WO2012020986A2 - 무기화합물의 제조장치 및 이를 사용한 무기화합물의 제조방법 - Google Patents
무기화합물의 제조장치 및 이를 사용한 무기화합물의 제조방법 Download PDFInfo
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- WO2012020986A2 WO2012020986A2 PCT/KR2011/005844 KR2011005844W WO2012020986A2 WO 2012020986 A2 WO2012020986 A2 WO 2012020986A2 KR 2011005844 W KR2011005844 W KR 2011005844W WO 2012020986 A2 WO2012020986 A2 WO 2012020986A2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/008—Processes carried out under supercritical conditions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/002—Nozzle-type elements
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/40—Polyphosphates
- C01B25/41—Polyphosphates of alkali metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/006—Compounds containing, besides germanium, two or more other elements, with the exception of oxygen or hydrogen
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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
- C01G45/02—Oxides; Hydroxides
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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—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
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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
- C01G49/02—Oxides; Hydroxides
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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
- C01G51/04—Oxides; Hydroxides
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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
- C01G53/04—Oxides; Hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- the present invention relates to an apparatus for continuously preparing an inorganic slurry by hydrothermal method, comprising: a precursor liquid or slurry stream comprising a precursor for preparing an inorganic material, and a supercritical liquid stream including water of a high temperature and a high pressure. liquid stream) and a reactor for continuously injecting the precursor liquid or slurry stream and the supercritical liquid stream to discharge the inorganic slurry resulting from the reaction after the hydrothermal reaction occurs, and the precursor liquid or slurry stream is introduced in the reactor.
- the direction relates to a hydrothermal synthesis apparatus in the range of 0 degrees to 60 degrees based on the discharge direction of the inorganic material stream comprising the inorganic slurry.
- Inorganic compounds are used as raw materials or final products in various fields, and are used as materials for electrode active materials in secondary batteries, which have recently increased rapidly.
- a lithium secondary battery which is a representative example of a secondary battery, generally uses lithium cobalt (LiCoO 2 ) as a positive electrode active material, carbon as a negative electrode active material, lithium hexafluorophosphate (LiPF 6 ) as an electrolyte, and the like.
- Lithium cobalt (LiCoO 2 ), lithium nickelate (LiNiO 2 ), and lithium manganate (LiMn 2 O 4 ) having a spinel structure are known as the positive electrode active material, but the cobalt is actually used commercially. Lithium acid is mostly.
- Dry firing method is a cathode active material by mixing a transition metal oxide or hydroxide such as cobalt (Co) and lithium carbonate or lithium hydroxide as a lithium source in a dry state, and then calcined at a high temperature of 700 °C to 1000 °C for 5 hours to 48 hours To prepare.
- the dry firing method is a technique that has been traditionally used for the manufacture of metal oxides, and thus has the advantage of easy access, but it is difficult to obtain homogeneous mixing of the raw materials, making it difficult to obtain a single phase product as well as two or more transitions.
- a multicomponent positive electrode active material made of a metal it is difficult to homogeneously arrange two or more elements up to the atomic level.
- even when doping or replacing a specific metal component to improve the electrochemical performance it is difficult to uniformly mix a small amount of the specific metal component, as well as a grinding and classification process to obtain particles of a desired size There is also a problem that loss inevitably occurs in the system.
- the positive electrode active material is wet precipitation.
- a transition metal-containing salt such as cobalt (Co) is dissolved in water, an alkali is added to precipitate the transition metal hydroxide, and then the precipitate is filtered and dried, and lithium carbonate or lithium hydroxide, which is a lithium source, is dried thereon.
- the positive electrode active material is prepared by baking for 1 to 48 hours at a high temperature of 700 °C to 1000 °C.
- the wet precipitation method is known to be easy to obtain a homogeneous mixture by co-precipitating two or more transition metal elements, but there is a problem that a long time is required for the precipitation reaction, the process is complicated, and waste acid is generated as a by-product.
- various methods such as a sol-gel method, a hydrothermal method, a spray pyrolysis method, and an ion exchange method have been proposed as a method for producing a positive electrode active material for a lithium secondary battery.
- a supercritical liquid stream including high temperature and high pressure water is introduced at the top of the reactor 100, and the precursor liquid or As the slurry stream is introduced, the reaction takes place in the reactor 100 for a short time, and the inorganic compound is prepared by a process in which the inorganic slurry stream is discharged downward.
- the inflow direction of the precursor liquid or slurry stream into the reactor 100 is at an angle of 90 degrees with respect to the discharge direction.
- the supercritical liquid stream is moving from the top to the bottom in the reactor 100 at a higher flow rate than the precursor liquid stream or the slurry stream, and the precursor liquid stream or the slurry stream moves rapidly in the direction of movement near the inlet of the precursor liquid stream or the slurry stream.
- this results in a great resistance and the synthesis reaction takes place in a short time, so that the reaction occurs near the inlet and starts to block at the edge.
- the continuous operation time of the hydrothermal synthesis apparatus is only about one week, there is a problem that takes a lot of labor and time, such as disassemble the clogged reactor and clean the inside.
- the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
- the inventors of the present application have a precursor liquid or slurry stream, a supercritical liquid stream, a reactor, and the like, and the apparatus for continuously preparing the inorganic slurry by hydrothermal method, as described later.
- the reactor when the inflow direction of the precursor liquid or slurry stream is set to a specific condition for the discharge direction of the inorganic slurry stream, it is surprisingly found that it is possible to minimize or completely eliminate the blockage of the liquid stream inlet, It was completed.
- the present invention is a device for continuously producing an inorganic slurry by the hydrothermal method, a precursor liquid or slurry stream containing a precursor for producing an inorganic material, supercritical liquid containing high temperature and high pressure water A stream (supercritical liquid stream) and a reactor for continuously discharging the inorganic slurry resulting from the reaction after introduction of the precursor liquid phase or the slurry stream and the supercritical liquid stream, followed by hydrothermal reaction, and the precursor liquid phase or slurry in the reactor.
- An inflow direction of the stream is provided in the range of 0 to 60 degrees with respect to the discharge direction of the inorganic material stream comprising the inorganic slurry.
- Supercritical liquid stream in the present invention means a liquid stream comprising water at high temperature and high pressure regardless of its name.
- the inflow direction of the precursor liquid phase or the slurry stream in the reactor is set to satisfy the above conditions with respect to the discharge direction of the inorganic slurry stream, thereby fundamentally solving the problems of the prior art as described above.
- the inflow direction of the precursor liquid or slurry stream is in the range of 0 degrees to 45 degrees based on the discharge direction of the inorganic slurry stream including the inorganic slurry.
- the inorganic slurry may have a content of the inorganic material of 0.05 to 5% by weight.
- the inorganic materials are different precursors according to the kind, and even if the same inorganic material is prepared, available precursors may be different. Selection of appropriate precursors as needed will be apparent to those skilled in the art. As a non-limiting example, when preparing Co 2 O 3 , cobalt nitrate (Co (NO 3 ) 3 ) or cobalt sulfate (Co 2 (SO 4 ) 3 ) may be used as a precursor.
- LiFePO 4 requires an iron precursor, a phosphorus precursor, a lithium precursor, or the like as a precursor, and such a precursor can be appropriately selected and used as necessary.
- iron sulfate, phosphoric acid, lithium hydroxide, or the like can be used as a precursor of LiFePO 4 .
- LiFePO 4 may be prepared by mixing an aqueous solution of iron sulfate and phosphoric acid and an aqueous solution of ammonia water and lithium hydroxide, and then introducing the precursor liquid or slurry stream into the reactor and reacting with high temperature and high pressure water. Can be.
- the hourly flow rate (flow rate) of the precursor liquid phase or slurry stream and the supercritical liquid stream may be 1: 2 to 1:50 (precursor liquid or slurry stream: supercritical liquid stream) based on the weight ratio.
- the ratio of the flow rate is less than 1: 2
- the amount of the supercritical liquid stream may be insufficient, so that the hydrothermal synthesis reaction may be difficult to proceed with a high yield. It is not preferable because the rise and the inorganic content in the slurry may be lowered, which may lower productivity.
- the above conditions are conditions for optimizing hydrothermal synthesis in the apparatus of the present invention, and may be changed according to various process conditions such as precursor, inorganic material, and production rate.
- the supercritical liquid stream may comprise, for example, high temperature and high pressure water having a temperature of 100 to 700 ° C. and a pressure of 10 to 550 bar. More preferably, it may include a supercritical water having a temperature of 374 to 700 ° C. and a pressure of 221 to 550 bar or subcritical water similar to supercritical temperature and pressure conditions.
- temperature and pressure can be arbitrarily set, but it is preferable to set the temperature in the range of 700 ° C. or less than 550 bar in consideration of equipment problems, control problems of the reaction, and the like.
- the supercritical liquid stream entering the main mixer may be one or more, more preferably two or more.
- the inlet position, angle, etc. of the supercritical liquid streams in the main mixer can be freely selected independently.
- the two or more supercritical liquid streams may be configured to have inflow directions opposed to each other.
- the supercritical liquid stream may consist of a first supercritical liquid stream and a second supercritical liquid stream, in which case the inflow direction of the first supercritical liquid stream and the inflow direction of the second supercritical liquid stream are Since the reaction atmosphere such as the reaction time can be adjusted according to the angle, it is possible to adjust in the appropriate range. That is, the angle can be adjusted to achieve the desired reaction atmosphere in the range of more than 0 degrees and less than 180 degrees based on the discharge direction of the inorganic slurry stream. Preferably it may range from 10 degrees to 170 degrees based on the discharge direction of the inorganic slurry stream.
- the inflow direction of the supercritical liquid stream is less than 10 degrees based on the discharge direction of the inorganic slurry stream, the reaction may not be performed smoothly and may be immediately discharged.
- the high pressure of the streams is undesirable because of the possibility of backflow in the reactor.
- the inflow direction of the supercritical liquid stream is more preferably in the range of 20 degrees to 160 degrees based on the discharge direction of the inorganic slurry stream.
- the supercritical liquid stream is the discharge direction of the inorganic slurry stream if the inflow direction of the supercritical liquid stream exceeds 90 degrees relative to the discharge direction of the inorganic slurry stream.
- the reaction can take place in the vicinity of the inlet of the precursor liquid phase or slurry stream as it has a speed in the opposite direction relative to. In this case, clogging of the inlet of the precursor liquid or slurry stream may occur. Therefore, it is preferable to set an angle within an appropriate range in consideration of the size of the reactor.
- the inlet direction of the precursor liquid phase or slurry stream in the reactor is in the range of 0 degrees to 60 degrees based on the discharge direction of the inorganic slurry stream, preferably in the range of 0 degrees to 45 degrees, more preferably. Preferably it may be in the range of 0 degrees to 30 degrees, particularly preferably in the range of 0 degrees to 20 degrees. Among them, a structure in which the condition at 0 degrees, that is, the inflow direction of the precursor liquid phase or the slurry stream and the discharge direction of the inorganic slurry stream are located in a straight line is most preferable.
- it may further include a premixer for preparing the precursor that provides the precursor liquid or slurry stream.
- the present invention also provides an inorganic slurry, which is prepared using the hydrothermal synthesis apparatus.
- the inorganic slurry can be used for various purposes according to its type.
- the inorganic slurry may be used as a cathode active material for secondary batteries. That is, the inorganic material obtained by drying the said inorganic material slurry can be used as a material of the positive electrode active material for secondary batteries.
- a secondary battery using such an inorganic material as a cathode active material is composed of a cathode, an anode, a separator, and a lithium-containing non-aqueous electrolyte.
- the positive electrode may be prepared by, for example, applying a slurry made by mixing a positive electrode mixture with a solvent such as NMP onto a negative electrode current collector, followed by drying and rolling.
- the positive electrode mixture may be an inorganic material prepared using the apparatus as a positive electrode active material, and may optionally include a conductive material, a binder, a filler, and the like.
- the conductive material is typically added in an amount of 1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
- a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
- the binder is a component that assists the bonding of the active material and the conductive material to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
- binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.
- the filler is optionally used as a component for inhibiting the expansion of the electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
- the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
- the positive electrode current collector is generally made to a thickness of 3 to 500 ⁇ m. Such a positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- the positive electrode current collector may be formed on a surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel. Surface-treated with carbon, nickel, titanium, silver, and the like can be used.
- the current collector may form fine irregularities on its surface to increase the adhesion of the positive electrode active material, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
- the negative electrode is prepared by, for example, applying a negative electrode mixture containing a negative electrode active material on a negative electrode current collector and then drying the negative electrode mixture.
- the negative electrode mixture may include, as necessary, a conductive material, a binder, a filler, and the like. The components of may be included.
- the negative electrode current collector is generally made to a thickness of 3 to 500 ⁇ m.
- a negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
- copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver and the like on the surface, aluminum-cadmium alloy and the like can be used.
- fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
- the separator is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used.
- the pore diameter of the separator is generally from 0.01 to 10 ⁇ m ⁇ m, thickness is generally 5 ⁇ 300 ⁇ m.
- a separator for example, olefin polymers such as chemical resistance and hydrophobic polypropylene; Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
- a solid electrolyte such as a polymer
- the solid electrolyte may also serve as a separator.
- the lithium salt-containing non-aqueous electrolyte solution consists of an electrolyte solution and a lithium salt, and a non-aqueous organic solvent, an organic solid electrolyte, an inorganic solid electrolyte, and the like are used as the electrolyte solution.
- non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and gamma Butyl lactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxorone, formamide, dimethylformamide, dioxolon , Acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbo Aprotic organic solvents such as nate derivatives, tetrahydrofuran derivatives, ethers, methyl pyroionate and ethyl propionate can be
- organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymerizers containing ionic dissociating groups and the like can be used.
- Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates and the like of Li, such as Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 S-SiS 2 , and the like, may be used.
- the lithium salt is a material that is readily soluble in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10 Cl 10, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide have.
- LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10 Cl 10, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide have.
- pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added. .
- halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics.
- the secondary battery as described above may not only be used in a battery cell used as a power source for a small device, but also includes a plurality of battery cells used as a power source for medium and large devices requiring high temperature stability, long cycle characteristics, and high rate characteristics. It can be preferably used as a unit cell in the medium-large battery module.
- Preferred examples of the medium-to-large device include a power tool driven by an electric motor; Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; Electric motorcycles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf carts, and the like, but are not limited thereto.
- Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like
- Electric motorcycles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf carts, and the like, but are not limited thereto.
- this invention is a method of manufacturing an inorganic slurry by hydrothermal synthesis method
- It comprises a; process for producing an inorganic slurry by the hydrothermal synthesis reaction in the reactor and continuously discharged;
- the inlet direction of the precursor liquid phase or slurry stream in the reactor is provided in the range of 0 to 60 degrees based on the discharge direction of the inorganic slurry stream including the inorganic slurry.
- Such hydrothermal synthesis can be applied to the production of inorganic materials that are difficult to be produced efficiently by conventional hydrothermal synthesis as well as inorganic materials that are known to be conventionally manufactured by hydrothermal synthesis due to the advantages described above.
- FIG. 1 is a schematic diagram of a hydrothermal synthesis apparatus according to the prior art
- FIG. 2 is a schematic diagram of a hydrothermal synthesis apparatus according to an embodiment of the present invention.
- FIG. 3 is a schematic diagram of a hydrothermal synthesis apparatus according to another embodiment of the present invention.
- FIGS. 4 and 5 are schematic diagrams of a structure in which a premixer is added to a hydrothermal synthesis apparatus according to another embodiment of the present invention.
- FIG. 2 shows a schematic diagram of a hydrothermal synthesis apparatus according to an embodiment of the present invention
- FIG. 3 shows a schematic schematic diagram of a hydrothermal synthesis apparatus according to another embodiment of the present invention.
- the precursor liquid phase or slurry stream enters the reactor 100 in a direction substantially the same as the discharge direction of the inorganic slurry stream, and supercritical liquid streams flow in opposite directions from both sides in a direction perpendicular thereto.
- the precursor liquid phase or slurry stream enters the reactor 100 in a direction substantially the same as the discharge direction of the inorganic slurry stream, and forms a predetermined angle ⁇ with respect to the discharge direction of the inorganic slurry stream.
- Supercritical liquid streams enter the sides opposite each other.
- the angle ⁇ can be appropriately adjusted according to the desired reaction atmosphere in a range of more than 0 degrees and less than 180 degrees with respect to the discharge direction of the inorganic slurry stream.
- the inflow direction of the precursor liquid or slurry stream and the discharge direction of the inorganic slurry stream are located almost in a straight line, so that the direction of the precursor liquid or slurry stream is substantially preserved and Since the manna reaction proceeds and is discharged in the form of an inorganic slurry, the resistance of the inlet is not greatly increased near the inlet, thereby significantly reducing the phenomenon that the inlet is blocked from the edge. As a result, clogging of the inlet port can be minimized. In addition, there is little loss of momentum in the advancing direction as the precursor liquid or slurry stream enters the reactor, so the inorganic content in the product is higher than in conventional equipment.
- FIGS. 4 and 5 show schematic diagrams of a structure in which a premixer is added to a hydrothermal synthesis apparatus according to another embodiment of the present invention.
- FIGS. 4 and 5 a schematic diagram of a structure in which a premixer 200 is added to a hydrothermal synthesis apparatus is illustrated.
- the basic configuration is the same as the apparatus of FIGS. 2 and 3, with the difference that a premixer 200 is added which can produce a precursor liquid or slurry stream.
- Such an apparatus for example, in preparing a LiFePO 4 inorganic slurry, first mixes Li precursors and Fe and P precursors in the premixer 200, and the precursor liquid phase or slurry stream obtained therefrom is introduced into the reactor, The reaction as described in connection with FIGS. 2 and 3 proceeds.
- clogging at the inlet of the liquid stream can be minimized, thereby increasing the continuous operation time and greatly increasing the process productivity and reducing the investment cost.
Abstract
Description
Claims (20)
- 수열법에 의해 무기물 슬러리를 연속적으로 제조하는 장치로서,무기물 제조용 전구체를 포함하는 전구체 액상 또는 슬러리 스트림(precursor liquid stream), 고온 및 고압의 물을 포함하는 초임계 액상 스트림(supercritical liquid stream), 및 상기 전구체 액상 또는 슬러리 스트림과 초임계 액상 스트림이 유입되어 수열 반응이 일어난 후 반응 결과물인 무기물 슬러리를 연속적으로 배출하는 반응기를 포함하고 있으며,상기 반응기에서 전구체 액상 또는 슬러리 스트림의 유입 방향은 무기물 슬러리를 포함하는 무기물 슬러리 스트림(inorganic material stream)의 배출 방향을 기준으로 0도 내지 60도의 범위 내에 있는 것을 특징으로 하는 수열 합성 장치.
- 제 1 항에 있어서, 상기 전구체 액상 또는 슬러리 스트림의 유입 방향은 무기물 슬러리를 포함하는 무기물 슬러리 스트림의 배출 방향을 기준으로 0도 내지 45도 범위 내에 있는 것을 특징으로 하는 수열 합성 장치.
- 제 1 항에 있어서, 상기 무기물 슬러리는 무기물의 함량이 0.05 내지 5 중량%인 것을 특징으로 하는 수열 합성 장치.
- 제 1 항에 있어서, 상기 제조 무기물 슬러리 중 무기물은 Co2O3, Fe2O3, LiMn2O4, MOx (M=Fe, Ni, Co, Mn, Al 등이고, 상기 x는 전기적 중성을 만족하는 수), MOOH(M=Fe, Ni, Co, Mn, Al 등), AaMmXxOoSsNnFf(A는 Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba로 이루어진 군에서 선택되는 하나 이상이고; M은 전이금속을 하나 이상 포함하고, 선택적으로 B, Al, Ga, In로 이루어진 군에서 선택되는 하나 이상을 포함할 수 있으며; X는 P, As, Si, Ge, Se, Te, C로 이루어진 군에서 선택되는 하나 이상이고; O는 산소; S는 황; N은 질소; F는 불소이며; a, m, x, o, s, n 및 f는 0 이상이고 전기적 중성을 만족하는 수)로 이루어진 군에서 선택되는 하나 이상인 것을 특징으로 하는 수열 합성 장치.
- 제 4 항에 있어서, 상기 무기물은 LiaMbM'cPO4(M=Fe, Ni, Co, Mn으로 이루어진 군에서 선택되는 하나 이상; M'=Ca, Ti, S, C, Mg로 이루어진 군에서 선택되는 하나 이상; a, b, c는 0 이상이고 전기적 중성을 만족하는 수)인 것을 특징으로 하는 수열 합성 장치.
- 제 5 항에 있어서, 상기 무기물은 LiFePO4인 것을 특징으로 하는 수열 합성 장치.
- 제 1 항에 있어서, 상기 전구체 액상 또는 슬러리 스트림과 초임계 액상 스트림의 시간당 유량(유속)은 중량비를 기준으로 1 : 2 ~ 1 : 50 (전구체 액상 또는 슬러리 스트림 : 초임계 액상 스트림)인 것을 특징으로 하는 수열 합성 장치.
- 제 1 항에 있어서, 상기 초임계 액상 스트림은 100 내지 700℃의 온도 및 10 내지 550 bar의 압력을 가진 고온 및 고압의 물을 포함하고 있는 것을 특징으로 하는 수열 합성 장치.
- 제 1 항에 있어서, 상기 초임계 액상 스트림은 하나 이상의 스트림들을 포함하고 있는 것을 특징으로 하는 수열 합성 장치.
- 제 9 항에 있어서, 상기 초임계 액상 스트림은 둘 이상의 스트림들을 포함하고 있는 것을 특징으로 하는 수열 합성 장치.
- 제 10 항에 있어서, 상기 둘 이상의 스트림들은 전구체 액상 또는 슬러리 스트림에 대해 서로 대향하는 유입 방향을 가지는 것을 특징으로 하는 수열 합성 장치.
- 제 10 항에 있어서, 상기 초임계 액상 스트림은 제 1 초임계 액상 스트림과 제 2 초임계 액상 스트림으로 구성되어 있는 것을 특징으로 하는 수열 합성 장치.
- 제 12 항에 있어서, 제 1 초임계 액상 스트림의 유입 방향과 제 2 초임계 액상 스트림의 유입 방향은 각각 무기물 슬러리 스트림의 배출 방향을 기준으로 0도 초과 내지 180도 미만인 것을 특징으로 하는 수열 합성 장치.
- 제 13 항에 있어서, 제 1 초임계 액상 스트림의 유입 방향과 제 2 초임계 액상 스트림의 유입 방향은 각각 무기물 슬러리 스트림의 배출 방향을 기준으로 10도 내지 170도 범위인 것을 특징으로 하는 수열 합성 장치.
- 제 1 항에 있어서, 상기 전구체 액상 또는 슬러리 스트림의 유입 방향과 무기물 슬러리 스트림의 배출 방향은 일직선 상에 위치하는 것을 특징으로 하는 수열 합성 장치.
- 제 1 항에 있어서, 상기 전구체 액상 또는 슬러리 스트림을 제공하는 전구체 제조용 프리믹서를 추가로 포함하고 있는 것을 특징으로 하는 수열 합성 장치.
- 제 1 항 내지 제 16 항 중 어느 하나에 따른 수열 합성 장치를 사용하여 제조되는 것을 특징으로 하는 무기물 슬러리.
- 제 17 항에 있어서, 상기 무기물 슬러리를 건조하여 얻어지는 것을 특징으로 하는 무기물.
- 제 18 항에 있어서, 상기 무기물은 이차전지용 양극 활물질로 사용되는 것을 특징으로 하는 무기물.
- 수열법에 의해 무기물 슬러리를 제조하는 방법으로서,무기물 제조용 반응 전구체를 포함하는 전구체 액상 또는 슬러리 스트림를 반응기에 유입하는 과정;고온 및 고압의 물을 포함하는 초임계 액상 스트림을 반응기에 유입하는 과정; 및반응기에서 수열 반응에 의해 무기물 슬러리를 제조하여 연속적으로 배출하는 과정;을 포함하고 있고,상기 반응기에서 전구체 액상 또는 슬러리 스트림의 유입 방향은 무기물 슬러리를 포함하는 무기물 슬러리 스트림의 배출 방향을 기준으로 0도 내지 60도의 범위 내에 있는 것을 특징으로 하는 제조 방법.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104812477A (zh) * | 2013-01-03 | 2015-07-29 | 株式会社Lg化学 | 用于制备锂复合过渡金属氧化物的装置、使用其制备的锂复合过渡金属氧化物以及制备锂复合过渡金属氧化物的方法 |
US20150270549A1 (en) * | 2012-11-27 | 2015-09-24 | Lg Chem, Ltd. | Apparatus for preparing inorganic compound and method of preparing inorganic compound using the same |
EP2886192A4 (en) * | 2012-11-27 | 2016-06-08 | Lg Chemical Ltd | HYDROTHERMIC SYNTHESIS APPARATUS AND PROCESS FOR PREPARING CATHODE ACTIVE MATERIAL USING THE SAME |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101655921B1 (ko) * | 2011-11-07 | 2016-09-09 | 주식회사 엘지화학 | 양극 활물질의 제조장치 및 이에 구비되는 교반장치 |
KR101490204B1 (ko) * | 2012-05-04 | 2015-02-06 | 주식회사 엘지화학 | 무기 화합물의 제조 장치 및 이를 사용한 무기 화합물의 제조방법 |
KR101498467B1 (ko) * | 2012-05-07 | 2015-03-04 | 주식회사 엘지화학 | 무기 화합물의 제조 장치 및 이를 사용한 무기화합물의 제조방법 |
KR101498469B1 (ko) * | 2012-05-07 | 2015-03-04 | 주식회사 엘지화학 | 무기 화합물의 제조 장치 및 이를 사용한 무기화합물의 제조방법 |
KR101640629B1 (ko) * | 2012-05-30 | 2016-07-18 | 주식회사 엘지화학 | 초임계 연속수열 합성 장치 및 방법 |
KR101720367B1 (ko) * | 2012-05-30 | 2017-03-27 | 주식회사 엘지화학 | 양극 활물질 제조용 필터링 장치 |
KR101655927B1 (ko) * | 2012-05-30 | 2016-09-08 | 주식회사 엘지화학 | 양극 활물질 제조용 교반장치 및 이를 포함하는 양극 활물질의 제조장치 |
KR101643444B1 (ko) * | 2012-05-30 | 2016-07-27 | 주식회사 엘지화학 | 양극 활물질 제조용 교반장치 |
KR101471433B1 (ko) * | 2012-05-31 | 2014-12-10 | 주식회사 엘지화학 | 무기 입자의 제조방법 |
KR101522526B1 (ko) * | 2012-11-26 | 2015-05-26 | 주식회사 엘지화학 | 무기 입자의 제조방법 및 그로부터 얻어진 무기 입자 |
EP3092067A1 (en) * | 2014-01-08 | 2016-11-16 | Teknologisk Institut | Method of preparing a catalyst structure |
FR3016536A1 (fr) * | 2014-01-21 | 2015-07-24 | Innoveox | Dispositif d'injection d'oxydant pour une installation de traitement d'un effluent aqueux par oxydation hydrothermale |
CN112374473B (zh) * | 2020-11-11 | 2022-04-19 | 深圳大学 | 一种基于含酚废水合成酚类有机物掺杂g-C3N4的方法 |
US20220251728A1 (en) * | 2021-02-08 | 2022-08-11 | Uchicago Argonne, Llc | Continuous hydrothermal manufacturing method for concentration-gradient monocrystalline battery material |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9413202D0 (en) * | 1994-06-30 | 1994-08-24 | Univ Bradford | Method and apparatus for the formation of particles |
GB9703673D0 (en) * | 1997-02-21 | 1997-04-09 | Bradford Particle Design Ltd | Method and apparatus for the formation of particles |
JPH11267607A (ja) * | 1998-03-26 | 1999-10-05 | Ube Ind Ltd | 廃棄物の処理方法およびその装置 |
JP4857459B2 (ja) * | 2000-03-06 | 2012-01-18 | 栗田工業株式会社 | 水熱反応方法および装置 |
JP2001290231A (ja) * | 2000-04-06 | 2001-10-19 | Fuji Photo Film Co Ltd | ハロゲン化銀乳剤の製造方法及び装置 |
JP2002102672A (ja) * | 2000-09-29 | 2002-04-09 | Kurita Water Ind Ltd | 水熱反応装置および方法 |
JP2003107608A (ja) * | 2001-09-28 | 2003-04-09 | Fuji Photo Film Co Ltd | ハロゲン化銀乳剤の製造方法及び装置 |
US7125453B2 (en) * | 2002-01-31 | 2006-10-24 | General Electric Company | High temperature high pressure capsule for processing materials in supercritical fluids |
GB0402963D0 (en) * | 2004-02-11 | 2004-03-17 | Univ Nottingham | Counter current mixing device for two different fluids |
JP5405126B2 (ja) * | 2006-02-17 | 2014-02-05 | エルジー・ケム・リミテッド | リチウム−金属複合酸化物の製造方法 |
JP4840916B2 (ja) * | 2006-07-06 | 2011-12-21 | 独立行政法人産業技術総合研究所 | 高温高圧マイクロミキサー |
JP5985134B2 (ja) * | 2009-01-23 | 2016-09-06 | 関東電化工業株式会社 | 無機微粒子の製造方法及びその製造装置 |
-
2011
- 2011-08-10 WO PCT/KR2011/005844 patent/WO2012020986A2/ko active Application Filing
- 2011-08-10 KR KR1020110079551A patent/KR101269544B1/ko active IP Right Grant
- 2011-08-10 EP EP11816602.4A patent/EP2604335A4/en not_active Withdrawn
- 2011-08-10 JP JP2013524041A patent/JP5657118B2/ja active Active
- 2011-08-10 CN CN201180036297.1A patent/CN103025419B/zh active Active
-
2013
- 2013-01-16 US US13/743,018 patent/US20130129596A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
None |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US20150270549A1 (en) * | 2012-11-27 | 2015-09-24 | Lg Chem, Ltd. | Apparatus for preparing inorganic compound and method of preparing inorganic compound using the same |
EP2886192A4 (en) * | 2012-11-27 | 2016-06-08 | Lg Chemical Ltd | HYDROTHERMIC SYNTHESIS APPARATUS AND PROCESS FOR PREPARING CATHODE ACTIVE MATERIAL USING THE SAME |
US9843035B2 (en) | 2012-11-27 | 2017-12-12 | Lg Chem, Ltd. | Hydrothermal synthesis device and method of preparing cathode active material using the same |
US9865874B2 (en) * | 2012-11-27 | 2018-01-09 | Lg Chem, Ltd. | Apparatus for preparing inorganic compound and method of preparing inorganic compound using the same |
CN104812477A (zh) * | 2013-01-03 | 2015-07-29 | 株式会社Lg化学 | 用于制备锂复合过渡金属氧化物的装置、使用其制备的锂复合过渡金属氧化物以及制备锂复合过渡金属氧化物的方法 |
JP2016506593A (ja) * | 2013-01-03 | 2016-03-03 | エルジー・ケム・リミテッド | リチウム複合遷移金属酸化物製造用装置、それを用いて製造されたリチウム複合遷移金属酸化物、及びその製造方法 |
CN104812477B (zh) * | 2013-01-03 | 2016-12-21 | 株式会社Lg 化学 | 用于制备锂复合过渡金属氧化物的装置、使用其制备的锂复合过渡金属氧化物以及制备锂复合过渡金属氧化物的方法 |
US10236503B2 (en) | 2013-01-03 | 2019-03-19 | Lg Chem, Ltd. | Mixing device for preparing lithium composite transition metal oxide, lithium composite transition metal oxide prepared using the same, and method of preparing lithium composite transition metal oxide |
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JP5657118B2 (ja) | 2015-01-21 |
EP2604335A2 (en) | 2013-06-19 |
CN103025419A (zh) | 2013-04-03 |
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