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WO2018143783A1 - Précurseur de matériau actif d'électrode positive pour une batterie secondaire au lithium et procédé de préparation de matériau actif d'électrode positive - Google Patents

Précurseur de matériau actif d'électrode positive pour une batterie secondaire au lithium et procédé de préparation de matériau actif d'électrode positive Download PDF

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Publication number
WO2018143783A1
WO2018143783A1 PCT/KR2018/001607 KR2018001607W WO2018143783A1 WO 2018143783 A1 WO2018143783 A1 WO 2018143783A1 KR 2018001607 W KR2018001607 W KR 2018001607W WO 2018143783 A1 WO2018143783 A1 WO 2018143783A1
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WIPO (PCT)
Prior art keywords
active material
positive electrode
transition metal
electrode active
material precursor
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PCT/KR2018/001607
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English (en)
Korean (ko)
Inventor
최상순
박현아
정원식
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180014230A external-priority patent/KR102086536B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880003900.8A priority Critical patent/CN109843810B/zh
Priority to US16/333,378 priority patent/US10892471B2/en
Publication of WO2018143783A1 publication Critical patent/WO2018143783A1/fr

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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
    • 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 cathode active material precursor for a lithium secondary battery and a method for producing a cathode active material.
  • lithium secondary batteries having high energy density and voltage, long cycle life, and low self discharge rate have been commercialized and widely used.
  • Lithium transition metal oxide is used as a positive electrode active material of a lithium secondary battery, and among these, lithium cobalt oxide of LiCoO 2 having a high operating voltage and excellent capacity characteristics is mainly used.
  • LiCoO 2 is very poor in thermal properties due to destabilization of crystal structure due to de-lithium and is expensive, there is a limit to using LiCoO 2 as a power source in fields such as electric vehicles.
  • lithium manganese oxide such as LiMnO 2 or LiMn 2 O 4
  • lithium iron phosphate compound such as LiFePO 4
  • lithium nickel oxide such as LiNiO 2
  • research and development of lithium nickel oxide which has a high reversible capacity of about 200mAh / g and is easy to implement a large-capacity battery, has been actively studied.
  • LiNiO 2 has a poor thermal stability as compared to LiCoO 2, and when an internal short circuit occurs due to pressure from the outside in a charged state, the positive electrode active material itself is decomposed to cause the battery to rupture and ignite.
  • 'NCM-based lithium oxides' nickel Nickel cobalt manganese-based lithium composite metal oxides
  • CSTR continuous reactor
  • a batch method is a method of discharging a precursor after the completion of the reaction by adding a raw material to a reactor volume for a predetermined time.
  • the continuous reactor (CSTR) method has an advantage of easily controlling the metal composition ratio, but since the input of raw materials and the discharge of the product are performed continuously at the same time, the positive electrode active material precursors generated in the reactor have a residence time and a reaction time in the reactor. There may be a deviation, there is a problem that the non-uniformity occurs in the size and composition of the particles produced accordingly.
  • the particle size is easy to control and there is a tendency to adopt a batch type method for preparing a cathode active material precursor having a uniform particle size, even if a batch reactor is used, the particle size is uniform.
  • the productivity is significantly reduced compared to the continuous reactor (CSTR) method.
  • the present invention is a method for producing a positive electrode active material precursor for a lithium secondary battery using a batch reactor, it is easy to control the particle size, can produce a positive electrode active material precursor with a uniform particle size, significantly increase the productivity It is intended to provide a way to do this.
  • the present invention provides a method for producing a positive electrode active material precursor for a lithium secondary battery using a batch reactor, comprising: 1) a transition metal-containing solution, an aqueous alkali solution and an ammonium ion containing a transition metal cation in a batch reactor; Continuously adding the containing solution to form positive electrode active material precursor particles; 2) stopping the addition of the solutions and precipitating the formed positive electrode active material precursor particles when the batch reactor becomes full; 3) discharging the generated supernatant after the precipitated positive electrode active material precursor particles; 4) adding a solution containing ammonium ion to adjust the pH lowered in the process of discharging the supernatant to pH 10 to pH 12; And 5) growing positive electrode active material precursor particles while continuously adding a transition metal-containing solution, an aqueous alkali solution, and an ammonium ion-containing solution to the batch type reactor again. It provides a method for producing a positive electrode active material precursor.
  • the present invention provides a method for producing a cathode active material for a lithium secondary battery comprising the step of mixing the positive electrode active material precursor with a lithium-containing raw material and firing.
  • the particle size control is easier than the conventional batch method, and a cathode active material precursor for a lithium secondary battery having a uniform particle size can be prepared, and the batch method is conventionally used.
  • the productivity of the positive electrode active material can be significantly increased.
  • FIG. 1A, 1B and 2 are schematic views illustrating a method of manufacturing a positive electrode active material precursor according to an embodiment of the present invention.
  • the method for preparing a cathode active material precursor for a lithium secondary battery of the present invention is prepared using a batch reactor, and 1) a transition metal-containing solution, an aqueous alkali solution and an ammonium ion containing a transition metal cation in a batch reactor.
  • step 1) for preparing the positive electrode active material precursor forms positive electrode active material precursor particles while continuously adding a transition metal-containing solution, an aqueous alkali solution, and an ammonium ion-containing solution to a batch reactor. do.
  • FIGS. 1A and 2 are schematic views illustrating a method of manufacturing a positive electrode active material precursor according to an embodiment of the present invention.
  • a transition metal-containing solution, an aqueous alkali solution and an ammonium ion-containing solution are continuously added to a batch reactor 100.
  • the pH value may be adjusted by first adding an aqueous alkali solution and an ammonium aqueous solution to a predetermined volume of the batch reactor 100.
  • the cathode active material precursor is prepared using a batch reactor, the reaction conditions such as concentration, temperature, and residence time of the reactants in the reactor are the same as compared to the continuous reactor (CSTR), so that the uniformity is relatively uneven.
  • the product can be prepared.
  • the transition metal-containing solution may include a cation of at least one transition metal selected from the group consisting of nickel (Ni), manganese (Mn), and cobalt (Co), and more preferably include two or more transition metal cations. Can be.
  • the transition metal-containing solution may include acetates, nitrates, sulfates, halides, sulfides, hydroxides, oxides or oxyhydroxides of the transition metals, and is not particularly limited as long as they can be dissolved in water.
  • the cobalt (Co) is Co (OH) 2 , CoOOH, Co (OCOCH 3 ) 2 4H 2 O, Co (NO 3 ) 2 6H 2 O, CoSO 4 or Co (SO 4 ) 2 7H 2 O and the like, any one or a mixture of two or more thereof may be used.
  • the nickel (Ni) is Ni (OH) 2, NiO, NiOOH, NiCO 3 ⁇ 2Ni (OH) 2 ⁇ 4H 2 O, NiC 2 O 2 ⁇ 2H 2 O, Ni (NO 3) 2 ⁇ 6H 2 O , NiSO 4 , NiSO 4 ⁇ 6H 2 O, fatty acid nickel salts or nickel halides, and the like, any one or a mixture of two or more thereof may be used.
  • the manganese (Mn) is a manganese oxide such as Mn 2 O 3 , MnO 2 , Mn 3 O 4 ;
  • Manganese salts such as MnCO 3 , Mn (NO 3 ) 2 , MnSO 4 , manganese acetate, manganese dicarboxylic acid, manganese citrate and fatty acid manganese; Oxy hydroxide, and manganese chloride, and the like, and any one or a mixture of two or more thereof may be used.
  • the final precursor is further included other metal elements (M) in addition to nickel (Ni), manganese (Mn) and cobalt (Co) (for example, M is W, Mo, Cr, Al, Zr, At least one or two or more elements selected from the group consisting of Ti, Mg, Ta, and Nb), and the metal element (M) -containing raw material may be optionally further added in the preparation of the transition metal-containing solution.
  • M metal elements
  • Ni nickel
  • Mn manganese
  • Co cobalt
  • M W, Mo, Cr, Al, Zr
  • the metal element (M) -containing raw material may be optionally further added in the preparation of the transition metal-containing solution.
  • Examples of the metal element (M) -containing raw material include acetates, nitrates, sulfates, halides, sulfides, hydroxides, oxides or oxyhydroxides containing metal elements (M), and one or two of them. Mixtures of the above may be used. For example, when M is W, tungsten oxide or the like may be used.
  • the aqueous alkali solution may include at least one selected from the group consisting of hydrates of alkali metals, hydroxides of alkali metals, hydrates of alkaline earth metals and hydroxides of alkaline earth metals.
  • the aqueous alkali solution may include NaOH, KOH, or Ca (OH) 2 , and as a solvent, a mixture of water or an organic solvent (specifically, alcohol, etc.) and water that may be uniformly mixed with water may be used. Can be.
  • the concentration of the aqueous alkali solution may be 2M to 10M.
  • the concentration of the aqueous alkali solution is less than 2M there is a fear that the particle formation time is long, the tap density is lowered and the yield of the coprecipitation reactant is lowered. If the concentration of the basic aqueous solution exceeds 10M, since the particles grow rapidly due to a rapid reaction, it is difficult to form uniform particles, and the tap density may also decrease.
  • the ammonium ion-containing solution may include at least one selected from the group consisting of NH 4 OH, (NH 4 ) 2 SO 4 , NH 4 NO 3 , NH 4 Cl, CH 3 COONH 4 , and NH 4 CO 3 .
  • the solvent a mixture of water or an organic solvent (specifically, alcohol, etc.) that can be mixed with water uniformly can be used.
  • Formation of the positive electrode active material precursor particles of step 1) a) by adjusting the amount of the alkaline aqueous solution and the ammonium ion-containing solution by coprecipitation reaction at pH 11 to pH 13 to produce a particle nucleus, b) after the nucleus is generated , By adjusting the dose of the alkali aqueous solution and the ammonium ion-containing solution to grow the particles by coprecipitation at pH 8 to pH 12.
  • an alkaline aqueous solution and an ammonium ion-containing solution may be first added to be in the range of pH 11 to 13, and thereafter, particle nuclei may be generated while introducing a transition metal-containing solution into the reactor.
  • the pH is controlled to maintain the pH 11 to pH 13 by continuously adding an aqueous alkali solution and an ammonium ion-containing solution together with the addition of the transition metal-containing solution. can do. If the pH value is satisfied, the generation of particle nuclei may occur preferentially, and the growth of particles may hardly occur.
  • the amount of the alkaline aqueous solution and the ammonium ion-containing solution may be adjusted to be in the range of pH 8 to pH 12, and the generated particle nucleus may be grown while the transition metal-containing solution is added.
  • the solution is controlled to maintain pH 8 to pH 12 by continuously adding an aqueous alkali solution and an ammonium ion-containing solution together with the addition of the transition metal-containing solution. can do.
  • the pH value is satisfied, new particle nuclei are hardly generated, and growth of particles may occur preferentially.
  • the addition rate of the transition metal-containing solution, the alkaline aqueous solution and the ammonium ion-containing solution of step 1) may satisfy the following Equation 1.
  • Equation 1 V is the batch reactor volume (mL), v is the volume of the solution (mL) filled in the batch reactor prior to the continuous addition of the transition metal containing solution, t is the total reaction time ( Min), ⁇ 1 is the addition rate (mL / min) of the transition metal-containing solution, ⁇ 2 is the addition rate (mL / min) of the aqueous alkali solution, ⁇ 3 is the addition rate (mL / min) of the ammonium ion-containing solution.
  • the transition metal-containing solution, the alkaline aqueous solution and the ammonium ion-containing solution are added at a flow rate within the range satisfying the above formula 1, it is about 2 to 30 times, more preferably about 2 times than the time required to fill the reactor.
  • the reactor can be filled in as little as 10 times faster.
  • the alkaline aqueous solution and the ammonium ion-containing solution When the feed rate of the transition metal-containing solution, the alkaline aqueous solution and the ammonium ion-containing solution is slower than the range of Formula 1, productivity may be lowered. If the transition rate exceeds the range of Formula 1, particle nucleation may not be stably generated and particle size may be reduced. Distribution control can be difficult.
  • the input rate of the existing transition metal-containing solution is about 5 mL / min
  • the alkali solution is about 1 mL / min
  • the ammonium ion-containing solution is about
  • the addition rate ( ⁇ 1 ) of the transition metal-containing solution may be 10 to 150mL / min, more preferably 15 to 50mL / min
  • the addition rate of the aqueous alkali solution ( ⁇ 2 ) may be 2 to 30 mL / min, more preferably 3 to 10 mL / min
  • an input rate ( ⁇ 3 ) of the ammonium ion-containing solution is 2 to 30 mL / min, more preferably 3 to 10 mL / min.
  • another embodiment of the present invention includes a first transition metal-containing solution including cations of two or more transition metals, and a cation of two or more transition metals as the transition metal-containing solution, and the first transition metal-containing solution.
  • a second transition metal-containing solution having different concentrations of transition metal cations may be used to prepare a precursor having a concentration gradient of the composition of the transition metal in the particles.
  • FIG. 1B is a view schematically showing a method of manufacturing a positive electrode active material precursor according to another embodiment of the present invention.
  • a first transition metal-containing solution and a second transition metal-containing solution having different concentrations of the transition metal cation and the first transition metal-containing solution are mixed and mixed through a mixer 10. ) May be added to the reactor (100).
  • the first and second transition metal-containing solution may include two or more transition metal cations, and more preferably at least two or more transition metals selected from the group consisting of nickel (Ni), manganese (Mn), and cobalt (Co). Cations may be included.
  • the first and second transition metal-containing solution may be different concentration of each transition metal cation.
  • the first transition metal-containing solution may be a solution having a higher concentration of nickel (Ni) cation than the second transition metal-containing solution.
  • the first transition metal-containing solution may have a molar ratio of at least 80% of the nickel (Ni) salt with respect to the total transition metal salt, and the second transition metal-containing solution may contain the nickel (Ni) with respect to the total transition metal salt.
  • the molar ratio of the salt may be 70% or less.
  • the first transition metal-containing solution may be a solution having a lower concentration of at least one transition metal cation of manganese (Mn) and cobalt (Co) than the second transition metal solution.
  • the first transition metal-containing solution may have a molar ratio of the manganese (Mn) and / or cobalt (Co) salts of 20% or less relative to the total transition metal salt, and the second transition metal-containing solution may include the total transition metal.
  • the molar ratio of the manganese (Mn) and / or cobalt (Co) salt relative to the salt may be 30% or more.
  • a precursor having a concentration gradient in the transition metal composition may be formed in the particles.
  • the rate of introduction of the first transition metal-containing solution may be gradually decreased, and the rate of introduction of the second transition metal-containing solution may be gradually increased to form a concentration gradient.
  • the mixing ratio of the first transition metal-containing solution and the second transition metal-containing solution is gradually mixed from 100% by volume to 0% by volume to 0% by volume to 100% by volume, and the surface from the center of the particle is mixed. It may be to form the positive electrode active material precursor particles having a concentration gradient gradually changing to.
  • the sum of the input speeds of the first and second transition metal-containing solutions may correspond to the input speed ( ⁇ 1 ) of the transition metal-containing solution in Equation 1.
  • the first transition metal-containing solution, the second transition metal-containing solution, the ammonium ion-containing solution, and the basic aqueous solution may be separately added to the reactor, or some or all of the solutions may be premixed before the reactor is added. You can also put in.
  • the first transition metal-containing solution and the second transition metal-containing solution are mixed using a static mixer, etc., and then introduced into the reactor, and the ammonium ion-containing solution and the basic aqueous solution are directly introduced into the reactor. It can be put in.
  • the pH in the batch reactor by the flow rate of Ni composition or alkaline aqueous solution contained in the transition metal-containing solution to be put into the reactor It may be controlled.
  • a mixed solution obtained by mixing a first transition metal-containing solution and a second transition metal-containing solution through a mixer is added to a batch reactor, and the pH in the batch reactor is mixed into the reactor. It may be controlled by the Ni composition contained in the solution.
  • the pH may be 11.5 to 12, preferably 11.6 to 11.9, where a positive electrode active material precursor particle nucleus is produced.
  • the pH of the reactor is adjusted to 10.5 to 11.5, preferably 11 to 11.4, wherein the particles may be grown. .
  • Equation 2 the pH in the batch reactor satisfies Equation 2 below.
  • pH t1 is the pH in the reactor at t1 time
  • pH 0 is the initial pH in the reactor
  • [Ni] 0 is the Ni molar concentration in the transition metal-containing solution initially introduced
  • [Ni] t1 at t1 time The molar Ni concentration in the incoming transition metal containing solution.
  • the pH at time t may be close to pH 0 ⁇ ([Ni] 0 ⁇ [Ni] t 1 ) ⁇ 0.02.
  • the pH in the batch reactor may be controlled by the flow rate of the alkaline aqueous solution, the flow rate of the alkaline aqueous solution is to satisfy the following equation 3.
  • Equation 3 ⁇ 2, t2 is the input flow rate of the alkaline aqueous solution at t2 time, ⁇ 2 , 0 is the initial input flow rate of the alkaline aqueous solution, [Ni] 0 is the Ni molar concentration in the initial metal-containing solution, [Ni] t2 is the Ni molar concentration in the transition metal containing solution introduced at t2 time.
  • step 2) when the batch reactor becomes a batch, the addition of the solutions is stopped and the positive electrode active material precursor particles are formed.
  • the transition metal-containing solution, the alkaline aqueous solution and the ammonium ion-containing solution are continuously added to the batch reactor 100 to react until the batch reactor 100 is almost completely filled. You can proceed.
  • the batch reactor 100 becomes full it may mean that the volume of the injected solutions is 95 to 100% of the volume of the batch reactor 100.
  • the reactor can be filled in about 2 to 10 times faster than the time required to fill the reactor because it proceeds by increasing the input rate of the solution as described above.
  • the reactor 100 When the reactor 100 is filled as described above, the addition of the solutions is stopped and the reaction is terminated, and the produced solid, that is, the positive electrode active material precursor particles are precipitated.
  • the positive electrode active material precursor particles When the positive electrode active material precursor particles are precipitated, they may be stirred at 5 to 50 rpm.
  • the positive electrode active material precursor particles when the positive electrode active material precursor particles are precipitated, by stirring at 5 to 50 rpm instead of completely stopping the stirring, the fine particles can be effectively removed without precipitating fine powder, and precursor particles having a more uniform particle size distribution can be produced.
  • the concentration gradient composition for example, the degree of concentration difference at the particle center and surface of Ni
  • the concentration gradient is finally removed by effectively removing the fine powder.
  • Precursor particles having a uniform composition eg, precursor particles having a similar degree of concentration difference at the particle center and surface of Ni
  • a supernatant may be formed on the precipitate.
  • step 3 the precipitated positive electrode active material precursor particles are discharged to the outside.
  • productivity can be improved by adding a transition metal-containing solution, an aqueous alkali solution and an ammonium ion-containing solution to the empty space of the batch reactor 100 to grow the positive electrode active material precursor particles. .
  • the precipitated positive electrode active material precursor particles are precipitated, and then the supernatant is removed and the solutions are added again to grow the particles.
  • the particles are added again to further grow the particles, thereby increasing the particle growth during the same reaction time. Can increase significantly.
  • the ratio of the liquid component to the transition metal cation is increased because the transition metal cation of the transition metal-containing solution is crystallized to form the positive electrode active material precursor particles.
  • the particles can be grown in a state where the transition metal cation is relatively high because the transition metal-containing solution is added again, and the fine powder generated during the reaction can be removed when the supernatant is removed. It is easier and can form uniform precursor particles.
  • step 4 after the supernatant is removed, an ammonium ion-containing solution is added to adjust the pH lowered in the process of discharging the supernatant to pH 10 to pH 12.
  • the transition metal-containing solution, the alkaline aqueous solution, and the ammonium ion-containing solution are added to the batch reactor 100 to grow the cathode active material precursor particles, and the pH value is lowered in the process of removing the supernatant. It is important to adjust the pH value by adding a solution containing ammonium ion before reacting again. In the process of removing the supernatant, since the pH value is about 0.3 to 1.0, the ammonium ion-containing solution may be added to adjust the pH to 10 to 12, more preferably to pH 10.5 to 11.5.
  • the alkaline aqueous solution and the ammonium ion-containing solution are added before the reaction, the pH value is lowered to compensate for the lowered pH at the beginning of the reaction.
  • the reaction proceeds while suddenly adding an excessive amount of the aqueous alkali solution, so that the particle growth does not occur preferentially, but new particle nuclei are generated to form fine powder, the particle size distribution is increased, and non-uniform precursor particles may be formed.
  • the precipitated positive electrode active material precursor particles may not be well dispersed in the reaction solution upon stirring, but when the ammonium ion-containing solution is added, the precipitated solids may be well dispersed. It can play a role.
  • step 5 grows the positive electrode active material precursor particles while continuously introducing the transition metal-containing solution, the alkaline aqueous solution and the ammonium ion-containing solution back into the batch reactor.
  • the transition metal-containing solution As described above, by discharging the supernatant, the transition metal-containing solution, the aqueous alkali solution, and the ammonium ion-containing solution are added to the empty space of the reactor, thereby increasing the productivity of the positive electrode active material precursor particles, and the particle size is more controlled. It becomes easy and can produce uniform precursor particles.
  • the cathode active material precursor particles may be further grown by repeatedly performing steps 2) to 5).
  • the time is about 2 to 30 times faster than the time required to fill the reactor, and more preferably about 2 to 10 times faster. It is possible to fill the reactor inside, to generate more particle nuclei in the reactor of the same size, and then to precipitate the resulting positive electrode active material precursor particles, remove the supernatant, and then add solutions again to grow the particles further This can make particle growth more efficient during the same reaction time, and the yield of precursor particles can be significantly increased.
  • the yield of the cathode active material precursor particles prepared as described above is 100% higher than that of the cathode active material precursor prepared without the step of removing the precipitate and the supernatant of the cathode active material precursor particles using a batch reactor of the same size.
  • the positive electrode active material precursor particles finally produced may be uniform particles having a (D 90 -D 10 ) / D 50 of 1.2 or less.
  • the present invention provides a method for producing a cathode active material through the step of firing after mixing the cathode active material precursor prepared as described above with a lithium-containing raw material.
  • lithium-containing raw material for example, lithium carbonate (Li 2 CO 3 ) or lithium hydroxide (LiOH) may be used, and the positive electrode active material precursor and the lithium-containing raw material are mixed in a 1: 1 to 1: 1.15 molar ratio. can do.
  • the lithium-containing raw material is mixed below the above range, the capacity of the positive electrode active material may be lowered.
  • the lithium-containing raw material is mixed above the above range, the particles are sintered during the firing process, and thus the production of the positive electrode active material It may be difficult, and capacity reduction and separation of the positive electrode active material particles (causing the positive electrode active material aggregation phenomenon) may occur after firing.
  • the firing may be carried out at a temperature of 800 °C to 1000 °C. If the firing temperature is less than 800 °C due to insufficient reaction may leave the raw material in the particles to reduce the high temperature stability of the battery, and the bulk density and crystallinity may be lowered structural stability. On the other hand, if the firing temperature exceeds 1000 °C non-uniform growth of the particles may occur, the particle size is too large to reduce the amount of particles that can be included per unit area, the volume capacity of the battery may be lowered. On the other hand, considering the particle size control, capacity, stability, and reduction of lithium-containing by-products of the prepared cathode active material, the firing temperature may be more preferably 850 °C to 950 °C.
  • the firing may be performed for 5 to 35 hours.
  • the baking time is less than 5 hours, the reaction time may be too short to obtain a highly crystalline positive electrode active material.
  • the baking time is greater than 35 hours, the size of the particles may be excessively large, and production efficiency may be reduced.
  • the cathode active material thus prepared is secondary particles formed by aggregation of primary particles, and the primary particles have a columnar structure.
  • the primary particles having a columnar structure having an aspect ratio of 1 may be aggregated toward the center direction of the secondary particles to form spherical secondary particles.
  • the lithium secondary battery positive electrode may be manufactured by including the positive electrode active material.
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer positioned on at least one surface of the positive electrode current collector and including the positive electrode active material.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • carbon, nickel, titanium on the surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel Surface treated with silver, silver or the like can be used.
  • the positive electrode current collector may have a thickness of about 3 to 500 ⁇ m, and may form fine irregularities on the surface of the current collector to increase the adhesion of the positive electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • the cathode active material layer may include a conductive material and a binder together with the cathode active material described above.
  • the cathode active material may be included in an amount of? T of 80 to 99% by weight, more specifically 85 to 98% by weight based on the total weight of the cathode active material layer.
  • the cathode active material may be included in an amount of? T of 80 to 99% by weight, more specifically 85 to 98% by weight based on the total weight of the cathode active material layer.
  • When included in the above content range may exhibit excellent capacity characteristics.
  • the conductive material is used to impart conductivity to the electrode.
  • the conductive material may be used without particular limitation as long as it has electronic conductivity without causing chemical change. Specific examples thereof include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black and carbon fiber; Metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Or conductive polymers such as polyphenylene derivatives, and the like, or a mixture of two or more kinds thereof may be used.
  • the conductive material may be included in an amount of 1 to 30 wt% based on the total weight of the positive electrode active material layer.
  • the binder serves to improve adhesion between the positive electrode active material particles and the adhesion between the positive electrode active material and the current collector.
  • Specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC).
  • the binder may be included in an amount of 1 to 30 wt% based on the total weight of the cathode active material layer.
  • the positive electrode may be manufactured according to a conventional positive electrode manufacturing method except for using the positive electrode active material described above.
  • the positive electrode active material and optionally, a composition for forming a positive electrode active material layer prepared by dissolving or dispersing a binder and a conductive material in a solvent may be applied onto a positive electrode current collector, followed by drying and rolling.
  • the type and content of the cathode active material, the binder, and the conductive material are as described above.
  • the solvent may be a solvent generally used in the art, and may include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone or acetone. Water, and the like, one of these alone or a mixture of two or more thereof may be used.
  • the amount of the solvent is sufficient to dissolve or disperse the positive electrode active material, the conductive material, and the binder in consideration of the coating thickness of the slurry and the production yield, and to have a viscosity that can exhibit excellent thickness uniformity during application for the production of the positive electrode. Do.
  • the positive electrode may be prepared by casting the composition for forming the positive electrode active material layer on a separate support, and then laminating the film obtained by peeling from the support onto a positive electrode current collector.
  • the electrochemical device may be specifically a battery, a capacitor, or the like, and more specifically, a lithium secondary battery.
  • the lithium secondary battery specifically includes a positive electrode, a negative electrode positioned to face the positive electrode, a separator and an electrolyte interposed between the positive electrode and the negative electrode, and the positive electrode is as described above.
  • the lithium secondary battery may further include a battery container for accommodating the electrode assembly of the positive electrode, the negative electrode, and the separator, and a sealing member for sealing the battery container.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer positioned on the negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • the negative electrode current collector may be formed on a surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper, or stainless steel. Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy and the like can be used.
  • the negative electrode current collector may have a thickness of 3 ⁇ m to 500 ⁇ m, and similarly to the positive electrode current collector, fine concavities and convexities may be formed on the surface of the current collector to enhance the bonding force of the negative electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • the negative electrode active material layer optionally includes a binder and a conductive material together with the negative electrode active material.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used.
  • Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fibers, and amorphous carbon;
  • Metallic compounds capable of alloying with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys or Al alloys;
  • Metal oxides capable of doping and undoping lithium such as SiO ⁇ (0 ⁇ ⁇ 2), SnO 2 , vanadium oxide, lithium vanadium oxide;
  • a composite including the metallic compound and the carbonaceous material such as a Si-C composite or a Sn-C composite, and any one or a mixture of two or more thereof may be used.
  • a metal lithium thin film may be used as the anode active material.
  • the carbon material both low crystalline carbon and high crystalline carbon can be used. Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is amorphous, plate, scaly, spherical or fibrous natural graphite or artificial graphite, Kish graphite (Kish) graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar pitch High-temperature calcined carbon such as derived cokes is typical.
  • the binder and the conductive material may be the same as described above in the positive electrode.
  • the negative electrode active material layer is, for example, coated with a negative electrode active material, and optionally a composition for forming a negative electrode active material layer prepared by dissolving or dispersing a binder and a conductive material in a solvent and dried, or for forming the negative electrode active material layer
  • the composition may be prepared by casting the composition on a separate support, and then laminating the film obtained by peeling from the support onto a negative electrode current collector.
  • the separator is to separate the negative electrode and the positive electrode and to provide a passage for the movement of lithium ions, if it is usually used as a separator in a lithium secondary battery can be used without particular limitation, in particular for ion transfer of the electrolyte It is desirable to have a low resistance against the electrolyte and excellent electrolytic solution-moisture capability.
  • a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer or the like Laminate structures of two or more layers may be used.
  • a porous nonwoven fabrics such as nonwoven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers and the like may be used.
  • a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be optionally used as a single layer or a multilayer structure.
  • examples of the electrolyte used in the present invention include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like, which can be used in manufacturing a lithium secondary battery. It doesn't happen.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • the organic solvent may be an ester solvent such as methyl acetate, ethyl acetate, ⁇ -butyrolactone or ⁇ -caprolactone; Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate, Carbonate solvents such as PC); Alcohol solvents such as ethyl alcohol and isopropyl alcohol; Nitriles, such as R-CN (R is a C2-C20 linear, branched or cyclic hydrocarbon group, which may include
  • carbonate-based solvents are preferable, and cyclic carbonates having high ionic conductivity and high dielectric constant (for example, ethylene carbonate or propylene carbonate) that can improve the charge and discharge performance of a battery, and low viscosity linear carbonate compounds (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate and the like is more preferable.
  • the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of about 1: 1 to about 1: 9, so that the performance of the electrolyte may be excellent.
  • the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 .
  • LiCl, LiI, or LiB (C 2 O 4 ) 2 and the like can be used.
  • the concentration of the lithium salt is preferably used within the range of 0.1 to 2.0M. When the concentration of the lithium salt is included in the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can move effectively.
  • the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri Ethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N-substituted imida
  • One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be included. In this case, the additive may be included in 0.1 to 5% by weight based on the total weight of the electrolyte.
  • the lithium secondary battery including the cathode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention rate
  • portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles ( It is useful for electric vehicle fields such as hybrid electric vehicle (HEV).
  • HEV hybrid electric vehicle
  • a battery module including the lithium secondary battery as a unit cell and a battery pack including the same are provided.
  • the battery module or the battery pack is a power tool (Power Tool); Electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Or it can be used as a power source for any one or more of the system for power storage.
  • Power Tool Electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Or it can be used as a power source for any one or more of the system for power storage.
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be cylindrical, square, pouch type, or coin type using a can.
  • the lithium secondary battery according to the present invention may not only be used in a battery cell used as a power source for a small device, but also preferably used as a unit battery in a medium-large battery module including a plurality of battery cells.
  • NiSO 4 , CoSO 4 , and MnSO 4 were mixed in water in an amount such that the molar ratio of nickel: cobalt: manganese was 80:10:10, to prepare a solution containing 2M of transition metal.
  • the vessel containing the transition metal containing solution was connected to enter a 20 L batch reactor set at 60 ° C. Further 25 wt% NaOH aqueous solution and 15 wt% NH 4 OH aqueous solution were prepared and connected to the reactor, respectively.
  • the transition metal-containing solution 25 ml / min of the transition metal-containing solution, 4 ml / min of NaOH aqueous solution, and 4 ml / min of NH 4 OH aqueous solution were added at a rate of 5 ml / min to react for 30 minutes to form particle nuclei of nickel manganese cobalt-based composite metal hydroxides.
  • the transition metal-containing solution was added to 25ml / min, NaOH aqueous solution 4ml / min, NH 4 OH aqueous solution at a rate of 5ml / min to increase the growth of nickel cobalt manganese-based composite metal hydroxide particles Induced. Since the reaction was maintained for 8 hours to grow nickel manganese cobalt-based composite metal hydroxide, the reactor (20L) was full.
  • NiSO 4 , CoSO 4 , MnSO 4 as a transition metal-containing solution was mixed in water in an amount such that the molar ratio of nickel: cobalt: manganese was 90: 5: 5 to prepare a solution containing the first transition metal at a concentration of 2M.
  • NiSO 4 , CoSO 4 and MnSO 4 were mixed in water so that the molar ratio of nickel: cobalt: manganese was 50:25:25, thereby preparing a second transition metal-containing solution having a concentration of 2M.
  • the vessels containing the first and second transition metal containing solutions were connected to a mixer, respectively, and a batch reactor 20L was connected to the outlet side of the mixer. Further 25 wt% NaOH aqueous solution and 15 wt% NH 4 OH aqueous solution were prepared and connected to the reactor, respectively.
  • the sum of the input rates of the first and second transition metal-containing solutions is equal to the input rate of the transition metal-containing solution of Example 1, but the input speed of the first transition metal-containing solution is gradually decreased in the entire reaction.
  • the rate of introduction of the second transition metal-containing solution was gradually increased throughout the reaction, and the concentration of nickel, pH, and NaOH aqueous solution of the transition metal-containing solution introduced into the reactor through a static mixer are shown in the following table.
  • the composition was carried out in the same manner as in Example 1, except that a precursor having a concentration gradient was prepared by reacting with changing as described in Example 1, and having an average composition of Ni 0.60 Co 0.20 Mn 0.20 (OH) 2 , Ni having a particle surface from the particle center. To decrease, Co and Mn prepared a precursor having a concentration gradient increases from the center of the particle to the particle surface.
  • Ni 0 . 60 Co 0 . 20 has Mn 0 .20 (OH) 2 of the average composition
  • Ni was prepared the precursor having a concentration gradient which decreases gradually from the center to the particle surface and particle, Co and Mn increases toward the particle surface from the center of the particle.
  • the precursor was prepared in the same manner as in Example 1 except that the supernatant was discharged to the outside.
  • the precursor was prepared in the same manner as in Example 1 except that the supernatant was discharged to the outside.
  • a precursor was prepared in the same manner as in Example 1 except that the composite metal hydroxide was grown, and the supernatant was removed and the process of inducing particle growth was not performed again.
  • NiSO 4 , CoSO 4 , MnSO 4 as a transition metal-containing solution was mixed in water in an amount such that the molar ratio of nickel: cobalt: manganese was 90: 5: 5 to prepare a solution containing the first transition metal at a concentration of 2M.
  • NiSO 4 , CoSO 4 and MnSO 4 were mixed in water so that the molar ratio of nickel: cobalt: manganese was 50:25:25, thereby preparing a second transition metal-containing solution having a concentration of 2M.
  • the vessels containing the first and second transition metal containing solutions were connected to a mixer, respectively, and a batch reactor 20L was connected to the outlet side of the mixer.
  • Ni has a mean composition of 0.60 Co 0.20 Mn 0.20 (OH) 2 , Ni decreases from the particle center toward the particle surface, and Co and Mn increases from the particle center to the particle surface.
  • a precursor having was prepared.
  • the solution was added to increase the rate, and when the reactor became full, the supernatant was removed, the ammonium ion-containing solution was added, and then the solutions were added again to grow particles.
  • Examples 1 to 5 showed narrower particle size distributions than Comparative Examples 1 and 3 to produce more uniform precursors, and in Comparative Example 2, in which no ammonium ion-containing solution was added in the middle, the supernatant was removed. Since the solution was added again in a state where the pH value was lowered, the reaction could not be suppressed to generate particle nuclei, resulting in fine powder and very uneven particle size distribution.

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Abstract

La présente invention concerne un procédé de préparation d'un précurseur de matériau actif d'électrode positive, pour une batterie secondaire au lithium, et un procédé de préparation d'un matériau actif d'électrode positive l'utilisant. Le procédé de préparation d'un précurseur de matériau actif d'électrode positive destiné à une batterie secondaire au lithium au moyen d'un réacteur de type discontinu comprend les étapes consistant : (1) à ajouter en continu dans un réacteur de type discontinu une solution contenant un métal de transition, comprenant des cations de métal de transition, une solution aqueuse alcaline et une solution contenant des ions ammonium et à former des particules précurseurs de matériau actif d'électrode positive ; (2) si le réacteur de type discontinu est plein, à arrêter l'ajout des solutions et à précipiter les particules précurseurs de matériau actif d'électrode positive formées ; (3) à évacuer vers l'extérieur un surnageant qui est produit après la précipitation des particules de précurseur de matériau actif d'électrode positive ; (4) à réguler le pH, qui a diminué pendant l'évacuation du surnageant, à un pH de 10 à 12 au moyen de l'ajout de la solution contenant des ions ammonium ; et (5) à ajouter en continu à nouveau dans le réacteur de type discontinu la solution contenant un métal de transition, comprenant des cations de métal de transition, la solution aqueuse alcaline et la solution contenant des ions ammonium et à faire croître les particules de précurseur de matériau actif d'électrode positive.
PCT/KR2018/001607 2017-02-06 2018-02-06 Précurseur de matériau actif d'électrode positive pour une batterie secondaire au lithium et procédé de préparation de matériau actif d'électrode positive WO2018143783A1 (fr)

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CN201880003900.8A CN109843810B (zh) 2017-02-06 2018-02-06 制备锂二次电池用正极活性材料前体和正极活性材料的方法
US16/333,378 US10892471B2 (en) 2017-02-06 2018-02-06 Methods of preparing positive electrode active material precursor for lithium secondary battery and positive electrode active material

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112142125A (zh) * 2020-09-29 2020-12-29 山东精工电子科技有限公司 二次生长法制备高镍三元正极材料的方法
CN113748541A (zh) * 2019-09-26 2021-12-03 株式会社Lg化学 二次电池用正极活性材料前体、其制备方法和正极活性材料的制备方法
CN114728812A (zh) * 2020-03-20 2022-07-08 株式会社Lg化学 制备锂二次电池用正极活性材料前体的方法、正极活性材料前体以及通过使用所述前体制备的正极活性材料、正极和锂二次电池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110083383A (ko) * 2010-01-14 2011-07-20 주식회사 에코프로 회분식 반응기(ｂａｔｃｈ ｒｅａｃｔｏｒ)를 사용하여 농도구배층을 가지는 리튬 이차 전지용 양극활물질 전구체, 양극활물질을 제조하는 방법, 및 이에 의하여 제조된 리튬 이차 전지용 양극활물질 전구체, 양극활물질
WO2012011785A2 (fr) * 2010-07-22 2012-01-26 주식회사 에코프로 Procédé de production d'une matière active d'anode utile pour un accumulateur au lithium, matière active d'anode pour un accumulateur au lithium produite au moyen du procédé et accumulateur au lithium utilisant ladite matière active d'anode
KR20130009739A (ko) * 2011-06-07 2013-01-23 스미토모 긴조쿠 고잔 가부시키가이샤 니켈 망간 복합 수산화물 입자와 그 제조 방법, 비수계 전해질 이차 전지용 양극 활물질 및 제조 방법과 비수계 전해질 이차 전지
KR20150050459A (ko) * 2013-10-31 2015-05-08 주식회사 엘지화학 리튬이차전지용 양극활물질 전구체 제조방법 및 이를 이용한 양극활물질 및 리튬이차전지
KR20150075200A (ko) * 2013-12-24 2015-07-03 주식회사 포스코 양극 활물질 전구체의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110083383A (ko) * 2010-01-14 2011-07-20 주식회사 에코프로 회분식 반응기(ｂａｔｃｈ ｒｅａｃｔｏｒ)를 사용하여 농도구배층을 가지는 리튬 이차 전지용 양극활물질 전구체, 양극활물질을 제조하는 방법, 및 이에 의하여 제조된 리튬 이차 전지용 양극활물질 전구체, 양극활물질
WO2012011785A2 (fr) * 2010-07-22 2012-01-26 주식회사 에코프로 Procédé de production d'une matière active d'anode utile pour un accumulateur au lithium, matière active d'anode pour un accumulateur au lithium produite au moyen du procédé et accumulateur au lithium utilisant ladite matière active d'anode
KR20130009739A (ko) * 2011-06-07 2013-01-23 스미토모 긴조쿠 고잔 가부시키가이샤 니켈 망간 복합 수산화물 입자와 그 제조 방법, 비수계 전해질 이차 전지용 양극 활물질 및 제조 방법과 비수계 전해질 이차 전지
KR20150050459A (ko) * 2013-10-31 2015-05-08 주식회사 엘지화학 리튬이차전지용 양극활물질 전구체 제조방법 및 이를 이용한 양극활물질 및 리튬이차전지
KR20150075200A (ko) * 2013-12-24 2015-07-03 주식회사 포스코 양극 활물질 전구체의 제조 방법

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113748541A (zh) * 2019-09-26 2021-12-03 株式会社Lg化学 二次电池用正极活性材料前体、其制备方法和正极活性材料的制备方法
US20220238871A1 (en) * 2019-09-26 2022-07-28 Lg Chem, Ltd. Positive Electrode Active Material Precursor for Secondary Battery, Preparation Method Thereof, and Method of Preparing Positive Electrode Active Material
CN114728812A (zh) * 2020-03-20 2022-07-08 株式会社Lg化学 制备锂二次电池用正极活性材料前体的方法、正极活性材料前体以及通过使用所述前体制备的正极活性材料、正极和锂二次电池
CN112142125A (zh) * 2020-09-29 2020-12-29 山东精工电子科技有限公司 二次生长法制备高镍三元正极材料的方法

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