WO2011126182A1 - Procédé de production de matériau actif de cathode pour batterie secondaire comprenant un oxyde métallique composite, et matériau actif de cathode pour batterie secondaire comprenant un oxyde métallique composite produit au moyen dudit procédé - Google Patents

Procédé de production de matériau actif de cathode pour batterie secondaire comprenant un oxyde métallique composite, et matériau actif de cathode pour batterie secondaire comprenant un oxyde métallique composite produit au moyen dudit procédé Download PDF

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WO2011126182A1
WO2011126182A1 PCT/KR2010/005732 KR2010005732W WO2011126182A1 WO 2011126182 A1 WO2011126182 A1 WO 2011126182A1 KR 2010005732 W KR2010005732 W KR 2010005732W WO 2011126182 A1 WO2011126182 A1 WO 2011126182A1
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active material
metal composite
composite oxide
secondary battery
cathode active
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English (en)
Korean (ko)
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박성준
신경
김직수
최문호
박석준
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주식회사 에코프로
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Publication of WO2011126182A1 publication Critical patent/WO2011126182A1/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
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a cathode active material for a secondary battery comprising a metal composite oxide, and a cathode active material for a secondary battery comprising a metal composite oxide prepared thereby, more specifically, a metal composite by a coprecipitation method using a dispersant. It relates to a method for producing a cathode active material for a secondary battery comprising an oxide and a metal composite oxide prepared thereby.
  • Nickel cadmium accumulators have been used as secondary batteries consistent with this purpose.
  • Lithium ion secondary batteries have been put into practical use as nickel-hydrogen accumulators and nonaqueous electrolyte secondary batteries as batteries with higher energy density.
  • LiCoO 2 for the positive electrode and carbon for the negative electrode.
  • LiCoO 2 is an excellent material having stable charge and discharge characteristics, excellent electronic conductivity, high stability, and flat discharge voltage characteristics. However, since Co is low in reserve and expensive and toxic to humans, it is desirable to develop other anode materials.
  • LiNiO 2 having a layered structure such as LiCoO 2 exhibits a large discharge capacity but has not been commercialized due to problems in cycle life, thermal instability, and safety at high temperatures.
  • LiNi x Co 1-x O 2 (x 1, 2) or LiNi 1-xy Co x Mn y O 2 (0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5).
  • a positive electrode active material of the composition was attempted but was not satisfactory enough to solve the problems mentioned above.
  • manganese is the most suitable first row transition metal element to replace cobalt at the anode of a lithium battery.
  • manganese oxide and lithium manganese oxide exist in various structures. For example, there are one-dimensional structures, two-dimensional layered structures, three-dimensional framework structures such as alpha-MnO 2 , beta-MnO 2 and gamma-MnO 2 . In many cases, even though lithium is occluded and released, the structural integrity of manganese oxide is not impaired. Therefore, manganese oxides having various structures have been proposed as new anode materials. In particular, complex oxides have been suggested as an alternative as the demand for high capacity batteries is increasing.
  • One such composite metal oxide as manganese oxide is xLi 2 MO 3- (1-x) LiMeO 2 (0 ⁇ x ⁇ 1) having a layered structure.
  • M is a metal element group including at least one element of Mn, Zr, and Ti
  • Me is at least one element of Ni, Co, Mn, Cr, Fe, V, Al, Mg, and Ti.
  • a metal element group is shown.
  • the metal complex oxide exhibits the same layered structure as that of two components of Li 2 MO 3 and LiMeO 2 as a solid solution material, and is present in a form in which excess lithium (overlithiation) is substituted in the transition metal layer.
  • the metal-based compound in the Li 2 MO 3 constituting the oxide In the example of the Mn of the Li 2 MnO 3 used, having the oxidation number of Mn is +4 during charging, the Mn 4 + / 5 + oxidation-reduction potential of oxygen in the band Since present, Mn does not contribute to electrical conduction. In addition, in the case of having a high capacity composition with a practical possibility, the excess of lithium causes lithium to occupy about 10 to 20% of the transition metal layer, so that Mn is basically more than twice the amount of lithium in the same layer.
  • the amount of transition metals, such as Ni and Co, which are involved in is limited, and as a result, the electrical conductivity of the positive electrode active material is reduced, and as a result, there is a problem that the electrical capacity is reduced.
  • the particle size should be reduced and the particle shape should be spherical.
  • Metal composite oxides are manufactured by applying various process methods such as coprecipitation method, solid phase method, spray drying method, etc., but double coprecipitation method is most preferable to increase particle spherical shape.
  • obtaining a final particle of uniform size requires a short nucleation cycle and uniform growth of their initial particles.
  • coprecipitation particles including manganese usually exhibit irregular platelets, and thus there is a problem that the tap density is only about half that of nickel or cobalt.
  • the present invention is to overcome the above-mentioned problems of the prior art, and has a uniform particle size distribution to manufacture a cathode active material for a secondary battery comprising a metal composite oxide having high electrical conductivity and high capacity and high voltage can be produced It is an object of the present invention to provide a cathode active material for a secondary battery comprising the method and the metal composite oxide prepared thereby.
  • the metal composite oxide is represented by the following Chemical Formula 1.
  • M is one or more elements of Al, Mg, Cr, Fe, V, Ti, and 0 ⁇ d ⁇ 0.05.
  • the complex in the step of preparing a composite hydroxide by a) co-precipitation method is ammonia
  • the metal salt including the nickel salt, cobalt salt, manganese salt and the ammonia has a weight ratio of 1: 0.1 to 1: 2.5
  • the pH is characterized in that to maintain a range of 10.5 to 12.5.
  • the step of preparing a composite hydroxide by the co-precipitation method is characterized in that the dispersing agent is added to the nickel salt, cobalt salt, manganese salt, 0.05 to 10wt% relative to the total weight of the complex.
  • the dispersant is sodium dodecyle sulphate (SDS), Cetyl trimethylammonium bromide (CTAB), alkyltrimethylammonium salts, Cetylpyridinium chloride (CPC), Polyethoxylated tallow amine (POEA), Benzalkonium chloride (BAC), Benzethonium chloride (BZT), Dodecyl betaine, Cocamidopropyl betaine, Coco ampho glycinate, Polyacrylate, Alkyl poly (ethylene oxide), Alkylphenol poly (ethylene oxide), polyvinyl alcohol (PVA), Copolymers of poly (ethylene oxide), poly (propylene oxide), Octyl glucoside, Decyl maltoside, Cetyl alcohol, Oleyl alcohol, Cocamide MEA, cocamide DEA, PEG, Polysorbates any one selected from the group consisting of, characterized in that the polyvinyl alcohol.
  • SDS sodium dodecyle sulphate
  • CPC Cety
  • the present invention provides a cathode active material for a secondary battery comprising a metal composite oxide represented by the following Chemical Formula 1.
  • M is one or more elements of Al, Mg, Cr, Fe, V, Ti, and 0 ⁇ d ⁇ 0.05.
  • the cathode active material for a secondary battery including the metal composite oxide has primary particles stacked to form spherical secondary particles, and the aspect ratio is set when the longest diameter of the primary particles is D1 and the shortest diameter is D2. It is characterized in that D1 / D2 is in the range of 1 to 3.5.
  • the cathode active material for a secondary battery including the metal composite oxide is characterized by having a particle size of 1 to 10 ⁇ m.
  • a spherical cathode active material having a uniform particle size distribution may be prepared by uniformly growing initial particles generated by using a dispersant.
  • FIG. 1 is a photograph of the FE-SEM ((a) 5,000 times, (b) 1,000 times) of the composite hydroxide according to an embodiment and a comparative example of the present invention.
  • Figure 3 is a graph showing the particle size distribution of the metal composite oxide according to one embodiment and comparative example of the present invention ((a) Example 1, (b) Comparative Example).
  • FIG. 4 is a graph showing the battery capacity of a lithium secondary battery using a metal composite oxide according to one embodiment and comparative example of the present invention.
  • FIG. 5 is a graph showing battery life of a lithium secondary battery using a metal composite oxide according to one embodiment and a comparative example of the present invention.
  • FIG. 6 is a graph illustrating a cyclic potential current of a lithium secondary battery using a metal composite oxide according to one embodiment and a comparative example of the present invention.
  • FIG. 7 is a graph showing a high rate discharge measurement result of a lithium secondary battery using a metal composite oxide according to one embodiment and a comparative example of the present invention.
  • the present invention provides a method for producing a cathode active material for a secondary battery comprising a metal composite oxide, comprising the steps of: a) preparing a composite hydroxide by coprecipitation by mixing nickel salt, cobalt salt, manganese salt and a complex; b) mixing the composite hydroxide and the lithium compound obtained in step a); And c) calcining the mixture obtained in step b).
  • the method provides a method of manufacturing a cathode active material for a secondary battery comprising a metal composite oxide represented by Chemical Formula 1, comprising: a.
  • the cathode active material for a metal composite oxide secondary battery includes secondary particles in which primary particles are stacked, and the longest diameter of the primary particles is D1 and the shortest diameter is D2.
  • D1 / D2, which is an aspect ratio at the time, is in the range of 1 to 3.5.
  • the cathode active material preferably has a particle size of 1 to 10 ⁇ m.
  • Ni a Co b Mn c is a nickel cobalt manganese metal composite hydroxide by reacting a nickel salt solution, cobalt salt solution, manganese salt solution and a complex (complex agent) and precipitant (OH) 2 is prepared.
  • the co-precipitation process will be described in more detail.
  • the metal salt solution, the complexing agent, and the precipitant are continuously supplied to the reactor, nickel, cobalt, and manganese metal are reacted to prepare Ni a Co b Mn c (OH) 2 .
  • the reaction tank at this time can use a 1-200 L continuous reaction tank, Preferably, a 10-100 L reaction tank can be used.
  • a gas of an inert atmosphere such as nitrogen or argon is flowed into the reactor, and a part of Mn (OH) 2 is MnO 2 , MnO 4, and Mn 2 O 3. Do not oxidize. At this time, the gas is characterized in that 0.1 ⁇ 20L / min.
  • the concentration of the total metal is preferably 1 to 3 M.
  • the concentration of the metal salt is less than 1M, the productivity is poor because the amount of material produced is small, and when the concentration of the metal salt is 3M or more, the metal salt may be precipitated.
  • heating must be performed at 50 ° C or higher. And particle control becomes difficult.
  • water may be used as the solvent.
  • Nickel hydroxide, nickel sulfate, nickel nitrate, nickel acetate, nickel chloride, and the like may be used as the nickel salt, and cobalt hydroxide, cobalt sulfate, cobalt nitrate, and cobalt chloride may be used as the cobalt salt.
  • manganese salt manganese acetate, manganese dioxide, manganese sulfate, manganese chloride may be used.
  • the temperature of the reaction tank can be maintained in the range of 30 to 60 °C.
  • the pH in the reactor is preferably maintained at 10.5 to 12.5.
  • the mixing ratio of the metal salt including the nickel salt, cobalt salt, manganese salt and the complex is preferably a molar ratio of 1: 0.1 to 1: 2.5, it is preferable to react the materials in these reactors while stirring at a rate of 200 to 1000rpm desirable.
  • the reaction time is preferably synthesized for 5 to 20 hours.
  • the ammonia used as a complexing agent serves to control the shape of the complex hydroxide to be formed
  • the alkaline solution is a pH adjusting agent to maintain a range of 10.5 to 12.5, which is a pH range suitable for coprecipitation in the mixed aqueous solution. It is desirable to.
  • Extracting the co-precipitation product at the beginning after co-precipitation forms a spherical (secondary particle) composite hydroxide of nickel-cobalt-manganese metal in which needle-like fine particles (primary particles) are aggregated.
  • a complex hydroxide having a uniform particle size may be prepared by simultaneously adding a predetermined amount of dispersant when the complex is added in the preparation of the composite hydroxide by coprecipitation.
  • obtaining a final active material particles of uniform size requires a short nucleation cycle and uniform growth of their initial particles. Therefore, in the present invention, the dispersant is added simultaneously for uniform growth of the initial particles produced.
  • the dispersants include sodium dodecyle sulphate (SDS), Cetyl trimethylammonium bromide (CTAB), alkyltrimethylammonium salts, Cetylpyridinium chloride (CPC), Polyethoxylated tallow amine (POEA), Benzalkonium chloride (BAC), Benzethonium chloride (BZT), Codecyldopropyle betaine, Coco ampho glycinate, Polyacrylate, Alkyl poly (ethylene oxide), Alkylphenol poly (ethylene oxide), polyvinyl alcohol (PVA), Copolymers of poly (ethylene oxide), poly (propylene oxide), Octyl glucoside, Decyl maltoside, Cetyl alcohol Oleyl alcohol, Cocamide MEA, cocamide DEA, PEG and Polysorbates can be used. Of these, polyvinyl alcohol (PVA) is most preferred.
  • the dispersant to be added is preferably added to 0.05 ⁇ 10wt% relative to the total weight of the nickel salt, cobalt salt, manganese salt, the complex.
  • the dispersant is less than 0.05wt% relative to the total weight of nickel salt, cobalt salt, manganese salt and complex, very non-uniform active material particles having insufficient stereostability of particles are formed, and when the amount of dispersant is 10wt% or more, the particle average diameter is 1 ⁇ m. The following particles are produced.
  • ammonia is used as the complexing agent, and the particle form of the composite hydroxide can be easily adjusted by adjusting the dispersant concentration, the ratio of the ammonia water and the metal salt, and the pH in the reactor.
  • the composite hydroxide obtained in the step of preparing hydroxide by the coprecipitation method is sufficiently mixed with the lithium compound, and the resulting mixture is calcined at 850 ° C to 1050 ° C.
  • Lithium metal composite oxide can be produced by calcination for 20 hours.
  • a cathode active material for a secondary battery including a metal composite oxide capable of implementing high capacity according to the present invention is a metal composite oxide particle composed of Li, Ni, Co, and Mn, and the metal composite oxide particle satisfies the following [Formula 1]. .
  • M is one or more elements of Al, Mg, Cr, Fe, V, Ti, and 0 ⁇ d ⁇ 0.05.
  • Nickel sulfate, cobalt sulfate, and manganese sulfate were mixed in a 2.5 M aqueous metal solution at a concentration of 0.29: 0.13: 0.58 at 0.8 liter / hour, and ammonia was maintained at 0.8 [concentration of ammonia solution / concentration of aqueous metal solution].
  • the aqueous solution was continuously added to the reactor.
  • 0.5% polyvinyl alcohol (PVA) solution compared to the ammonia metal salt was simultaneously added to the aqueous ammonia solution for controlling the particle size and uniform distribution.
  • the pH was adjusted to maintain a pH of 11.5 by supplying a 25% sodium hydroxide aqueous solution to adjust the pH, the average residence time of the solution was adjusted to a flow rate of about 10 hours, the average temperature of the reactor maintained at 45 °C ⁇ 55 °C It was.
  • a precursor and a cathode active material powder in the form of a composite hydroxide were obtained in the same manner as in Example 1, except that alkyl poly was used instead of polyvinyl alcohol as the dispersant.
  • Example 2 In the same manner as in Example 1, except that a polyethylene glycol (PEG) solution having a molecular weight of 600 was used instead of polyvinyl alcohol, a precursor and a positive electrode active material powder in the form of a gold complex hydroxide were obtained.
  • PEG polyethylene glycol
  • a precursor and a cathode active material powder in the form of a composite hydroxide were obtained in the same manner as in Example 1 except that a polyethylene glycol (PEG) solution having a molecular weight of 4,000 was used instead of polyvinyl alcohol.
  • PEG polyethylene glycol
  • a precursor and a cathode active material powder in the form of a composite hydroxide were obtained in the same manner as in Example 1 except that a polyacrylate solution was used instead of polyvinyl alcohol as a dispersant.
  • Example 2 Except not using a polyvinyl alcohol solution as a dispersant in the same manner as in Example 1 to obtain a precursor and a positive electrode active material powder in the form of a composite hydroxide.
  • Figure 1 shows the FE-SEM ((a) 5,000 times, (b) 1,000 times) photograph of the composite hydroxide form precursors made in Examples and Comparative Examples
  • Figure 2 is a FE of the positive electrode active material made in Examples and Comparative Examples -SEM ((a) 5,000 times, (b) 1,000 times) The photograph is shown.
  • the precursor of the composite hydroxide type synthesized according to the present invention and the positive electrode active material of the metal composite oxide type have elliptical primary particles, but the secondary particles aggregated with the primary particles have a spherical shape.
  • the primary particles produced in the comparative example were close to elliptical or needle-shaped, and the secondary particles in which the primary particles were agglomerated maintained a spherical shape, but a macromolecule of 20 ⁇ m or more was distributed.
  • Example 1 The results of analyzing the composite hydroxide particle size distribution of Example 1 and Comparative Example are shown in FIG. 3. As shown in FIG. 3, the particle size was more uniformly distributed in the embodiment of the present invention using the dispersant than in the comparative example in which the dispersant was not used in the coprecipitation reaction.
  • the positive electrode active material for a lithium secondary battery prepared according to Example 1 and Comparative Example, and acetylene black as a conductive agent, and polyvinylidene fluoride (PVdF product name: solef6020) as a binder were mixed at a weight ratio of 90: 5: 5 to slurry.
  • the slurry was uniformly applied to an aluminum foil having a thickness of 20 ⁇ m, and vacuum dried at 130 ° C. to prepare a cathode for a lithium secondary battery.
  • Coin battery was prepared by the conventional method.
  • the lithium secondary battery of Preparation Example 1 was evaluated for the positive electrode active material characteristics using an electrochemical analyzer in the range 2.0 to 4.55V.
  • the battery capacity was measured by charging and discharging at 0.170 mW, and the results are shown in FIG. 4 and Table 1 below.
  • the discharge capacity of the cathode active material prepared in Example 1 is 210 mAh / g or more, which is higher than 160mAh / g, which is an average discharge capacity of currently commercialized LiCoO 2 , and higher than that of the comparative example. It was confirmed that it has.
  • Discharge capacity was measured while charging and discharging the lithium secondary battery of Preparation Example 1 at 0.7 mAh / g 50 times in a range of 2.2 to 4.55 V, and the results are shown in FIG. 5. As shown in FIG. 5, the lithium secondary battery using the cathode active material prepared in Example 1 was confirmed that the discharge capacity hardly changed even after 50 times of charge and discharge.
  • the discharge capacity retention rate gradually decreased according to the number of cycles, and thus it was confirmed that the lithium secondary battery became less than 90% after 50 charge and discharge cycles.
  • Example 1 the current began to increase at about 4.0V during the first reduction process, and exhibited a maximum current at about 4.5V.
  • the current increase due to lithium deposition was found at about 4.0V.
  • a current peak due to oxidation of lithium reduced at 3.6V was observed.
  • the peak of 3.6V is an oxidation peak corresponding to the reduction peak at 4.0V, and it can be seen that one type of redox reaction other than lithium precipitation occurs.
  • the current began to increase at about 3.8V in the first reduction process, and showed a maximum current at about 4.6V.
  • the current increase due to lithium deposition was found at about 3.8V.
  • a current peak due to oxidation of lithium reduced at 4.4V was observed.
  • the peak of 4.6V is an oxidation peak corresponding to the reduction peak at 4.4V, and it was confirmed that other types of redox reactions appeared.
  • the peak which appeared at 4.4V during discharge disappeared and the oxidation peak appeared at 3.7V and 2.0V. This shows a potential plateau at a lower potential than the first redox process, i.e., it can be seen that the reaction proceeds differently from the first reduction process.
  • the discharge capacity (0.1C, 1.0C, 1.5C, 2.0C, and 5C) of the batteries of Example 1 and Comparative Example were measured at 0.1C, 1.0C, 1.5C, 2.0C, and 5C rates, respectively, and as a result, Are shown in FIG. 7 and Table 2, respectively.
  • Example 1 Comparative example mAh / g % 0.1C 233.6 219.7 100.0% 100.0% 0.2C 218.3 200.8 93.5% 91.4% 0.5C 201.5 178.9 86.3% 81.4% 1.0C 187.3 159.3 80.2% 72.5% 1.5C 176.9 148.6 75.7% 67.6% 2.0C 168.9 138.4 72.3% 63.0% 5.0C 149.3 108.9 63.9% 49.6%
  • Example 1 As shown in FIG. 7 and Table 2, in the low-rate discharge (0.1C), the battery characteristics of Example 1 and the comparative example were almost similar, but as the high-rate discharge, the battery of Example 1 had a much smaller reduction in discharge capacity than the battery of the comparative example. It was confirmed that less.

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Abstract

L'invention concerne un procédé de production de matériau actif de cathode pour batterie secondaire comprenant un oxyde métallique composite, et un matériau actif de cathode pour batterie secondaire comprenant un oxyde métallique composite produit au moyen dudit procédé. Le matériau actif de cathode pour batterie secondaire comprenant un oxyde métallique composite produit selon l'invention est un oxyde métallique composite composé de Li, Ni, Co et Mn, et satisfait la formule chimique 1 suivante: Li(1+a)NixCo[(1-a)(1-y)-x]Mn[a+(1-a)y] MdO(a+2) (où, 0,01≤a≤0,30, 0,01≤x≤0,6, 0,01≤y≤0,8, M représente Al, Mg, Cr, Fe, V, et/ou Ti, et 0≤d≤0,05.)
PCT/KR2010/005732 2010-04-09 2010-08-26 Procédé de production de matériau actif de cathode pour batterie secondaire comprenant un oxyde métallique composite, et matériau actif de cathode pour batterie secondaire comprenant un oxyde métallique composite produit au moyen dudit procédé WO2011126182A1 (fr)

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CN114956202A (zh) * 2022-04-28 2022-08-30 南通金通储能动力新材料有限公司 一种钠离子正极材料的前驱体、制备方法及正极材料
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CN115004413A (zh) * 2021-09-15 2022-09-02 宁德新能源科技有限公司 一种电化学装置和电子装置
CN114956202A (zh) * 2022-04-28 2022-08-30 南通金通储能动力新材料有限公司 一种钠离子正极材料的前驱体、制备方法及正极材料
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