[go: up one dir, main page]

WO2013042986A2 - Appareil utilisant un équipement de réaction à tourbillons de taylor-couette pour préparer un précurseur de matière active de cathode pour batterie secondaire au lithium - Google Patents

Appareil utilisant un équipement de réaction à tourbillons de taylor-couette pour préparer un précurseur de matière active de cathode pour batterie secondaire au lithium Download PDF

Info

Publication number
WO2013042986A2
WO2013042986A2 PCT/KR2012/007594 KR2012007594W WO2013042986A2 WO 2013042986 A2 WO2013042986 A2 WO 2013042986A2 KR 2012007594 W KR2012007594 W KR 2012007594W WO 2013042986 A2 WO2013042986 A2 WO 2013042986A2
Authority
WO
WIPO (PCT)
Prior art keywords
active material
cathode active
couette
material precursor
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2012/007594
Other languages
English (en)
Other versions
WO2013042986A9 (fr
WO2013042986A3 (fr
Inventor
Hyung Mo Kim
Byoung Soo Kim
Young-Ho RHO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SKC Co Ltd
Original Assignee
SKC Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SKC Co Ltd filed Critical SKC Co Ltd
Publication of WO2013042986A2 publication Critical patent/WO2013042986A2/fr
Publication of WO2013042986A9 publication Critical patent/WO2013042986A9/fr
Publication of WO2013042986A3 publication Critical patent/WO2013042986A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 an apparatus for preparing a cathode active material precursor for a lithium secondary battery, and, more particularly, to an apparatus for preparing a cathode active material precursor for a lithium secondary battery using Couette-Taylor vortexes.
  • lithium secondary batteries are commonly and widely used because they have high energy density, a high operating voltage, a long lifecycle and a low self-discharge rate.
  • Litlii n-containing cobalt oxide (LiCoO 2 ) is generally used as a cathode active material of a lithium secondary battery. Additionally, the use of Uthium-containing manganese oxide such as LiMnO 2 having a layered ciystal structure, LiMn 2 O having a spinel crystal structure or the like, Uthium-containing nickel oxide (LiNiO 2 ) or lithium- containing three-component oxide (LiNi x Mn y CO ( i -x-y) 0 2 ) as the cathode active material is also being considered. Generally, a cathode active material of a lithium secondary battery is prepared by a solid-state reaction at a high temperature of 700 ° C or more.
  • the method of preparing a cathode active material using a solid-state reaction is problematic in that, since raw materials are physically mixed and pulverized, the obtained mixture is nonuniform, so that the mixture must be further mixed and pulverized several times, with the result that the time required to prepare the cathode active material increases, thereby increasing the manufacturing cost thereof.
  • the co-precipitation process is a process of preparing oxide powder by precipitating chloride, nitride or sulfide into hydroxide using a co-precipitation solution and then calcining the hydroxide precipitate.
  • the pH, temperature and stirring condition of the co-precipitation solution must be controlled.
  • an aspect of the present invention provides an apparatus for preparing a cathode active material precursor for a lithium secondary battery, comprising:
  • a Couette-Taylor reactor where a reaction mixture comprising a solution of mixed metal salts and an alkali solution is admixed to be coprecipitated to form a slurry including the cathode active material precursor;
  • a particle separation unit comprising a separation tank connected to the Couette-Taylor reactor through a slurry supply line and a pulverizer for pulverizing the slurry including the cathode active material precursor, wherein the cathode active material precursor is separated and recovered;
  • a precipitation unit connected to the Couette-Taylor reactor through a waste solution discharge line, wherein a waste solution discharged from the Couette-Taylor reactor is cooled such that an alkali salt is precipitated and removed.
  • the cathode active material precursor is prepared using a Couette-Taylor reactor, the cathode active material can be prepared in a short period of time to increase productivity, the particle size distribution of the prepared cathode active material can be improved, and the size of the reactor can be reduced so that the space for providing equipment is used more efficiently.
  • the apparatus and method for manufacturing a cathode active material precursor for a lithium secondary battery according to the present invention have many advantages, such as the reduction of waste water containing the alkali salts (side products) occurring during co-precipitation, the reduction of waste water over the entire process, the reduction of impurities in products, the improvement of production yield, and the like.
  • FIG. 1 is a schematic view showing an apparatus for preparing a cathode active material precursor for a lithium secondary battery according to the present invention
  • FIG. 2 is a schematic view showing the Couette-Taylor reactor used in the apparatus for preparing a cathode active material precursor for a lithium secondary battery according to the present invention
  • FIG. 3 is scanning electron microscope (SEM) photographs of the cathode active material precursors according to the present invention.
  • FIG. 4 is a graph of the results of X-ray diffraction analysis of the cathode active material precursors according to the present invention.
  • FIG. 5 is a graph of the charge-discharge capacity of the hthium secondary battery which was prepared by using the cathode active material precursors according to Example 1;
  • FIG. 6 is a graph of the charge-discharge capacity of the lithium secondary battery which was prepared by using the cathode active material precursors according to Example 2;
  • FIG. 7 is a graph of the charge-discharge capacity of the lithium secondary battery which was prepared by using the cathode active material precursors according to Example 3;
  • FIG. 8 is a graph of the charge-discharge capacity of the lithium secondary battery which was prepared by using the cathode active material precursors according to Example 4;
  • FIG. 9 is a graph of the charge-discharge capacity of the lithium secondary battery which was prepared by using the cathode active material precursors according to Example 5;
  • FIG. 10 is a graph of the charge-discharge capacity of the lithium secondary battery which was prepared by using the cathode active material precursors according to Comparative Example 1.
  • driving unit 220 slurry discharge line (or slurry supply line)
  • chiller 340 second heat exchang
  • An apparatus for preparing a cathode active material precursor for a lithium secondary battery of the present invention comprising:
  • a Couette-Taylor reactor where a reaction mixture comprising a solution of mixed metal salts and an alkali solution is admixed to be coprecipitated to form a slurry including the cathode active material precursor;
  • a particle separation unit comprising a separation tank connected to the Couette-Taylor reactor through a slurry supply line and a pulverizer for pulverizing the slurry including the cathode active material precursor, wherein the cathode active material precursor is separated and recovered;
  • a precipitation unit connected to the Couette-Taylor reactor through a waste solution discharge line, wherein a waste solution discharged from the Couette-Taylor reactor is cooled such that an alkali salt is precipitated and removed.
  • the cathode active material precursor may be nickel-cobalt-manganese hydroxide represented by Formula 1 below: [Formula 1]
  • the cathode active material precursor may be prepared by precipitating the nickel-cobalt-manganese hydroxide precursor particles.
  • the mixed metal salt solution may be a mixture of nickel sulfate, cobalt sulfate and manganese sulfate.
  • the concentration of the mixed metal salt solution may be 1.0 ⁇ 4.0 M, preferably, 1.5 ⁇ 3.0 M. When the concentration thereof is less than 1.0 M, the yield of precursor particles is reduced.
  • the prepared cathode active material precursor is mixed with a suitable amount of a lithium raw material, and then the mixture is calcined at 800 ⁇ 1300°C for 15 - 24 hours to prepare a cathode active material including lithium-transition metal composite oxide.
  • the cathode active material particles are stably grown, and the adhesivity between crystals is improved, thus obtaining cathode active material particles having uniform particle size.
  • the lithium-transition metal composite oxide prepared using the precursor containing Ni, Co and Mn exhibits excellent lifecycle characteristics when it is charged in a voltage of 4.3 V. However, when it is charged and discharged in a high voltage range of 4.5 V or more, its lifecycle characteristics remarkably deteriorate.
  • the Uthium-transition metal composite oxide is doped with a metal selected from the group consisting of Fe, Ga, Ge, Al, Ti, V, Cu, Zn, Si, P, Nb, Ta, Zr, Zn, Sn, Sb, Pt, hi, Ag, Au, Bi, Pd, W and Nb, thus remarkably improving the lifecycle characteristics thereof in a high voltage range.
  • the doping of the lithium-transition metal composite oxide using the metal may be performed by additionally introducing a metal salt solution including the metal selected from the group consisting of Fe, Ga, Ge, Al, Ti, V, Cu, Zn, Si, P, Nb, Ta, Zr, Zn, Sn, Sb, Pt, In, Ag, Au, Bi, Pd, W and Nb in the step of introducing the mixed metal salt solution into a reactor.
  • a metal salt solution including the metal selected from the group consisting of Fe, Ga, Ge, Al, Ti, V, Cu, Zn, Si, P, Nb, Ta, Zr, Zn, Sn, Sb, Pt, In, Ag, Au, Bi, Pd, W and Nb in the step of introducing the mixed metal salt solution into a reactor.
  • the alkali solution may be a sodium hydroxide solution or an aqueous ammonia solution, or may include both a sodium hydroxide solution and an aqueous ammonia solution.
  • the sodium hydroxide solution or the aqueous ammonia solution can be used as a coprecipitating agent, and serves to appropriately control the pH of the metal salt solution introduced into the reactor.
  • the pH of the metal salt solution introduced into the reactor may be 10 ⁇ 13, preferably, 11 ⁇ 12.
  • the pH of the metal salt solution is less than 10, a part of the precursor particle precipitate is redissolved, and thus the desired composition ratio of the prepared precursor particles cannot be obtained. Further, when the pH thereof is more than 13, spherical precursor particles cannot be obtained, thus deteriorating the uniformity of the precursor particles.
  • reaction mixture comprising the mixed metal salt solution and the alkali solution is introduced, stirred and coprecipitated to obtain a reaction product (a slurry) including precursor particles.
  • the stirring speed of the Couette-Taylor reactor may be 500 ⁇ 1000 rpm.
  • the method of preparing a cathode active material precursor for a lithium secondary battery according to the present invention comprises the steps of:
  • reaction mixture comprising a solution of mixed metal salts and an alkali solution in a Couette-Taylor reactor, wherein the reaction mixture is coprecipitated to form a slurry including the cathode active material precursor;
  • pulverizing the slurry including the cathode active material precursor in a particle separation unit comprising a separation tank connected to the Couette-Taylor reactor through a slurry supply line and a pulverizer, wherein the cathode active material precursor is separated and recovered;
  • FIG. 1 is a schematic view showing an apparatus for preparing a cathode active material precursor for a lithium secondary battery according to an embodiment of the present invention.
  • the apparatus for preparing a cathode active material precursor for a lithium secondary battery comprises: a Couette-Taylor reactor 100 where a reaction mixture comprising a solution of mixed metal salts and an alkali solution is admixed to be coprecipitated to form a slurry including the cathode active material precursor; a particle separation unit 200 for pulverizing agglomerated particles in the slurry obtained from the Couette-Taylor reactor 100 to separate the desired cathode active material precursor; and a precipitation unit 300 for continuously removing an alkali salt, which is a byproduct obtained during a coprecipitation reaction, to miriimize the generation of alkali salt-containing waste water.
  • the apparatus for preparing a cathode active material precursor for a hthium secondary battery further comprises the particle separation unit 200 for continuously and efficiently separating precursor particles and the precipitation unit 300 for removing an alkali salt, which is a byproduct, in addition to the Couette-Taylor reactor 100, uniform precursor particles can be produced with high yield and the occurrence of waste water can be minimized.
  • FIG. 2 is a schematic view showing the Couette-Taylor reactor 100 used in the apparatus for preparing a cathode active material precursor for a lithium secondary battery according to the present invention.
  • the Couette-Taylor reactor 100 includes: an outer cylinder 110 which is provided at one end thereof with a first outlet 111 and a second outlet 112; and a rotary cylinder 120 which is provided in the outer cylinder 110 with a predetermined interval therebetween and is rotated by a drive motor 130, one end of which is located at the first inlet 111 and second inlet 112 of the outer cylinder 110 and is blocked by a closing wall 112, and the other end of which defines a passage between the outer cylinder 110 and the rotary cylinder 120.
  • the one end of the rotary cylinder 120 is provided with an inlet 140 that passes the outer cylinder 110 and is located near the closing wall 121 of the outer cylinder 110.
  • the outer cylinder 110 is provided with auxiliary inlets 141 through which reactants are additionally supplied. Both ends of the outer cylinder 110 are provided with pH sensors 180 such that the pH in the Couette-Taylor reactor 100 is measured and controlled.
  • the outer cylinder 110 is provided with an outer cover 160, and a coolant flows between the outer cylinder 110 and the outer cover 160.
  • the coolant is introduced through a coolant inlet 190, and serves to maintain the temperature of the outer cylinder 110.
  • the introduced coolant is discharged through a coolant outlet 191, and is circulated by a coolant pump (not shown).
  • the space between a shaft 131 of the drive motor 130 and the outer cylinder 110 may be sealed such that reactants do not leak from the reactor, and may be provided with a bearing 150 such that the shaft 131 of the drive motor 130 easily rotates.
  • the reactants introduced through the inlet 140 flow between the outer cylinder 110 and the rotary cylinder 120 along the longest distance in an axial direction.
  • the reaction mixture flows between the outer cylinder 110 and the rotary cylinder 120, and, when the rotary cylinder 120 is rotated by the operation of the drive motor 130, eddy flux, that is, Taylor vortexes are formed between the outer cylinder 110 and the rotary cylinder 120, and move along in the axial direction. Subsequently, the reaction mixture flows between the outer cylinder 110 and the rotary cylinder 120, and moves along an axial direction while forming Taylor vortexes. The reaction product is discharged through the first outlet 111 of the external cylinder 110.
  • a reaction mixture supply line 170 for introducing a reaction mixture of a mixed metal salt solution and an alkali solution, a fine particle circulation line 230 connected to the particle separation unit 200, a slurry discharge line 220 connected to the particle separation unit 200, and a waste solution discharge line 113 connected to the precipitation unit 300 are respectively connected to the Couette- Taylor reactor 100.
  • the reaction mixture of a mixed metal salt solution and an alkali solution is continuously introduced into the Couette-Taylor reactor 100, and then stirred and coprecipitated to obtain a reaction product.
  • the reaction product the amount of which is equivalent to that of the introduced reaction mixture, is discharged to the particle separation unit 200 in the form of a slurry through the slurry discharge line 220 connected to the first outlet 111 of the Couette-Taylor reactor 100.
  • the particle separation unit 200 includes: a separation tank 210 for receiving the slurry-type reaction product from the Couette-Taylor reactor 100 and then loosening and dispersing the agglomerated particles in the slurry to separate the cathode active material precursor particles therefrom using gravity; a slurry supply line 220 which is connected between the Couette-Taylor reactor 100 and the slurry inlet of the separation tank 210 and through which the slurry-type reaction product is supplied from the Couette-Taylor reactor 100; a pulverizer for pulverizing the slurry-type reaction product transferred into the separation tank 210; and a fine particle circulation line 230 which is connected between the Couette-Taylor reactor 100 and the upper end of the separation tank 210 to recycle the solution including remaining fine particles separated from the precursor particles in the separation tank 210 into the Couette-Taylor reactor 100.
  • the agglomerated particles in the slurry supplied from the Couette-Taylor reactor 100 are loosened and dispersed by the pulverizer, and then relatively heavy particles and relatively light particles become separated by gravity. That is, precursor particles which are relatively heavy move to the bottom of the separation tank 210, and are then stored in a storage tank 240 through a passage connected to the bottom of the separation tank 210. Further, the solution including relatively light fine particles separated from the precursor particles is recycled to the Couette-Taylor reactor 100 through a fine particle circulation line 230 connected to the top of the separation tank 210.
  • the ultrasonic disperser may include: an ultrasonic generator 211 which is provided in the separation tank 210 and which is provided with an ultrasonic vibrator to transfer ultrasonic vibrations into the separation tank 210 to disperse the agglomerated particles in the slurry; and a driving unit 212 for driving the ultrasonic vibrator.
  • the second outlet 112 of the Couette-Taylor reactor 100 is connected to a waste solution discharge line 113 such that the waste solution produced by a coprecipitation reaction is discharged.
  • the Couette-Taylor reactor 100 may be configured such that the waste solution is discharged together with the slurry solution through the first outlet U 1.
  • the waste solution produced by a coprecipitation reaction in the Couette- Taylor reactor 100 is discharged to the precipitation unit 300 through the waste solution discharge line 113.
  • the precipitation unit 300 serves to precipitate and remove an alkali salt from the waste solution, and includes: a cooling means; and a precipitation tank 320 in which an alkali salt is precipitated from the cooled waste solution.
  • the precipitated alkali salt may be an alkali metal salt which is generated in the Couette-Taylor reactor, but not coprecipitated.
  • exemplary alkali salts include metal hydroxides such as nickel hydroxide, cobalt hydroxide, manganese hydroxide and a mixture thereof.
  • the cooling means is configured such that the waste solution discharged from the Couette-Taylor reactor 100 through the waste solution discharge line 113 passes through the cooling means and such that a coolant also passes through the cooling means.
  • the cooling means includes: a first heat exchanger 310 for cooling the waste solution using heat exchange between the waste solution and the coolant and then discharging the cooled waste solution to the precipitation tank 320 through the waste solution discharge line 113; and a chiller 330 for supplying the coolant to the first heat exchanger 320.
  • the waste solution discharged from the Couette-Taylor reactor 100 to the precipitation tank 320 through the waste solution discharge line 113 passes through the first heat exchanger 310 to be cooled, and thus the alkali salt is precipitated on the bottom of the precipitation tank 320 to be removed from the waste solution.
  • waste water obtained by removing the alkali salt from the waste solution in the precipitation tank 320 is discharged through a waste water discharge line 321.
  • the waste water from which the alkali salt is removed passes through an additionally-provided second exchanger 340 to be reheated, and then the reheated waste water is recycled to the Couette-Taylor reactor 100.
  • NiSO 4 -6H 2 O, CoSO 4 -7H 2 O and MnSO 4 H 2 O were dissolved in distilled water at a molar ratio of 1 : 1 : 1 to prepare a 2 M metal salt solution.
  • the prepared metal salt solution was introduced into a Couette-Taylor reactor at a flow rate of 120 mL/hr through a metal salt solution supply line.
  • a 6M NI ⁇ OH solution was prepared using a 25% N3 ⁇ 4, and then the prepared 6M N3 ⁇ 4OH solution was introduced into the Couette-Taylor reactor at a flow rate of 10 mL/hr through an aqueous ammonia solution supply line.
  • a 4M NaOH solution was automatically introduced into the Couette-Taylor reactor while maintaining the 4M NaOH solution at a pH of 11 using a pH meter and a controller.
  • the temperature of the Couette-Taylor reactor was set at 40 ° C, and the mixed solution was stirred at a rotation speed of 700 rpm to prepare a cathode active material precursor.
  • Example 2
  • a cathode active material precursor was prepared in the same manner as in Example 1, except that NiSO 4 -6H 2 O, CoSO 4 -7H 2 O and MnSO 4 -H 2 O were mixed at a molar ratio of 5:2:3.
  • a cathode active material precursor was prepared in the same manner as in Exainple 1, except that the prepared metal salt solution was introduced at a flow rate of 192 mL/hr, the N3 ⁇ 4OH solution was introduced at a flow rate of 16 mL hr, and the mixed solution was stirred at a rotation speed of 900 rpm.
  • Example 4
  • a cathode active material precursor was prepared in the same manner as in Example 1, except that the prepared metal salt solution was introduced at a flow rate of 80 mL/hr, the ⁇ 3 ⁇ 4 ⁇ solution was introduced at a flow rate of 6.67 mL/hr, and the mixed solution was stirred at a rotation speed of 600 rpm.
  • a cathode active material precursor was prepared in the same manner as in Example 1, except that NiSO 4 -6H 2 O, CoSO 4 -7H 2 O and MnSO 4 -H 2 O were mixed at a molar ratio of 6:2:2, and the mixed solution was stirred at a rotation speed of 600 rpm.
  • NiSO 4 -6H 2 O, CoSO 4 -7H 2 O and MnSO 4 H 2 O were dissolved in distilled water at a molar ratio of 1 : 1 : 1 to prepare a 2 M metal salt solution.
  • the prepared metal salt solution was introduced into a Couette-Taylor reactor at a flow rate of 152 mL/hr. Further, a 6M N3 ⁇ 4OH solution was prepared using a 25% NH 3 , and then the prepared 6M N]3 ⁇ 4OH solution was introduced into the Couette-Taylor reactor at a flow rate of 30 mL/hr through an aqueous ammonia solution supply line.
  • a 4M NaOH solution was automatically introduced into the Couette-Taylor reactor while mamtaining the 4M NaOH solution at a pH of 11 using a pH meter and a controller.
  • the temperature of the Couette-Taylor reactor was set at 40 ° C, and the mixed solution was stirred at a rotation speed of 800 rpm for 12 firs to prepare a cathode active material precursor.
  • the reaction time the time it takes to allow the average particle size (D50) of the prepared cathode active material precursor to reach 10 m, the sphericity and the tap density in the preparation of the cathode active materials of Examples 1 to 5 and Comparative Example 1 are given in Table 1 below.
  • FIG. 3 shows the scanning electron microscope (SEM) photographs of the cathode active material precursors of Examples 1 to 5 and Comparative Example 1. Referring to FIG. 3, it can be ascertained that the particle size distribution of each of the cathode active material precursors of Examples 1 to 5 is uniform, and that the particle size distribution of the cathode active material precursor of Comparative Example 1 is nonuniform.
  • SEM scanning electron microscope
  • the cathode active material prepared in Preparation Example 1 , a conducting material and a binder were mixed at a mixing ratio of 95: 3: 2 to obtain a slurry, and the slurry was applied onto aluminum (AT) foil using a doctor blade method to obtain an electrode.
  • Lithium metal was used as an anode, and an electrolyte in which 1M LiPF 6 is included in a mixture of EC and EMC (1:2) was used as an electrolyte, and a separation membrane was disposed between the anode and the cathode to manufacture a coin half cell.
  • Example 2 was measured by discharging a current of 0.1 C and 2 C until the discharge voltage thereof reached 3.0 V.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention porte sur un appareil pour préparer un précurseur de matière active de cathode pour batterie secondaire au lithium, comprenant : un réacteur de Taylor-Couette où un mélange réactif comprenant une solution de sels métalliques mélangés et une solution alcaline est mélangé pour être co-précipité pour former une bouillie comprenant le précurseur de matière active de cathode ; une unité de séparation de particules comprenant un réservoir de séparation relié au réacteur de Taylor-Couette à travers une ligne d'alimentation en bouillie et un pulvérisateur pour pulvériser la bouillie comprenant le précurseur de matière active de cathode, le précurseur de matière active de cathode étant séparé et récupéré ; et une unité de précipitation reliée au réacteur de Taylor-Couette à travers une ligne de décharge de solution de déchets, une solution de déchets déchargée du réacteur de Taylor-Couette étant refroidie de telle sorte qu'un sel alcalin est précipité et retiré.
PCT/KR2012/007594 2011-09-21 2012-09-21 Appareil utilisant un équipement de réaction à tourbillons de taylor-couette pour préparer un précurseur de matière active de cathode pour batterie secondaire au lithium Ceased WO2013042986A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020110095257A KR101275845B1 (ko) 2011-09-21 2011-09-21 쿠에트 테일러 와류를 이용한 리튬 이차전지용 양극 활물질 전구체 제조 장치
KR10-2011-0095257 2011-09-21

Publications (3)

Publication Number Publication Date
WO2013042986A2 true WO2013042986A2 (fr) 2013-03-28
WO2013042986A9 WO2013042986A9 (fr) 2013-05-16
WO2013042986A3 WO2013042986A3 (fr) 2013-07-04

Family

ID=47915030

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2012/007594 Ceased WO2013042986A2 (fr) 2011-09-21 2012-09-21 Appareil utilisant un équipement de réaction à tourbillons de taylor-couette pour préparer un précurseur de matière active de cathode pour batterie secondaire au lithium

Country Status (2)

Country Link
KR (1) KR101275845B1 (fr)
WO (1) WO2013042986A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2810706A4 (fr) * 2012-02-01 2015-10-07 Lg Chemical Ltd Réacteur de préparation d'un précurseur d'un oxyde de métal de transition composite au lithium, et procédé de préparation du précurseur
CN105283985A (zh) * 2013-06-14 2016-01-27 莱米纳有限公司 核-壳粒子的制造装置及利用该装置的核-壳粒子制造方法
US20160104879A1 (en) * 2014-10-14 2016-04-14 University-Industry Cooperation Group Of Kyung Hee University Method for preparing core-shell structured particle by using continuous couette-taylor crystallizer
CN106029575A (zh) * 2014-02-13 2016-10-12 宜安德株式会社 利用库埃特泰勒反应器的镍钴锰复合前驱体的连续式制备方法
CN111111593A (zh) * 2020-01-06 2020-05-08 湖南中伟新能源科技有限公司 一种三元前驱体材料的制备设备以及制备方法

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160099876A (ko) 2015-02-13 2016-08-23 주식회사 이엔드디 고밀도 니켈―코발트―망간 복합 전구체의 제조 방법
KR101719575B1 (ko) 2015-06-10 2017-03-24 한국기계연구원 나노 입자를 위한 제조장치 및 양자점 제조방법
KR101775609B1 (ko) 2015-06-24 2017-09-07 가천대학교 산학협력단 전단 유동을 이용한 고품질 그래핀 제조 방법 및 장치
WO2017150756A1 (fr) * 2016-03-03 2017-09-08 주식회사 이엔드디 Procédé de revêtement d'un hétéroatome sur un précurseur de composite de nickel-cobalt-manganèse à l'aide d'un réacteur de couette-taylor
KR102533157B1 (ko) 2016-07-27 2023-05-17 삼성에스디아이 주식회사 리튬 이차전지의 양극 활물질의 제조방법
WO2018155746A1 (fr) 2017-02-27 2018-08-30 주식회사 이엔드디 Procédé de production de précurseur de complexe de nickel-cobalt-manganèse à surface spécifique élevée
WO2018155745A1 (fr) 2017-02-27 2018-08-30 주식회사 이엔드디 Procédé d'application d'une couche hétéroatomique sur un précurseur composite nickel-cobalt-manganèse
CN108321426B (zh) * 2018-01-22 2024-05-14 北京圣比和科技有限公司 一种单粒子形貌的镍锰钴酸锂材料的制备方法及设备
KR20200034273A (ko) 2018-09-21 2020-03-31 주식회사 이엔드디 니켈―코발트―망간 복합 전구체의 제조 방법
KR102182289B1 (ko) 2018-12-18 2020-11-24 주식회사 이엔드디 고밀도 니켈―코발트―망간 복합전구체의 제조 방법
KR102212713B1 (ko) * 2019-08-13 2021-02-04 경희대학교 산학협력단 양극 활물질의 전구체를 제조하는 방법 및 장치
KR102465642B1 (ko) * 2020-12-04 2022-11-14 한국생산기술연구원 쿠에트-테일러 반응기를 이용한 고용량 양극소재의 제조방법 및 그를 포함하는 리튬이차전지의 제조방법
KR102602517B1 (ko) * 2021-08-19 2023-11-15 한국생산기술연구원 일체형 양극복합소재를 포함하는 전고체 리튬이차전지 및 그의 제조방법
WO2023229354A1 (fr) * 2022-05-24 2023-11-30 주식회사 엘지화학 Dispositif de préparation de précurseur et procédé de préparation de précurseur

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996002563A1 (fr) * 1994-07-13 1996-02-01 Cornell Research Foundation, Inc. Proteine de l'antigene nucleaire 1 du virus epstein barr, son expression et sa recuperation
US6306542B1 (en) * 1998-05-22 2001-10-23 Kabushiki Kaisha Toyota Chuo Kenkyusho Lithium manganese composite oxide for lithium secondary battery cathode active material, manufacturing method thereof, and lithium secondary battery using the composite oxide as cathode active material
KR100733969B1 (ko) * 2006-07-20 2007-07-02 케이엔디티앤아이 주식회사 연속식 용석 결정화 분리장치
KR100721868B1 (ko) 2006-07-20 2007-05-28 케이엔디티앤아이 주식회사 쿠에트-테일러 반응기를 이용한 구아닐산나트륨 결정화공정 시스템
KR100887186B1 (ko) * 2007-09-18 2009-03-10 한국화학연구원 리튬 이차 전지용 양극 활물질 전구체 제조 장치 및 방법

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2810706A4 (fr) * 2012-02-01 2015-10-07 Lg Chemical Ltd Réacteur de préparation d'un précurseur d'un oxyde de métal de transition composite au lithium, et procédé de préparation du précurseur
US9899675B2 (en) 2012-02-01 2018-02-20 Lg Chem, Ltd. Method for preparing precursor of lithium composite transition metal oxide using a reactor
CN105283985A (zh) * 2013-06-14 2016-01-27 莱米纳有限公司 核-壳粒子的制造装置及利用该装置的核-壳粒子制造方法
EP3010074A4 (fr) * 2013-06-14 2017-01-04 Laminar Co., Ltd. Dispositif permettant de préparer des particules coeur-écorce et procédé de préparation de particules coeur-écorce au moyen du dispositif
US10601035B2 (en) 2013-06-14 2020-03-24 Posco Method of preparing core-shell particles
CN106029575A (zh) * 2014-02-13 2016-10-12 宜安德株式会社 利用库埃特泰勒反应器的镍钴锰复合前驱体的连续式制备方法
US20160104879A1 (en) * 2014-10-14 2016-04-14 University-Industry Cooperation Group Of Kyung Hee University Method for preparing core-shell structured particle by using continuous couette-taylor crystallizer
US10347913B2 (en) * 2014-10-14 2019-07-09 Lg Chem, Ltd. Method for preparing core-shell structured particle by using continuous Couette-Taylor crystallizer
CN111111593A (zh) * 2020-01-06 2020-05-08 湖南中伟新能源科技有限公司 一种三元前驱体材料的制备设备以及制备方法

Also Published As

Publication number Publication date
KR20130031588A (ko) 2013-03-29
KR101275845B1 (ko) 2013-06-17
WO2013042986A9 (fr) 2013-05-16
WO2013042986A3 (fr) 2013-07-04

Similar Documents

Publication Publication Date Title
WO2013042986A9 (fr) Appareil utilisant un équipement de réaction à tourbillons de taylor-couette pour préparer un précurseur de matière active de cathode pour batterie secondaire au lithium
Entwistle et al. Co-precipitation synthesis of nickel-rich cathodes for Li-ion batteries
JP5614334B2 (ja) ニッケルコバルト複合水酸化物およびその製造方法、ならびに該複合水酸化物を用いて得られる非水系電解質二次電池用正極活物質
US8492030B2 (en) Cathode material for lithium batteries
US10439215B2 (en) Nickel lithium ion battery positive electrode material having concentration gradient, and preparation method therefor
CN101447566B (zh) 层状-尖晶石共生结构锂离子电池正极材料及制备方法
US10903516B2 (en) Method of preparing cathode material for secondary battery
CN105449169B (zh) 锂离子电池正极材料、制备方法及锂离子电池
CN109311696B (zh) 具有可调粒径分布的电池材料的可升级沉淀合成方法
KR101313575B1 (ko) 리튬 이차 전지 양극활물질 전구체의 제조방법, 이에 의하여 제조된 리튬 이차전지 양극활물질 전구체, 및 상기 리튬 이차전지 양극활물질 전구체를 이용한 리튬 이차전지 양극활물질의 제조방법, 이에 의하여 제조된 리튬 이차전지 양극활물질
CN110867573A (zh) 三元正极材料及其制备方法、锂离子电池和电动汽车
CN103094576B (zh) 一种镍基正极材料及其制备方法和电池
CN104600285B (zh) 一种球形镍锰酸锂正极材料的制备方法
KR20120098631A (ko) 니켈?코발트?망간계 화합물 입자 분말 및 그의 제조 방법, 리튬 복합 산화물 입자 분말 및 그의 제조 방법, 및 비수전해질 이차 전지
CN105118983B (zh) 一种镍锰酸锂正极材料的制备方法
CN105594030A (zh) 用于含高锂和锰的阴极材料的碳酸盐前体
US11952287B2 (en) Method for the precipitation of particles of a metal carbonate material without use of a chelating agent
KR20130059029A (ko) 복합 금속 수산화물의 제조방법
CN103066271B (zh) 一种高电压锂离子电池正极材料及其制备方法
CN115832281B (zh) 一种富镍层状氧化物材料及其制备方法和应用
CN115485243B (zh) 固相合成的正极活性材料及其制造方法
CN110863245A (zh) 三元正极材料及其制备方法、锂离子电池和电动汽车
KR20110111058A (ko) 결정성의 망간복합산화물, 리튬이차전지용 리튬망간복합산화물 및 그 제조방법
KR100668050B1 (ko) 망간복합산화물, 이를 이용한 리튬이차전지 스피넬형양극활물질 및 그 제조방법
CN111162273B (zh) 正极活性材料及包括其的锂离子电化学系统

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12832813

Country of ref document: EP

Kind code of ref document: A2

122 Ep: pct application non-entry in european phase

Ref document number: 12832813

Country of ref document: EP

Kind code of ref document: A2