) of the rotary motion.
In one embodiment, the reaction vessel performs oscillating or rocking rotary motions.
In one embodiment of the present invention, the reaction vessel performs the oscillating rotary motion at a frequency of 0.1 to 100 pendulum motions per minute, preferably at 1 to 50 pendulum motions per minute and more preferably at 2 to pendulum motions per minute. One pendulum motion describes the to and fro movement until the same position is traversed in the same direction of motion, for example from one end deflection into the other and back again.
The inventive process is carried out by heating to reaction temperatures in the range from 600 to 1200 C and preferably from 650 to 1050 C. Said heating can be effected directly or indirectly or through combinations of direct and indirect heating.
Temperatures preferably relate to the maximum temperature and more particularly to the temperature which can be measured in the gas space above and in the vicinity of the reaction mixture.
In the practice of the inventive process, the reaction vessel performs incomplete rotary motions about one axis, preferably about the longitudinal axis.
Incomplete rotary motions comprise continuous incomplete rotary motions in one embodiment of the present invention and discontinuous incomplete rotary motions in another embodiment of the present invention.
"Incomplete rotary motions" in the context of the present invention is to be understood as meaning that the rotary motions amount to rotation of less than 360 but not to rotation by 360 . The extent of the rotary motions can be characterized for example by the field of traverse of the incomplete rotary motion. In one embodiment of the present invention, the field of traverse of the incomplete rotary motion is in the range from 40 to 300 , preferably in the range from 60 to 250 and more preferably in the range from 80 to 180 . It is very particularly preferable for the field of traverse of the incomplete rotary motion to be in the range from 90 to 130 . The field of traverse of the incomplete rotary motion may preferably be determined between the two end deflections (points of reversal) of the rotary motion.
In one embodiment, the reaction vessel performs oscillating or rocking rotary motions.
In one embodiment of the present invention, the reaction vessel performs the oscillating rotary motion at a frequency of 0.1 to 100 pendulum motions per minute, preferably at 1 to 50 pendulum motions per minute and more preferably at 2 to pendulum motions per minute. One pendulum motion describes the to and fro movement until the same position is traversed in the same direction of motion, for example from one end deflection into the other and back again.
The inventive process is carried out by heating to reaction temperatures in the range from 600 to 1200 C and preferably from 650 to 1050 C. Said heating can be effected directly or indirectly or through combinations of direct and indirect heating.
Temperatures preferably relate to the maximum temperature and more particularly to the temperature which can be measured in the gas space above and in the vicinity of the reaction mixture.
6 In one embodiment of the present invention, the temperature within the reaction vessel is the same or essentially the same, i.e., maximum temperature and minimum temperature differ by 25 C at most. In another embodiment of the present invention, the reaction vessel has a temperature profile where maximum temperature and minimum temperature can differ by up to 500 C and preferably by up to 250 C.
In one embodiment of the present invention, the axis about which the above-described incomplete rotary motions are performed and thus the reaction vessel has an inclination in the range from 1 to 20 relative to the horizontal plane, preferably 2 to 10 and more preferably to 7 .
In one embodiment of the present invention, the reaction vessel comprises a pendulum kiln. Pendulum kilns are known as such and for example in EP 0 985 642 A.
In one embodiment of the present invention, the inventive process is performed in an oxygen-containing atmosphere, for example air, or in an oxygen-enriched atmosphere.
In one embodiment of the present invention, the inventive process is performed in an oxygen atmosphere comprising merely volatile reaction products as well as oxygen.
In one embodiment of the present invention, speed and extent of incomplete rotary motions on the one hand and the inclination of the reaction vessel on the other are adjusted such that the average residence time of the mixture in the reaction vessel is in the range from half an hour up to 15 hours and preferably in the range from one to 10 hours. The extent of incomplete rotary motions and the inclination of the reaction vessel are adapted as a function of the resulting movement characteristics of the mixture.
The reaction vessel is preferably operated in a steady state.
In one embodiment of the present invention, the reaction vessel includes an inlet housing and an outlet housing or discharge housing, which are preferably positioned essentially opposite each other at the respective ends of the reaction space.
One embodiment of the present invention utilizes mixture of oxides selected from oxides, hydroxides, carbonates and nitrates of Li and of M in pulverulent or pasty form.
To use the mixture of oxides selected from oxides, hydroxides, carbonates and nitrates of Li and of M in pasty form, the paste can be prepared with water or an alcohol. Useful alcohols include for example C1-C4 alkanols, more particularly ethanol, or polyethylene glycol, for example having an average molecular weight Mw in the range from 500 to 2000 g/mol. A suitable paste can have for example a solids content in the range from 20% to 95% by weight and preferably in the range from 40% to 90% by weight.
The
In one embodiment of the present invention, the axis about which the above-described incomplete rotary motions are performed and thus the reaction vessel has an inclination in the range from 1 to 20 relative to the horizontal plane, preferably 2 to 10 and more preferably to 7 .
In one embodiment of the present invention, the reaction vessel comprises a pendulum kiln. Pendulum kilns are known as such and for example in EP 0 985 642 A.
In one embodiment of the present invention, the inventive process is performed in an oxygen-containing atmosphere, for example air, or in an oxygen-enriched atmosphere.
In one embodiment of the present invention, the inventive process is performed in an oxygen atmosphere comprising merely volatile reaction products as well as oxygen.
In one embodiment of the present invention, speed and extent of incomplete rotary motions on the one hand and the inclination of the reaction vessel on the other are adjusted such that the average residence time of the mixture in the reaction vessel is in the range from half an hour up to 15 hours and preferably in the range from one to 10 hours. The extent of incomplete rotary motions and the inclination of the reaction vessel are adapted as a function of the resulting movement characteristics of the mixture.
The reaction vessel is preferably operated in a steady state.
In one embodiment of the present invention, the reaction vessel includes an inlet housing and an outlet housing or discharge housing, which are preferably positioned essentially opposite each other at the respective ends of the reaction space.
One embodiment of the present invention utilizes mixture of oxides selected from oxides, hydroxides, carbonates and nitrates of Li and of M in pulverulent or pasty form.
To use the mixture of oxides selected from oxides, hydroxides, carbonates and nitrates of Li and of M in pasty form, the paste can be prepared with water or an alcohol. Useful alcohols include for example C1-C4 alkanols, more particularly ethanol, or polyethylene glycol, for example having an average molecular weight Mw in the range from 500 to 2000 g/mol. A suitable paste can have for example a solids content in the range from 20% to 95% by weight and preferably in the range from 40% to 90% by weight.
The
7 alcohol can undergo combustion under the reaction conditions, in which case it is preferable to use an oxygen-enriched atmosphere to ensure complete combustion.
In one embodiment of the present invention, the inventive process involves at least one of the following reactions:
2 LiON-1-120 + 2 M(OH)2 + 1/202 , 2 LiM02 + 5 H20 Li2CO3 + 2 M(OH)2 + 1/2 02 -, 2 LiM02 + 2 H20 + CO2 LiNO3 + M(OH)2 -> LiM02 + NO2 + H20 Instead of M(OH)2, MO=aq can be used to carry out the aforementioned reactions.
In one embodiment, by-products which are gaseous under the reaction conditions such as for example water, CO2 and nitrogen oxides such as NO2 for example are withdrawn from the reaction vessel in a continuous manner. In another embodiment of the present invention, by-products which are gaseous under the reaction conditions can be withdrawn from the reaction vessel in intervals.
It is naturally preferable to clean up the stream of by-products which are gaseous under the reaction conditions and optionally to effect measures for exit gas cleaning or waste heat recovery. Exit gas cleaning can be necessary particularly when nitrates are used on a comparatively large scale. Exit gas cleaning can comprise for example an NOx decomposition and/or a removal of dust.
One embodiment of the present invention utilizes a reaction vessel consisting essentially of one or more ceramic materials of construction or lined, for example brickworked, with ceramic material.
One embodiment of the present invention may utilize a reaction vessel at least partially lined with ceramic tiles or ceramic bricks, for example with ceramic tiles or ceramic bricks based on A1203 or based on MgO-doped A1203.
One embodiment of the present invention may comprise direct heating of the reaction vessel, for example through one or more burners which are each installed on the inside surface of the reaction vessel and which may each comprise for example a radiant electric heater or a combination of two or more radiant electric heaters.
Burners operated with gas, preferably with natural gas, can be used in one version.
The inventive process provides oxidic compound of unitary chemical composition and preferably narrow particle diameter distribution. The oxidic compounds obtained
In one embodiment of the present invention, the inventive process involves at least one of the following reactions:
2 LiON-1-120 + 2 M(OH)2 + 1/202 , 2 LiM02 + 5 H20 Li2CO3 + 2 M(OH)2 + 1/2 02 -, 2 LiM02 + 2 H20 + CO2 LiNO3 + M(OH)2 -> LiM02 + NO2 + H20 Instead of M(OH)2, MO=aq can be used to carry out the aforementioned reactions.
In one embodiment, by-products which are gaseous under the reaction conditions such as for example water, CO2 and nitrogen oxides such as NO2 for example are withdrawn from the reaction vessel in a continuous manner. In another embodiment of the present invention, by-products which are gaseous under the reaction conditions can be withdrawn from the reaction vessel in intervals.
It is naturally preferable to clean up the stream of by-products which are gaseous under the reaction conditions and optionally to effect measures for exit gas cleaning or waste heat recovery. Exit gas cleaning can be necessary particularly when nitrates are used on a comparatively large scale. Exit gas cleaning can comprise for example an NOx decomposition and/or a removal of dust.
One embodiment of the present invention utilizes a reaction vessel consisting essentially of one or more ceramic materials of construction or lined, for example brickworked, with ceramic material.
One embodiment of the present invention may utilize a reaction vessel at least partially lined with ceramic tiles or ceramic bricks, for example with ceramic tiles or ceramic bricks based on A1203 or based on MgO-doped A1203.
One embodiment of the present invention may comprise direct heating of the reaction vessel, for example through one or more burners which are each installed on the inside surface of the reaction vessel and which may each comprise for example a radiant electric heater or a combination of two or more radiant electric heaters.
Burners operated with gas, preferably with natural gas, can be used in one version.
The inventive process provides oxidic compound of unitary chemical composition and preferably narrow particle diameter distribution. The oxidic compounds obtained
8 PCT/1B2011/050371 according to the present invention are therefore very useful in the manufacture of electrodes, for example anodes or cathodes, for lithium ion batteries. The oxidic compounds obtained according to the present invention therefore generally comprise only a very low level of undesired impurities from the wall material of the reaction vessel.
In addition, the oxidic compounds obtained by the inventive process are obtainable with high space-time yields and with high capacities.
In addition, the oxidic compounds obtained by the inventive process are obtainable with high space-time yields and with high capacities.
Claims (9)
1. A process for producing oxidic compounds of the general formula (l) Li z M x O y (I) where M is selected from the group consisting of Co, Mn, Ni, Fe, Al and Mg, x is from 1 to 2, y is from 2 to 4, and z is from 0.5 to 1.5, which process comprises heating a mixture comprising at least one first compound and at least one second compound together, - the at least one first compound being selected from the group consisting of oxides of Li, hydroxides of Li, carbonates of Li and nitrates of Li, and - the at least one second compound being selected from the group consisting of oxides of M, hydroxides of M, carbonates of M and nitrates of M, M being as defined above, to reaction temperatures in the range from 600 to 1200°C in a reaction vessel performing incomplete rotary motions about one axis.
2. The process according to claim 1, wherein the reaction vessel has an inclination in the range from 1 to 20°.
3. The process according to claim 1, wherein the axis about which incomplete rotary motions are performed has an inclination in the range from 1 to 20°
relative to the horizontal plane.
relative to the horizontal plane.
4. The process according to any one of claims 1 to 3, wherein the reaction vessel comprises a pendulum kiln.
5. The process according to any one of claims 1 to 4, wherein said process is further carried out in an oxygen-containing atmosphere or an oxygen-enriched atmosphere.
6. The process according to any one of claims 1 to 5, wherein said mixture is in a pulverulent form or a pasty form.
7. The process according to claim 6, wherein said mixture is in the pasty form, and wherein said pasty form is obtained by adding water or an alcohol to said mixture.
8. The process according to any one of claims 1 to 7, wherein the field of traverse of the incomplete rotary motion is in the range from 60 to 250°.
9. The process according to any one of claims 1 to 8, wherein the reaction temperatures are at least partially obtained by direct heating.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29935610P | 2010-01-29 | 2010-01-29 | |
| US61/299,356 | 2010-01-29 | ||
| EP10152110.2 | 2010-01-29 | ||
| EP10152110 | 2010-01-29 | ||
| EP10153684 | 2010-02-16 | ||
| EP10153684.5 | 2010-02-16 | ||
| PCT/IB2011/050371 WO2011092648A1 (en) | 2010-01-29 | 2011-01-28 | Producing oxidic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2787373A1 CA2787373A1 (en) | 2011-08-04 |
| CA2787373C true CA2787373C (en) | 2018-03-06 |
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ID=44170571
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2787373A Active CA2787373C (en) | 2010-01-29 | 2011-01-28 | Producing oxidic compounds |
Country Status (8)
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| US (1) | US20120319035A1 (en) |
| EP (1) | EP2368850B1 (en) |
| JP (1) | JP5363661B2 (en) |
| KR (1) | KR20120123464A (en) |
| CN (1) | CN102725886B (en) |
| CA (1) | CA2787373C (en) |
| TW (1) | TW201136837A (en) |
| WO (1) | WO2011092648A1 (en) |
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| JP6335797B2 (en) * | 2012-02-15 | 2018-05-30 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Particle, production method thereof and use thereof |
| US11462732B2 (en) | 2018-02-28 | 2022-10-04 | Basf Se | Process for making a coated electrode active material |
| JP7103840B2 (en) * | 2018-05-07 | 2022-07-20 | 株式会社ノリタケカンパニーリミテド | Powder material manufacturing method using a core tube external heat type powder material firing device and a core tube external heat type powder material firing device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB576462A (en) * | 1943-08-11 | 1946-04-04 | Ford Motor Co | Improvements in kilns |
| US4278745A (en) * | 1980-02-25 | 1981-07-14 | Medtronic, Inc. | Cathode materials for electrochemical cells |
| JPH02145432A (en) * | 1988-11-25 | 1990-06-04 | Chuo Denki Kogyo Kk | Production of coralliform manganese dioxide and production thereof |
| JPH04299828A (en) * | 1991-03-28 | 1992-10-23 | Shin Etsu Handotai Co Ltd | Semiconductor substrate treatment device |
| DE19520874A1 (en) * | 1994-12-15 | 1996-06-20 | Basf Magnetics Gmbh | Spinels containing lithium and manganese (III / IV) |
| CN1177728A (en) * | 1996-09-24 | 1998-04-01 | 夏重力 | Ferrite prefiring material rotary kiln |
| DE59907608D1 (en) | 1998-08-13 | 2003-12-11 | Von Roll Umwelttechnik Ag | Methods and devices for producing aggregates from expandable green moldings for lightweight materials |
| US6576215B1 (en) * | 1999-04-08 | 2003-06-10 | Mitsui Mining & Smelting Co., Ltd. | Method for preparing lithium manganate having spinel structure |
| JP2001223008A (en) * | 1999-12-02 | 2001-08-17 | Honjo Chemical Corp | Lithium ion secondary battery, positive electrode active material therefor and method for producing the same |
| JP2002260655A (en) * | 2001-02-28 | 2002-09-13 | Nichia Chem Ind Ltd | Method for producing positive electrode active material for lithium ion secondary battery |
| US7241532B2 (en) * | 2002-03-28 | 2007-07-10 | Mitsubishi Chemical Corporation | Positive-electrode material for lithium secondary battery, secondary battery employing the same, and process for producing positive-electrode material for lithium secondary battery |
| US20040148868A1 (en) * | 2003-02-05 | 2004-08-05 | 3M Innovative Properties Company | Methods of making ceramics |
| KR100727332B1 (en) * | 2003-09-26 | 2007-06-12 | 미쓰비시 가가꾸 가부시키가이샤 | Lithium composite oxide particles for positive electrode material of lithium secondary battery, positive electrode and lithium secondary battery for lithium secondary battery using same |
| CN100342569C (en) * | 2005-07-15 | 2007-10-10 | 广州鸿森材料有限公司 | Method for synthesizing lithium ion cell positive cell polar material rotary furnace |
| WO2007116718A1 (en) * | 2006-03-30 | 2007-10-18 | Zeon Corporation | Composite particles for electrochemical element electrode, process for producing composite particles for electrochemical element electrode, and electrochemical element electrode |
| DE102007024587B3 (en) | 2007-05-25 | 2008-09-25 | Riedhammer Gmbh | Low furnace for burning carbon anodes, carbon cathodes or carbon electrodes comprises chambers arranged behind and next to each other forming an annular shape, a suction unit for removing waste gas and a mobile suction unit |
| CN101679074B (en) * | 2008-02-04 | 2012-02-22 | 松下电器产业株式会社 | Method for producing lithium-containing transition metal oxide |
-
2011
- 2011-01-27 TW TW100103163A patent/TW201136837A/en unknown
- 2011-01-28 US US13/575,499 patent/US20120319035A1/en not_active Abandoned
- 2011-01-28 KR KR1020127022003A patent/KR20120123464A/en not_active Ceased
- 2011-01-28 CA CA2787373A patent/CA2787373C/en active Active
- 2011-01-28 EP EP11152455A patent/EP2368850B1/en not_active Not-in-force
- 2011-01-28 CN CN201180007507.4A patent/CN102725886B/en not_active Expired - Fee Related
- 2011-01-28 JP JP2012550547A patent/JP5363661B2/en active Active
- 2011-01-28 WO PCT/IB2011/050371 patent/WO2011092648A1/en not_active Ceased
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| KR20120123464A (en) | 2012-11-08 |
| WO2011092648A1 (en) | 2011-08-04 |
| EP2368850A1 (en) | 2011-09-28 |
| JP2013518024A (en) | 2013-05-20 |
| JP5363661B2 (en) | 2013-12-11 |
| CA2787373A1 (en) | 2011-08-04 |
| US20120319035A1 (en) | 2012-12-20 |
| EP2368850B1 (en) | 2012-12-26 |
| CN102725886B (en) | 2016-08-31 |
| TW201136837A (en) | 2011-11-01 |
| CN102725886A (en) | 2012-10-10 |
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