WO2012132072A1 - Procédé de production de matériau actif d'électrode positive pour batteries lithium-ion et matériau actif d'électrode positive pour batteries lithium-ion - Google Patents

Procédé de production de matériau actif d'électrode positive pour batteries lithium-ion et matériau actif d'électrode positive pour batteries lithium-ion Download PDF

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Publication number
WO2012132072A1
WO2012132072A1 PCT/JP2011/072861 JP2011072861W WO2012132072A1 WO 2012132072 A1 WO2012132072 A1 WO 2012132072A1 JP 2011072861 W JP2011072861 W JP 2011072861W WO 2012132072 A1 WO2012132072 A1 WO 2012132072A1
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Prior art keywords
positive electrode
active material
electrode active
lithium ion
firing
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PCT/JP2011/072861
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English (en)
Japanese (ja)
Inventor
保大 川橋
梶谷　芳男
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Jx日鉱日石金属株式会社
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Publication of WO2012132072A1 publication Critical patent/WO2012132072A1/fr

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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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a positive electrode active material for a lithium ion battery and a positive electrode active material for a lithium ion battery.
  • a lithium transition metal composite oxide is known as a positive electrode active material for a lithium ion battery.
  • a lithium transition metal composite oxide is prepared by mixing a lithium compound and a transition metal compound to produce a positive electrode active material precursor for a lithium ion battery, and then firing the composite. It is manufactured by making.
  • Lithium ion batteries are used for a long period of time and are repeatedly charged and discharged for various purposes, so various characteristics such as cycle characteristics and storage characteristics are required, and a high capacity at an extremely high level is required. It's getting on.
  • demand for consumer devices such as mobile phones and personal computers and lithium batteries for vehicles is increasing, it is required to manufacture lithium ion batteries efficiently at low cost.
  • a process of firing and compositing a positive electrode active material precursor for a lithium ion battery is required.
  • a precursor is used.
  • a method is used in which a baking container filled with is provided in a baking furnace (stationary furnace) and heated by a conveyor system or a batch system. When firing using a stationary furnace in this manner, a large number of precursors can be fired relatively efficiently by successively sending firing containers filled with a large number of precursors into the furnace.
  • the positive electrode active material precursor for a lithium ion battery before firing contains a large amount of gas and moisture such as carbon dioxide and nitrogen oxide. For this reason, when it is carried into a stationary furnace and firing is started, gas and moisture are first released. Therefore, even if the precursor is filled in the firing container, only the part that is actually fired and combined is only the portion left after the gas or moisture is released from the precursor initially filled in the firing container. This is actually only about 45 to 50% of the charged precursor, and is problematic from the viewpoint of efficient production of lithium ion batteries. Further, in firing using a stationary furnace, it is difficult to uniformly heat the precursor filled in the firing container, which may cause uneven firing, resulting in variations in the characteristics of the produced lithium transition metal composite oxide. There is also a problem.
  • an object of the present invention is to provide a method for producing a high-quality positive electrode active material for a lithium ion battery at a low cost.
  • the inventors of the present invention as a result of intensive investigations, the inventors of the present invention, as a result of calcining a positive electrode active material precursor for a lithium ion battery, a first stage in which gas and moisture are released is temporarily calcined in a rotary kiln, and a precursor from which gas and moisture are sufficiently released It was found that the production efficiency is improved by performing the main firing to the composite. Moreover, it discovered that a high quality positive electrode active material for lithium ion batteries could be obtained by firing the precursor without unevenness by carrying out the firing using a rotary kiln.
  • the present invention completed on the basis of the above knowledge, in a lithium kiln that is a positive electrode active material precursor for a lithium ion battery, by performing temporary firing in a rotary kiln,
  • This is a method for producing a positive electrode active material for a lithium ion battery, which includes a step of increasing the mass% of the metal by 1 to 105% as compared with that before the preliminary firing and then performing a main firing using a rotary kiln.
  • the percentage increase in mass% of all metals in the lithium-containing carbonate by temporary firing is 50 to 97%.
  • pre-baking is performed at 200 to 1200 ° C. for 30 to 120 minutes.
  • a first main baking step in which main baking is performed at 700 to 1200 ° C. for 0.5 to 12 hours, and 0 to 500 to 900 ° C. is performed.
  • the second main baking step performed for 5 to 24 hours and the third main baking step performed at 400 to 700 ° C. for 0.5 to 12 hours.
  • the first to third main firing steps are performed using at least two rotary kilns.
  • the positive electrode active material has a composition formula: Li x Ni 1- y My O 2 + ⁇
  • M is one or more selected from Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B and Zr. Yes, 0.9 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.7, and 0.05 ⁇ ⁇ .) It is represented by
  • M is one or more selected from Mn and Co.
  • the present invention provides a composition formula: Li x Ni 1- y My O 2 + ⁇
  • M is one or more selected from Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B and Zr. Yes, 0.9 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.7, and 0.05 ⁇ ⁇ .
  • a positive electrode active material for a lithium ion battery having a tap density of 1.8 to 2.2 g / cc.
  • M is at least one selected from Mn and Co.
  • FIG. 1 It is the schematic of a temporary baking apparatus.
  • FIG. 1 is a schematic view of a firing mode in which the main firing is performed using a single rotary kiln.
  • FIG. 1 is a schematic view of a firing mode in which the main firing is performed using two rotary kilns.
  • FIG. 1 is a schematic view of a firing mode in which the main firing is performed using three rotary kilns.
  • a compound useful as a positive electrode active material for a general positive electrode for lithium ion batteries can be widely used.
  • lithium cobalt oxide (LiCoO 2 ) lithium-containing transition metal oxides such as lithium nickelate (LiNiO 2 ) and lithium manganate (LiMn 2 O 4 ) are preferably used.
  • the positive electrode active material for a lithium ion battery produced using such a material is, for example, Composition formula: Li x Ni 1- y My O 2 + ⁇
  • M is one or more selected from Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B and Zr. Yes, 0.9 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.7, and 0.05 ⁇ ⁇ .
  • the ratio of lithium to all metals in the positive electrode active material for a lithium ion battery is 0.9 to 1.2. If the ratio is less than 0.9, it is difficult to maintain a stable crystal structure, and if it exceeds 1.2, the capacity is high. This is because of a low.
  • oxygen is expressed as O 2 + ⁇ (0.05 ⁇ ⁇ ) as described above in the composition formula and is excessively contained. Battery characteristics such as capacity, rate characteristics and capacity retention ratio are improved.
  • ⁇ is preferably ⁇ > 0.15, more preferably ⁇ > 0.20, and typically 0.05 ⁇ ⁇ ⁇ 0.25.
  • M is preferably one or more selected from Mn and Co in the composition formula.
  • the positive electrode active material for a lithium ion battery of the present invention has a tap density of 1.8 to 2.2 g / cc, and when used in a lithium ion battery, the battery characteristics such as capacity, rate characteristics and capacity retention ratio are good. It becomes.
  • the lithium-containing carbonate that is a precursor is fired only in a stationary furnace, it is difficult to improve the tap density because the particles of the precursor are sparse.
  • the particles are granulated and become heavy, thereby improving the tap density.
  • a metal salt solution is prepared.
  • the metal is at least one selected from Ni and Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr. It is.
  • the metal salt is sulfate, chloride, nitrate, acetate, etc., and nitrate is particularly preferable.
  • each metal contained in the metal salt is adjusted so as to have a desired molar ratio. Thereby, the molar ratio of each metal in the positive electrode active material is determined.
  • lithium carbonate is suspended in pure water, and then the metal salt solution of the metal is added to prepare a lithium salt solution slurry. At this time, fine particles of lithium-containing carbonate precipitate in the slurry. If the lithium compound does not react during heat treatment such as sulfate or chloride as a metal salt, it is washed with a saturated lithium carbonate solution and then filtered off. When the lithium compound reacts as a lithium raw material during the heat treatment, such as nitrate or acetate, it can be used as a calcined precursor by washing and drying as it is without washing. Next, the lithium-containing carbonate separated by filtration is dried to obtain a lithium salt composite (precursor for lithium ion battery positive electrode material) powder.
  • the precursor for the lithium ion battery positive electrode material contains 20 to 40 mass% of lithium, nickel, manganese, cobalt and the like as metals in total.
  • the firing apparatus 20 includes a rotary kiln 10, a powder input unit 11, a gas supply unit 12, a bag filter 13, and a powder discharge unit 14.
  • the rotary kiln 10 includes a reactor core tube 17, an outer cylinder 15 formed so as to surround the reactor core tube 17, and a heater 16 that is provided outside the outer cylinder 15 and heats the reactor core tube 17.
  • the core tube 17 is formed to have a predetermined inner diameter and length depending on the amount of the precursor to be preliminarily fired, the pre-baking time, and the like. it can.
  • the core tube 17 may be formed with stirring blades (not shown) for stirring the powder to be calcined so as to stand up from the inner wall of the core tube 17.
  • the core tube 17 is preferably formed of a material that transfers heat from the heater 16 well and does not generate contaminants that may be mixed into the precursor, such as Ni, Ti, stainless steel, or ceramic. can do.
  • the outer cylinder 15 is also preferably formed of a material that conducts heat from the heater 16 well, and can be formed of, for example, Ni, Ti, stainless steel, or ceramic.
  • the position of the heater 16 is not particularly limited as long as it is outside the outer cylinder 15. Moreover, although the heater 16 is installed in one place in FIG. 1, you may install in several places.
  • the rotary kiln 10 is inclined so as to descend from the front end portion to the rear end portion so that the precursor charged from the front end portion moves backward while being baked.
  • the inclination angle is not particularly limited, and can be set according to the temporary firing time or the like.
  • the powder input part 11 is provided with a precursor to be temporarily fired.
  • the powder input part 11 is provided in the front-end part of the rotary kiln 10, and a precursor is injected
  • the powder discharger 14 is provided at the rear end of the rotary kiln 10. From the powder discharge section 14, the powder (preliminary fired body) that has been fired through the furnace core tube 17 is discharged.
  • the gas supply unit 12 supplies a gas that circulates in the baking apparatus 20.
  • An inert gas such as nitrogen or argon, oxygen, or the like is supplied from the gas supply unit 12.
  • a path indicated by an arrow in FIG. 1 is a circulation path of the gas supplied from the gas supply unit 12.
  • the bag filter 13 is provided at the front end of the rotary kiln 10. The bag filter 13 collects the precursor mixed in the exhaust gas.
  • the bag filter 13 is formed by using a woven fabric or a non-woven fabric as a filter medium and stacking them in a cylindrical shape.
  • the inclination angle and rotation speed of the core tube 17 are appropriately set according to the firing time and firing temperature of the pre-firing with respect to the mass of the precursor for the lithium ion battery positive electrode material to be charged later.
  • the mass of the precursor is 20 to 110 g
  • the temporary baking time is 30 to 120 minutes
  • the temporary baking temperature is 200 to 1200 ° C.
  • the inclination angle of the core tube 17 is 8 to 15 ° and the rotation speed is 3 .6 to 9.6 radians / second can be set.
  • a precursor for a lithium ion battery positive electrode material is charged from the powder loading unit 11 to the front end of the furnace tube 17.
  • the charged precursor for the lithium ion battery positive electrode material is transferred to the rear end of the core tube 17 while being stirred and heated in the rotating core tube 17. In this way, the precursor is calcined.
  • gas and moisture such as carbon dioxide and nitrogen oxide are released from the precursor for the lithium ion battery positive electrode material, and the mass% of the total metal in the precursor is 1 to 105%, preferably 50%, compared with that before the preliminary firing. It has increased by 97%.
  • powder such as a precursor mixed with the supply gas and discharged from the core tube 17 is collected by the bag filter 13.
  • the precursor recovered by the bag filter 13 may be used again as a raw material after purification.
  • the precursor that has been pre-baked is discharged from the powder discharge unit 14 to the outside of the apparatus, and then the following main baking is performed.
  • the main firing step is performed in a rotary kiln without using a firing furnace (stationary furnace). For this reason, there is no possibility that the firing unevenness of the precursor which occurs when the firing container is filled and heated in firing using the firing furnace is not generated. For this reason, a high quality positive electrode active material for lithium ion batteries is obtained.
  • this baking can be performed in steps by the function which raises the density of a positive electrode active material, the function which arranges crystallinity, etc. About each of these steps, it can also carry out using an integral rotary kiln, and can also carry out using several rotary kilns.
  • each arrow line indicates a rotary kiln.
  • the main kiln rotary kiln 31 is provided such that its powder input portion is positioned below the powder discharge portion of the pre-baking rotary kiln 10 and is inclined in substantially the same direction. It has been.
  • the rotary kiln 32 for main firing is provided such that the powder input portion is positioned below the powder discharge portion of the rotary kiln 10 for temporary firing and is inclined in a substantially reverse direction. It has been.
  • the main firing step first, heating by the heater is started while rotating the furnace core tubes of the rotary kilns 31 and 32. Heating may be performed in stages for each function such as a function of increasing the density of the positive electrode active material and a function of adjusting crystallinity. In this way, by performing the heating of the main firing step by step for each function, a higher quality positive electrode active material for a lithium ion battery can be produced.
  • the main baking step includes a first main baking step for forming a layered rock salt type crystal structure and increasing the tap density of the positive electrode active material, a second main baking step for baking the positive electrode active material, and cooling.
  • a first main baking step for forming a layered rock salt type crystal structure and increasing the tap density of the positive electrode active material
  • a second main baking step for baking the positive electrode active material
  • cooling When dividing into the 3rd main baking process for this, each range divided into 3 from the front-end part of the rotary kilns 31 and 32 to the rear-end part is heated by changing temperature with a separate heater.
  • the first main baking step is performed at 700 to 1200 ° C. for 0.5 to 12 hours
  • the second main baking step is performed at 500 to 900 ° C. for 0.5 to 24 hours
  • the third main baking step can be performed at 400 to 700 ° C. for 0.5 to 12 hours.
  • the inclination angle and rotation speed of the furnace core tubes of the rotary kilns 31 and 32 are appropriately set according to the mass of the pre-fired body and the firing time of the main firing. For example, when the mass of the pre-fired body is 20 to 110 g and the main firing time is 1.5 to 48 hours, the inclination angle of the core tube is 2 to 10 ° and the rotation speed is 3.6 to 9.6 radians.
  • the temporarily fired body discharged from the rotary kiln 10 is charged from the powder charging part to the front end part of the furnace core tube.
  • the introduced temporary fired body is transferred to the rear end of the core tube while being stirred and heated in the rotating core tube, and main firing is performed during this period.
  • the main fired powder is discharged from the powder discharge section, and the powder is pulverized to obtain a positive electrode active material powder. Since the obtained positive electrode active material uses a rotary kiln in the firing step, firing unevenness is suppressed.
  • the rotary kiln used for the main firing a rotary kiln having the same configuration as that shown in FIG. 1 can be used.
  • positioning form of the rotary kiln used by temporary baking and the rotary kiln used by this baking is not specifically limited, For example, it can be set as a form as shown in FIG. In FIG. 3, each arrow line indicates a rotary kiln.
  • the first rotary kiln 41 for main firing has its powder input portion positioned below the powder discharge portion of the rotary kiln 10 for preliminary firing and is inclined in substantially the same direction. It is provided as follows.
  • the second rotary kiln 42 of the main firing is provided such that its powder input portion is located below the powder discharge portion of the first rotary kiln 41 and is inclined in substantially the same direction.
  • the first rotary kiln 43 for main firing has its powder input part positioned below the powder discharge part of the rotary kiln 10 for temporary firing, and is inclined substantially in the reverse direction.
  • the second rotary kiln 44 of the main firing is provided such that the powder input portion is located below the powder discharge portion of the first rotary kiln 43 of the main firing and is inclined substantially in the reverse direction. Yes.
  • FIG. 3B the first rotary kiln 43 for main firing has its powder input part positioned below the powder discharge part of the rotary kiln 10 for temporary firing, and is inclined substantially in the reverse direction.
  • the first rotary kiln 45 of the main firing has its powder input portion positioned below the powder discharge portion of the pre-fired rotary kiln 10 and is inclined substantially in the reverse direction. It is provided as follows. Further, the second rotary kiln 46 for main firing is provided such that the powder input portion thereof is located below the powder discharge portion of the first rotary kiln 45 for main firing and is inclined substantially in the same direction. Yes. In the form shown in FIG. 3D, the first rotary kiln 47 for main firing has its powder input portion positioned below the powder discharge portion of the pre-fired rotary kiln 10 and inclined in substantially the same direction. It is provided as follows.
  • the second rotary kiln 48 of the main firing is provided such that the powder input portion thereof is located below the powder discharge portion of the first rotary kiln 47 of the main firing and is inclined substantially in the reverse direction.
  • the first rotary kiln 49 for the main firing is provided such that its powder input portion is located below the powder discharge portion of the rotary kiln 10 for preliminary firing.
  • the second rotary kiln 50 for main firing is provided such that its powder input portion is located below the powder discharge portion of the first rotary kiln 49 for main firing.
  • the pre-fired rotary kiln 10, the first fired first rotary kiln 49, and the second rotary kiln 50 are arranged so as to be inclined downward while forming a substantially triangular shape when viewed from above.
  • the main firing step first, heating by the heater is started while rotating the furnace core tubes of the first and second rotary kilns 41 to 50 in the main firing. Heating is performed in stages for each function such as a function of increasing the density of the positive electrode active material and a function of adjusting crystallinity. In this way, by performing the heating of the main firing step by step for each function, a higher quality positive electrode active material for a lithium ion battery can be produced.
  • the main baking step includes a first main baking step for forming a layered rock salt type crystal structure and increasing the tap density of the positive electrode active material, a second main baking step for baking the positive electrode active material, and cooling.
  • a third firing step is performed.
  • the first firing process is performed in the first rotary kilns 41, 43, 45, 47, and 49
  • the second and third firing processes are performed in the second rotary kilns 42, 44, 46, 48, and 50.
  • each range divided from the front end portion to the rear end portion of the first and / or second rotary kilns 41 to 50 in the main firing is heated by changing the temperature with separate heaters.
  • the first main baking step is performed at 700 to 1200 ° C. for 0.5 to 12 hours
  • the second main baking step is performed at 500 to 900 ° C. for 0.5 to 24 hours
  • the third main baking step can be performed at 400 to 700 ° C. for 0.5 to 12 hours.
  • the inclination angle and rotation speed of the furnace core tubes of the first and second rotary kilns 41 to 50 in the main firing are appropriately set according to the mass of the pre-fired body and the firing time in the main firing.
  • the mass of the pre-fired body is 20 to 110 g and the main firing time is 1.5 to 48 hours
  • the inclination angle of the core tube is 2 to 10 ° and the rotation speed is 3.6 to 9.6 radians. / Sec can be set.
  • the temporarily fired body discharged from the rotary kiln 10 is transferred from the powder charging parts of the first rotary kilns 41, 43, 45, 47 and 49 to the core tube. Insert into the front end.
  • the introduced pre-fired body is transferred to the rear end of the core tube while being stirred and heated in the rotating core tube, and is discharged from the powder discharge unit.
  • the fired bodies discharged from the powder discharge portions of the first rotary kilns 41, 43, 45, 47 and 49 are subsequently put into the powder input portions of the second rotary kilns 42, 44, 46, 48 and 50 below. Is done.
  • the fired bodies charged into the powder charging portions of the second rotary kilns 42, 44, 46, 48 and 50 are subsequently transferred to the rear end of the core tube while being stirred and heated in the rotating core tube, and then subjected to main firing. Is completed and discharged from the powder discharge section.
  • the main fired powder is discharged from the powder discharge section, and the powder is pulverized to obtain a positive electrode active material powder. Since the obtained positive electrode active material uses a rotary kiln in the firing step, firing unevenness is suppressed.
  • the rotary kiln used for the main firing a rotary kiln having the same configuration as that shown in FIG. 1 can be used.
  • positioning form of the rotary kiln used by temporary baking and the rotary kiln used by this baking is not specifically limited, For example, it can be set as the form shown in FIG. In FIG. 4, each arrow line indicates a rotary kiln.
  • the first rotary kiln 61 for main firing has its powder input portion positioned below the powder discharge portion of the rotary kiln 10 for preliminary firing and is inclined in substantially the same direction. It is provided as follows.
  • the second rotary kiln 62 of the main firing is provided such that its powder input portion is located below the powder discharge portion of the first rotary kiln 61 and is inclined in substantially the same direction.
  • the third rotary kiln 63 of the main firing is provided such that the powder input portion is positioned below the powder discharge portion of the second rotary kiln 62 and is inclined in substantially the same direction.
  • the first rotary kiln 64 for main firing has its powder input portion positioned below the powder discharge portion of the rotary kiln 10 for preliminary firing, and is inclined substantially in the reverse direction. It is provided as follows.
  • the second rotary kiln 65 of the main firing is provided such that the powder input portion is located below the powder discharge portion of the first rotary kiln 64 and is inclined substantially in the reverse direction.
  • the third rotary kiln 66 for main firing is provided such that the powder input portion thereof is positioned below the powder discharge portion of the second rotary kiln 65 and is inclined substantially in the reverse direction.
  • the first rotary kiln 67 for main firing is provided such that its powder input portion is located below the powder discharge portion of the rotary kiln 10 for preliminary firing.
  • the second rotary kiln 68 for main firing is provided such that its powder input portion is positioned below the powder discharge portion of the first rotary kiln 67 for main firing.
  • the third rotary kiln 69 for main firing is provided such that its powder input portion is positioned below the powder discharge portion of the second rotary kiln 68 for main firing.
  • the pre-fired rotary kiln 10 and the main-fired first to third rotary kilns 67, 68, 69 are disposed so as to be inclined downward while forming a substantially rectangular shape when viewed from above.
  • the main firing step first, heating by the heater is started while rotating the core tubes of the first to third rotary kilns 61 to 69 of the main firing. Heating is performed in stages for each function such as a function of increasing the density of the positive electrode active material and a function of adjusting crystallinity. In this way, by performing the heating of the main firing step by step for each function, a higher quality positive electrode active material for a lithium ion battery can be produced.
  • the main baking step includes a first main baking step for forming a layered rock salt type crystal structure and increasing the tap density of the positive electrode active material, a second main baking step for baking the positive electrode active material, and cooling.
  • the 1st baking process is performed in the 1st rotary kiln 61,64,67
  • the 2nd baking process is performed in the 2nd rotary kiln 62,65,68
  • the 3rd rotary kiln A third firing step is performed at 63, 66, and 69.
  • the first main baking step is performed at 700 to 1200 ° C. for 0.5 to 12 hours
  • the second main baking step is performed at 500 to 900 ° C. for 0.5 to 24 hours
  • the third main baking step can be performed at 400 to 700 ° C. for 0.5 to 12 hours.
  • the inclination angle and rotation speed of the furnace core tubes of the first to third rotary kilns 61 to 69 for main firing are appropriately set according to the mass of the pre-fired body and the firing time for main firing. For example, when the mass of the pre-fired body is 20 to 110 g and the main firing time is 1.5 to 48 hours, the inclination angle of the core tube is 2 to 10 ° and the rotation speed is 3.6 to 9.6 radians. / Sec can be set.
  • the temporarily fired body discharged from the rotary kiln 10 is charged from the powder charging portion of the first rotary kiln 61, 64, 67 to the front end portion of the furnace core tube. To do.
  • the introduced pre-fired body is transferred to the rear end of the core tube while being stirred and heated in the rotating core tube, and is discharged from the powder discharge unit.
  • the fired bodies discharged from the powder discharge portions of the first rotary kilns 61, 64, and 67 are subsequently put into the powder input portions of the second rotary kilns 62, 65, and 68 below.
  • the fired body charged in the powder charging section of the second rotary kiln 62, 65, 68 is transferred to the rear end of the core tube while being stirred and heated in the rotating core tube, and is then discharged from the powder discharge section. Discharged.
  • the fired bodies discharged from the powder discharge portions of the second rotary kilns 62, 65, and 68 are subsequently put into the powder input portions of the third rotary kilns 63, 66, and 69 below.
  • the fired body charged into the powder charging portion of the third rotary kiln 63, 66, 69 is subsequently transferred to the rear end of the core tube while being stirred and heated in the rotating core tube, and the main firing is completed. It is discharged from the powder discharge section.
  • the main fired powder is discharged from the powder discharge section, and the powder is pulverized to obtain a positive electrode active material powder. Since the obtained positive electrode active material uses a rotary kiln in the firing step, firing unevenness is suppressed.
  • the main baking step is performed with one rotary kiln
  • the preliminary baking and the main baking step are performed with one rotary kiln
  • the number of rotary kilns is small, which is advantageous in terms of work space.
  • the heating conditions are uniform in one rotary kiln, so firing can be performed with a simple apparatus configuration.
  • Examples 1 to 17 First, after suspending lithium carbonate of the input amount shown in Table 1 in 3.2 liters of pure water, 4.8 liter of metal salt solution was charged. Here, the nitrate hydrate of each metal was adjusted so that each metal might become the composition ratio of Table 1, and the total metal mole number might be set to 14 mol.
  • the suspended amount of lithium carbonate was such that the product (lithium ion secondary battery positive electrode material, ie, positive electrode active material) was Li x Ni 1- y My O 2 + ⁇ and x was a value shown in Table 1. Are respectively calculated by the following equations.
  • A is a numerical value to be multiplied in order to subtract the amount of lithium from the lithium compound other than lithium carbonate remaining in the raw material after filtration from the amount of suspension in addition to the amount necessary for the precipitation reaction. is there.
  • A is 0.9 when lithium salt reacts as a firing raw material such as nitrate or acetate, and “1” when lithium salt does not react as a firing raw material such as sulfate or chloride. 0.
  • fine particles of lithium-containing carbonate were precipitated in the solution, and this precipitate was filtered off using a filter press. Subsequently, the precipitate was dried to obtain a lithium-containing carbonate (a precursor for a lithium ion battery positive electrode material). At this time, the concentration of all metals in the precursor was 29 to 33% by mass.
  • a pre-baking apparatus as shown in FIG. 1 is prepared, and heating is performed while oxygen is circulated in the system from the gas supply unit.
  • the rotary kiln was rotated at a rotation speed of 9.6 radians / second.
  • the inclination angle of the rotary kiln was 10 °.
  • the precursor was charged into the furnace core tube from the powder charging portion while maintaining the temperature.
  • the input amount of the precursor was 110 g / min.
  • the precursor charged in the core tube is temporarily fired by stirring and transporting in the rotating core tube, and gas and moisture are released.
  • the precursor subjected to the preliminary firing is discharged out of the apparatus from the powder discharge unit.
  • the total metal concentration in the discharged precursor was 54-58% by weight.
  • each rotary kiln a rotary kiln manufactured by Takasago Industry Co., Ltd. (core tube: total length 2000 mm ⁇ inner diameter 250 mm) was used.
  • heating of the heater was started while circulating oxygen from the gas supply unit, and each rotary kiln was rotated at a rotation speed of 9.6 radians / second.
  • the inclination angle of each rotary kiln was 10 °.
  • the precursor was charged into the core tube from the powder charging part while maintaining the temperature.
  • the input amount of the precursor was 110 g / min.
  • the precursor charged in the core tube is temporarily fired by stirring and transporting in the rotating core tube, and gas and moisture are released.
  • the precursor subjected to the preliminary firing is discharged from the powder discharge portion to the powder input portion of the first rotary kiln for the main firing below.
  • the concentration of all metals in the discharged precursor was 31 to 63% by mass.
  • the first main baking process is performed at 700 to 1200 ° C. for 0.5 to 12 hours using the first rotary kiln, and then the second main baking process is performed at 500 to 900 ° C. for 0.5 to 12 hours. This was performed for 24 hours, and further, the third main baking step was performed at 400 to 700 ° C. for 0.5 to 12 hours using a third rotary kiln, whereby main baking was performed to obtain an oxide.
  • the obtained oxide was crushed to obtain a powder of a lithium ion secondary battery positive electrode material.
  • Example 18 Example 18 was carried out except that each metal of the raw material had the composition shown in Table 1, the metal salt was chloride, the lithium-containing carbonate was precipitated, washed with a saturated lithium carbonate solution, and filtered. The same treatment as in Examples 1 to 17 was performed.
  • Example 19 Example 19 was carried out except that each material of the raw material had the composition shown in Table 1, the metal salt was sulfate, the lithium-containing carbonate was precipitated, washed with a saturated lithium carbonate solution, and filtered. The same treatment as in Examples 1 to 17 was performed.
  • the metal content in each positive electrode material was measured with an inductively coupled plasma optical emission spectrometer (ICP-OES), and the composition ratio (molar ratio) of each metal was calculated.
  • the oxygen content was measured by the LECO method and ⁇ was calculated. As a result, it was confirmed that the results were as shown in Table 1.
  • the tap density was the density after 200 taps.
  • Each positive electrode material, conductive material, and binder are weighed in a ratio of 85: 8: 7, and the positive electrode material and the conductive material are mixed into a slurry in which the binder is dissolved in an organic solvent (N-methylpyrrolidone). And coated on an Al foil, dried and pressed to obtain a positive electrode.
  • a 2032 type coin cell for evaluation with Li as the counter electrode was prepared, and 1M-LiPF 6 dissolved in EC-DMC (1: 1) was used as the electrolyte, and the current density was 0.2C.
  • the discharge capacity was measured. Further, a rate characteristic was obtained by calculating a ratio of the discharge capacity when the current density was 2C to the battery capacity when the current density was 0.2C.
  • the capacity retention was measured by comparing the initial discharge capacity obtained with a 1 C discharge current at room temperature with the discharge capacity after 100 cycles. Test conditions and results are shown in Tables 1-3.
  • Examples 1 to 19 all showed excellent tap density and battery characteristics. In particular, Examples 1 to 17 exhibited better battery characteristics than Examples 18 and 19 because the metal salt used as a raw material was nitrate. In each of Comparative Examples 1 to 3, firing was performed only once in a stationary furnace, and it was difficult to fire the precursor without unevenness, so that the tap density and battery characteristics were inferior to those of Examples. .

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé de production d'un matériau d'électrode positive de haute qualité pour batteries lithium-ion. Le procédé de production du matériau actif d'électrode positive pour batteries lithium-ion comprend une étape dans laquelle : un carbonate contenant du lithium, étant un précurseur pour le matériau actif d'électrode positive pour batteries lithium-ion, est pré-calciné dans un four rotatif, ce qui augmente le pourcentage en masse de métaux totaux dans le carbonate contenant du lithium de 1 %-105 % par rapport à avant la pré-calcination ; et ledit carbonate contenant du lithium est alors calciné dans le four rotatif.
PCT/JP2011/072861 2011-03-29 2011-10-04 Procédé de production de matériau actif d'électrode positive pour batteries lithium-ion et matériau actif d'électrode positive pour batteries lithium-ion WO2012132072A1 (fr)

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WO2013111378A1 (fr) * 2012-01-26 2013-08-01 Jx日鉱日石金属株式会社 Matière active d'électrode positive ainsi qu'électrode positive pour batterie au lithium-ion, et batterie au lithium-ion
WO2013111379A1 (fr) * 2012-01-26 2013-08-01 Jx日鉱日石金属株式会社 Matière active d'électrode positive ainsi qu'électrode positive pour batterie au lithium-ion, et batterie au lithium-ion
JP2014523070A (ja) * 2011-06-24 2014-09-08 ビーエーエスエフ コーポレーション 層状酸化物カソード組成物の合成のための方法
US8993160B2 (en) 2009-12-18 2015-03-31 Jx Nippon Mining & Metals Corporation Positive electrode for lithium ion battery, method for producing said positive electrode, and lithium ion battery
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US9263732B2 (en) 2009-12-22 2016-02-16 Jx Nippon Mining & Metals Corporation Positive electrode active material for lithium-ion battery, positive electrode for a lithium-ion battery, lithium-ion battery using same, and precursor to a positive electrode active material for a lithium-ion battery
US9327996B2 (en) 2011-01-21 2016-05-03 Jx Nippon Mining & Metals Corporation Method for producing positive electrode active material for lithium ion battery and positive electrode active material for lithium ion battery
WO2017221554A1 (fr) * 2016-06-23 2017-12-28 日立金属株式会社 Procédé de production de matériau actif d'électrode positive pour accumulateurs lithium-ion, matériau actif d'électrode positive pour accumulateurs lithium-ion, et accumulateur lithium-ion
US9911518B2 (en) 2012-09-28 2018-03-06 Jx Nippon Mining & Metals Corporation Cathode active material for lithium-ion battery, cathode for lithium-ion battery and lithium-ion battery
WO2018070517A1 (fr) * 2016-10-13 2018-04-19 住友化学株式会社 Procédé de production de matériau actif d'électrode positive de batterie secondaire au lithium
US10122012B2 (en) 2010-12-03 2018-11-06 Jx Nippon Mining & Metals Corporation Positive electrode active material for lithium-ion battery, a positive electrode for lithium-ion battery, and lithium-ion battery
JP2020144976A (ja) * 2019-03-04 2020-09-10 川崎重工業株式会社 廃リチウムイオン電池の焙焼装置

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US9263732B2 (en) 2009-12-22 2016-02-16 Jx Nippon Mining & Metals Corporation Positive electrode active material for lithium-ion battery, positive electrode for a lithium-ion battery, lithium-ion battery using same, and precursor to a positive electrode active material for a lithium-ion battery
US9231249B2 (en) 2010-02-05 2016-01-05 Jx Nippon Mining & Metals Corporation Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery
US9118076B2 (en) 2010-02-05 2015-08-25 Jx Nippon Mining & Metals Corporation Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery and lithium ion battery
US9216913B2 (en) 2010-03-04 2015-12-22 Jx Nippon Mining & Metals Corporation Positive electrode active substance for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery
US9240594B2 (en) 2010-03-04 2016-01-19 Jx Nippon Mining & Metals Corporation Positive electrode active substance for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery
US9090481B2 (en) 2010-03-04 2015-07-28 Jx Nippon Mining & Metals Corporation Positive electrode active material for lithium-ion battery, positive electrode for lithium-ion battery, and lithium-ion battery
US9225020B2 (en) 2010-03-04 2015-12-29 Jx Nippon Mining & Metals Corporation Positive electrode active substance for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery
US10122012B2 (en) 2010-12-03 2018-11-06 Jx Nippon Mining & Metals Corporation Positive electrode active material for lithium-ion battery, a positive electrode for lithium-ion battery, and lithium-ion battery
US9327996B2 (en) 2011-01-21 2016-05-03 Jx Nippon Mining & Metals Corporation Method for producing positive electrode active material for lithium ion battery and positive electrode active material for lithium ion battery
US9221693B2 (en) 2011-03-29 2015-12-29 Jx Nippon Mining & Metals Corporation Method for producing positive electrode active material for lithium ion batteries and positive electrode active material for lithium ion batteries
US9214676B2 (en) 2011-03-31 2015-12-15 Jx Nippon Mining & Metals Corporation Positive electrode active material for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery
JP2018150231A (ja) * 2011-06-24 2018-09-27 ビーエーエスエフ コーポレーション 層状酸化物カソード組成物の合成のための方法
JP2014523070A (ja) * 2011-06-24 2014-09-08 ビーエーエスエフ コーポレーション 層状酸化物カソード組成物の合成のための方法
WO2013073633A1 (fr) * 2011-11-16 2013-05-23 Ａｇｃセイミケミカル株式会社 Procédé pour produire un oxyde composite contenant du lithium
US9224515B2 (en) 2012-01-26 2015-12-29 Jx Nippon Mining & Metals Coporation Cathode active material for lithium ion battery, cathode for lithium ion battery, and lithium ion battery
US9224514B2 (en) 2012-01-26 2015-12-29 Jx Nippon Mining & Metals Corporation Cathode active material for lithium ion battery, cathode for lithium ion battery, and lithium ion battery
WO2013111379A1 (fr) * 2012-01-26 2013-08-01 Jx日鉱日石金属株式会社 Matière active d'électrode positive ainsi qu'électrode positive pour batterie au lithium-ion, et batterie au lithium-ion
WO2013111378A1 (fr) * 2012-01-26 2013-08-01 Jx日鉱日石金属株式会社 Matière active d'électrode positive ainsi qu'électrode positive pour batterie au lithium-ion, et batterie au lithium-ion
US9911518B2 (en) 2012-09-28 2018-03-06 Jx Nippon Mining & Metals Corporation Cathode active material for lithium-ion battery, cathode for lithium-ion battery and lithium-ion battery
JP2021022576A (ja) * 2016-06-23 2021-02-18 日立金属株式会社 リチウムイオン二次電池用正極活物質及びリチウムイオン二次電池
JPWO2017221554A1 (ja) * 2016-06-23 2019-02-21 日立金属株式会社 リチウムイオン二次電池用正極活物質の製造方法及びリチウムイオン二次電池用正極活物質、並びにリチウムイオン二次電池
WO2017221554A1 (fr) * 2016-06-23 2017-12-28 日立金属株式会社 Procédé de production de matériau actif d'électrode positive pour accumulateurs lithium-ion, matériau actif d'électrode positive pour accumulateurs lithium-ion, et accumulateur lithium-ion
JP7160075B2 (ja) 2016-06-23 2022-10-25 日立金属株式会社 リチウムイオン二次電池用正極活物質及びリチウムイオン二次電池
US11764356B2 (en) 2016-06-23 2023-09-19 Proterial, Ltd. Method for producing positive electrode active material for lithium ion secondary batteries
WO2018070517A1 (fr) * 2016-10-13 2018-04-19 住友化学株式会社 Procédé de production de matériau actif d'électrode positive de batterie secondaire au lithium
JP2020144976A (ja) * 2019-03-04 2020-09-10 川崎重工業株式会社 廃リチウムイオン電池の焙焼装置
EP3936631A4 (fr) * 2019-03-04 2022-12-07 Kawasaki Jukogyo Kabushiki Kaisha Appareil pour le grillage de déchets de batterie au lithium-ion
JP7195181B2 (ja) 2019-03-04 2022-12-23 川崎重工業株式会社 廃リチウムイオン電池の焙焼装置

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