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WO2019190217A1 - Précurseur de matériau actif de cathode et accumulateur au lithium l'utilisant - Google Patents

Précurseur de matériau actif de cathode et accumulateur au lithium l'utilisant Download PDF

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Publication number
WO2019190217A1
WO2019190217A1 PCT/KR2019/003624 KR2019003624W WO2019190217A1 WO 2019190217 A1 WO2019190217 A1 WO 2019190217A1 KR 2019003624 W KR2019003624 W KR 2019003624W WO 2019190217 A1 WO2019190217 A1 WO 2019190217A1
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Prior art keywords
active material
positive electrode
material precursor
electrode active
secondary battery
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
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PCT/KR2019/003624
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English (en)
Korean (ko)
Inventor
노미정
김직수
김상복
하동욱
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SK Innovation Co Ltd
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SK Innovation Co Ltd
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Priority claimed from KR1020190033031A external-priority patent/KR102495992B1/ko
Application filed by SK Innovation Co Ltd filed Critical SK Innovation Co Ltd
Priority to CN201980023350.0A priority Critical patent/CN112219297B/zh
Priority to US17/041,959 priority patent/US12512468B2/en
Publication of WO2019190217A1 publication Critical patent/WO2019190217A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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 positive electrode active material precursor and a lithium secondary battery using the same. More specifically, the present invention relates to a positive electrode active material precursor including a plurality of metal elements and a lithium secondary battery using the same.
  • Secondary batteries are batteries that can be repeatedly charged and discharged and have been widely applied to portable electronic communication devices such as camcorders, mobile phones, notebook PCs, etc. according to the development of the information communication and display industries.
  • Examples of secondary batteries include lithium secondary batteries, nickel-cadmium batteries, nickel-hydrogen batteries, and the like.
  • lithium secondary batteries have a high operating voltage and high energy density per unit weight, and are advantageous for charging speed and light weight. It has been actively developed and applied in that respect.
  • the lithium secondary battery may include an electrode assembly including a positive electrode, a negative electrode, and a separator (separator), and an electrolyte impregnating the electrode assembly.
  • the lithium secondary battery may further include, for example, a pouch type exterior material containing the electrode assembly and the electrolyte.
  • Lithium metal oxide may be used as an active material for a positive electrode of a lithium secondary battery.
  • the lithium metal oxide include nickel-based lithium metal oxides.
  • Nickel-containing precursor compounds are used to prepare the nickel-based lithium metal oxides.
  • the content of nickel has been increased to secure sufficient capacity and output characteristics.
  • the proportion of nickel in the nickel-containing precursor increases. do.
  • the reliability of the positive electrode active material may decrease due to mismatches and side reactions with lithium.
  • Korean Patent Publication No. 10-0821523 discloses a method of manufacturing a positive electrode active material using a lithium composite metal oxide, but does not consider the above-described nickel-containing precursor.
  • One object of the present invention is to provide a positive electrode active material precursor that can provide improved output and stability.
  • One object of the present invention is to provide a positive electrode active material and a lithium secondary battery prepared from a positive electrode active material precursor capable of providing improved output and stability.
  • the positive electrode active material precursor according to the exemplary embodiments includes nickel (Ni) and cobalt (Co), and contains an excess of nickel, and the area (A 001 ) of the (001) plane peak by X-ray diffraction analysis.
  • the ratio of the area (A 101 ) of the (101) plane peak to (A 101 / A 001 ) may be greater than or equal to 1, and the intensity of the (101) plane peak with respect to the intensity (I 001 ) of the ( 001 ) plane peak (I 101).
  • the ratio I 101 / I 001 may be one or more.
  • a 101 / A 001 can range from 1 to 2.
  • I 101 / I 001 may range from 1 to 2.
  • the cathode active material precursor may be represented by Formula 1 below.
  • M is Mg, Sr, Ba, B, Al, Si, Mn, Ti, Zr or W There may be at least one.
  • the content ratio of Ni in Ni, Co, and Mn may be 0.75 to 0.95.
  • the content of Co may be higher than the content of Mn.
  • a cathode active material formed from the cathode active material precursor is provided.
  • the cathode active material may be represented by Formula 2 below.
  • the long axis length of the primary particles of the positive electrode active material may be 1.5 to 7 times the short axis length.
  • a lithium secondary battery including a positive electrode including a positive electrode active material formed from the positive electrode active material precursor, and a separator disposed between the positive electrode and the negative electrode is provided.
  • the positive electrode active material precursor according to embodiments of the present invention may include, for example, an excessive amount of nickel to provide high output and high capacity.
  • the positive electrode active material precursor has a predetermined A 101 / A 001 range through XRD analysis, and may have an improved crystallinity.
  • the positive electrode active material and the lithium secondary battery may have a high output, a high capacity, and an improved long life and stability through the positive electrode active material precursor.
  • FIG. 1 is a schematic cross-sectional view of a lithium secondary battery according to example embodiments.
  • 2A and 2B are XRD and capacity retention analysis graphs of the positive electrode active material precursor and the secondary battery according to Example 1 and Comparative Example 1, respectively.
  • 3A and 3B are XRD and capacity retention analysis graphs of the positive electrode active material precursor and the secondary battery according to Example 2 and Comparative Example 2, respectively.
  • 4A and 4B are XRD and capacity retention analysis graphs of the positive electrode active material precursor and the secondary battery according to Example 3 and Comparative Example 3, respectively.
  • 5A and 5B are XRD and capacity retention analysis graphs of the positive electrode active material precursor and the secondary battery according to Example 4 and Comparative Example 4, respectively.
  • 6A and 6B are XRD and capacity retention analysis graphs of the positive electrode active material precursor and the secondary battery according to Example 5 and Example 6, respectively.
  • Embodiments of the present invention are, for example, nickel-cobalt-based containing nickel (Ni) and cobalt (Co) -based, in one embodiment nickel-cobalt-manganese (NCM) -based positive electrode active material can be prepared as a precursor A positive electrode active material precursor having a predetermined A 101 / A 001 range by X-ray diffraction analysis is provided.
  • NCM nickel-cobalt-manganese
  • embodiments of the present invention provides a lithium secondary battery including a cathode active material prepared through the cathode active material precursor, and a cathode manufactured from the cathode active material.
  • the cathode active material precursor according to exemplary embodiments of the present invention includes a nickel-cobalt-based compound, preferably a nickel-cobalt-manganese (NCM) -based compound, and may include, for example, an NCM-based hydroxide.
  • NCM nickel-cobalt-manganese
  • the cathode active material precursor may be represented by the following Chemical Formula 1.
  • M represents a dopant or a transition metal.
  • M may include, for example, Mg, Sr, Ba, B, Al, Si, Mn, Ti, Zr or W. These may be included alone or in combination of two or more.
  • the positive electrode active material precursor includes an excess (for example, the highest amount) of Ni among the metal elements included, and the content or concentration of Ni may be about 0.6 or more. Accordingly, the output and capacity of a sufficient secondary battery can be secured through the use of excess Ni.
  • the content of Ni can be adjusted in the range of about 0.75 to 0.95.
  • Co may be included to improve life stability and capacity retention characteristics through Mn while maintaining electrical conductivity.
  • M may be included as a dopant to further enhance long-term stability and high temperature stability.
  • the content or concentration of Co may be greater than Mn. Accordingly, the conductivity can be increased by lowering the resistance through the cathode active material. Relatively decreasing the long-term capacity stability due to the decrease in the Mn content or concentration can be compensated for or improved through the adjustment of A 101 / A 001 which will be described later.
  • the cathode active material precursor may have about 1 or more A 101 / A 001 .
  • a 101 represents the peak area of the (101) plane by X-ray diffraction (XRD) analysis of the positive electrode active material precursor
  • a 001 refers to the (001) plane of the (001) plane by XRD analysis. The peak area is shown. Accordingly, A 101 / A 001 represents the area ratio of the XRD peak of the (101) plane to the (001) plane.
  • the XRD analysis is performed using a diffraction angle of 15 ° to 90 ° using Cu K ⁇ rays as a light source for a powder sample dried at 110 ° C to 250 ° C after synthesizing the positive electrode active material precursor. 2 ⁇ ) at a scan rate of 0.02 o / step.
  • the positive electrode active material generated through the positive electrode active material precursor having the range XRD analysis result has excellent crystallinity, and thus it is possible to stably maintain excellent output and capacity characteristics for a long time even during repeated charging and discharging operations.
  • the Ni content when the Ni content is increased, cation disturbance due to interchange of Ni and lithium (Li) may occur, and Ni ions may occupy Li ion sites. Accordingly, sufficient crystallinity of the cathode active material may not be secured from the cathode active material precursor.
  • the firing temperature is increased to increase the crystallinity, a desired crystal structure may not be formed due to a topotactic transition in which lithium ions in the cathode active material precursor are substituted.
  • a 101 / A 001 of the positive electrode active material precursor may be adjusted to about 1 or more to obtain a positive electrode active material that produces excellent crystallinity while using high content Ni without excessively increasing the firing temperature. . Therefore, a secondary battery having improved high output, high capacity, and long lifespan can be obtained.
  • a 101 / A 001 of the positive electrode active material precursor may be adjusted by changing the amount of O 2 , reaction time, reaction temperature, etc. in the coprecipitation reaction for forming the precursor.
  • a 101 / A 001 can be adjusted in the range of about 1 to 2, preferably in the range of about 1 to about 1.6.
  • the cathode active material precursor may have about 1 or more I 101 / I 001 .
  • I 101 refers to the peak intensity (or peak height) of the (101) plane by X-ray diffraction (XRD) analysis of the positive electrode active material precursor, and "I 001 Indicates peak intensities of the (001) plane by XRD analysis. Accordingly, I 101 / I 001 represents the intensity ratio of the XRD peak of the (101) plane to the (001) plane.
  • XRD X-ray diffraction
  • both the above-described area ratio (A 101 / A 001 ) and strength ratio (I 101 / I 001 ) satisfy at least one, so that it is easier and more effective to implement the improved crystallinity and high content Ni structure. have.
  • I 101 / I 001 can be adjusted in the range of about 1 to 2, preferably in the range of about 1 to 1.6.
  • the positive electrode active material precursor described above may be prepared through coprecipitation of metal salts.
  • the metal salts may include nickel salts, manganese salts and cobalt salts.
  • nickel salts examples include nickel sulfate, nickel hydroxide, nickel nitrate, nickel acetate, hydrates thereof, and the like.
  • manganese salts examples include manganese sulfate, manganese acetate, hydrates thereof, and the like.
  • cobalt salts examples include cobalt sulfate, cobalt nitrate, cobalt carbonate, and hydrates thereof.
  • the metal salts may be mixed with a precipitant and / or a chelating agent in a ratio that satisfies the content or concentration ratio of each metal described with reference to Formula 1 to prepare an aqueous solution.
  • the aqueous solution may be co-precipitated in a reactor to prepare a cathode active material precursor.
  • the precipitant may include an alkaline compound such as sodium hydroxide (NaOH), sodium carbonate (Na 2 CO 3 ), and the like.
  • the chelating agent may include, for example, ammonia water (eg, NH 3 H 2 O), ammonium carbonate (eg, NH 3 HCO 3 ), and the like.
  • the temperature of the coprecipitation reaction can be controlled, for example, in the range of about 40 ° C to 60 ° C.
  • the reaction time can be adjusted in the range of about 24 to 72 hours.
  • Embodiments of the present invention provide a cathode active material formed from the cathode active material precursor described above.
  • the cathode active material may be represented by Formula 2 below.
  • a lithium precursor compound may be mixed with the cathode active material precursor and reacted through a coprecipitation method to prepare a cathode active material.
  • the lithium precursor compound may include, for example, lithium carbonate, lithium nitrate, lithium acetate, lithium oxide, lithium hydroxide, and the like. These may be used alone or in combination of two or more.
  • lithium impurities or unreacted precursors may be removed through a water washing process, and metal particles may be fixed or crystallinity may be increased through a heat treatment process.
  • the heat treatment temperature may range from about 600 °C to 1000 °C.
  • the primary particles of the cathode active material prepared from the cathode active material precursor may have rods, ellipses, or rods having different major and minor axes.
  • the length of the long axis of the primary particles may be about 1.5 to 7 times the length of the short axis.
  • Embodiments of the present invention provide a lithium secondary battery including a cathode active material prepared from the cathode active material precursor described above.
  • FIG. 1 is a schematic cross-sectional view of a lithium secondary battery according to example embodiments.
  • a lithium secondary battery may include a positive electrode 130, a negative electrode 140, and a separator 150 interposed between the positive electrode and the negative electrode.
  • the positive electrode 130 may include the positive electrode active material layer 115 formed by applying the positive electrode active material to the positive electrode current collector 110.
  • the cathode active material may be manufactured using the cathode active material precursor according to the above-described exemplary embodiments.
  • the positive electrode active material precursor may be, for example, represented by Formula 1 and may have an A 101 / A 001 of about 1 or more.
  • the cathode active material represented by Chemical Formula 2 may be manufactured through the cathode active material precursor. Accordingly, a lithium secondary battery in which a high crystallinity of the positive electrode is increased and a high output and high capacity characteristics are stably maintained for a long time can be manufactured.
  • a slurry may be prepared by mixing and stirring the positive electrode active material in a solvent, a binder, a conductive material and / or a dispersant, and the like. After coating the slurry on the positive electrode current collector 110, the cathode 130 may be manufactured by compressing and drying the slurry.
  • the positive electrode current collector 110 may include, for example, stainless steel, nickel, aluminum, titanium, copper, or an alloy thereof, and may preferably include aluminum or an aluminum alloy.
  • the binder is, for example, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethylmethacryl Organic binders such as polymethylmethacrylate, or aqueous binders such as styrene-butadiene rubber (SBR), and may be used together with a thickener such as carboxymethyl cellulose (CMC).
  • PVDF series binder can be used as a binder for positive electrode formation. In this case, the amount of the binder for forming the positive electrode active material layer may be reduced, thereby improving output and capacity of the secondary battery.
  • the conductive material may be included to promote electron transfer between active material particles.
  • the conductive material may be a carbon-based conductive material such as graphite, carbon black, graphene, carbon nanotubes, and / or perovskite materials such as tin, tin oxide, titanium oxide, LaSrCoO 3 , and LaSrMnO 3. It may include a metal-based conductive material including a.
  • the negative electrode 140 may include the negative electrode current collector 120 and the negative electrode active material layer 125 formed by coating the negative electrode active material on the negative electrode current collector 120.
  • the negative electrode active material may be used without particular limitation that is known in the art that can occlude and desorb lithium ions.
  • carbon-based materials such as crystalline carbon, amorphous carbon, a carbon composite, carbon fiber; Lithium alloys; Silicon or tin and the like can be used.
  • the amorphous carbon include hard carbon, coke, mesocarbon microbead (MCMB) fired at 1500 ° C. or lower, mesophase pitch-based carbon fiber (MPCF), and the like.
  • Examples of the crystalline carbon include graphite-based carbon such as natural graphite, graphitized coke, graphitized MCMB, graphitized MPCF, and the like.
  • the element included in the lithium alloy include aluminum, zinc, bismuth, cadmium, antimony, silicon, lead, tin, gallium or indium.
  • the negative electrode current collector 120 may include, for example, gold, stainless steel, nickel, aluminum, titanium, copper, or an alloy thereof, and may preferably include copper or a copper alloy.
  • a slurry may be prepared by mixing and stirring the negative electrode active material in a solvent, a binder, a conductive material and / or a dispersant, and the like. After coating the slurry on the negative electrode current collector 120, the negative electrode 140 may be manufactured by compressing and drying the slurry.
  • the binder and the conductive material materials substantially the same as or similar to those described above may be used.
  • the binder for the formation of the negative electrode may include an aqueous binder such as styrene-butadiene rubber (SBR), for example, for compatibility with the carbon-based active material, and such as carboxymethyl cellulose (CMC). Can be used with thickeners.
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • the separator 150 may be interposed between the anode 130 and the cathode 140.
  • the separator 150 may include a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / methacrylate copolymer, and the like.
  • the separator may include a nonwoven fabric formed of high melting glass fibers, polyethylene terephthalate fibers, or the like.
  • an area eg, contact area of the separator 150
  • a volume of the cathode 140 may be larger than that of the anode 130. Accordingly, lithium ions generated from the anode 130 may be smoothly moved to the cathode 140 without being deposited in the middle. Therefore, the effect of simultaneous improvement of output and stability through the combination with the above-described positive electrode active material precursor or the positive electrode active material can be more easily realized.
  • the electrode cell 160 is defined by the anode 130, the cathode 140, and the separator 150, and the plurality of electrode cells 160 are stacked to, for example, jelly rolls ( An electrode assembly in the form of a jelly roll may be formed.
  • the electrode assembly may be formed by winding, laminating, or folding the separator.
  • the electrode assembly may be accommodated together with an electrolyte in the exterior case 170 to define a lithium secondary battery.
  • a nonaqueous electrolyte may be used as the electrolyte.
  • the non-aqueous electrolyte comprising an electrolyte of a lithium salt and an organic solvent, wherein the lithium salt is for example Li + X - is represented by the lithium salt anion (X -) as F -, Cl -, Br -, I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, ( CF 3) 5 PF -, ( CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO - , (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3
  • organic solvent examples include propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC).
  • PC propylene carbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • Methylpropyl carbonate, dipropyl carbonate, dimethylsulfuroxide, acetonitrile, dimethoxyethane, diethoxyethane, vinylene carbonate, sulfolane, gamma-butyrolactone, propylene sulfite, tetrahydrofuran and the like can be used. . These may be used alone or in combination of two or more.
  • Electrode tabs may be formed from the positive electrode collector 110 and the negative electrode collector 120 belonging to each electrode cell, respectively, and may extend to one side of the exterior case 170.
  • the electrode tabs may be fused together with the one side of the exterior case 170 to form an electrode lead extending or exposed to the outside of the exterior case 170.
  • the lithium secondary battery may be manufactured in, for example, a cylindrical shape, a square shape, a pouch type or a coin type using a can.
  • NiSO 4 , CoSO 4 , and MnSO 4 were mixed at a ratio of 0.75: 0.15: 0.10 using distilled water from which internal dissolved oxygen was removed by bubbling with N 2 for 24 hours.
  • a precipitating agent respectively, and a chelating agent as a positive electrode active material precursor of 14 ⁇ m Ni 0.75 Co 0.15 Mn 0.1 ( OH) 2 was obtained.
  • the precursor obtained was dried at 80 ° C. for 12 hours and then re-dried at 110 ° C. for 12 hours.
  • Lithium hydroxide and the positive electrode active material precursor were added to the dry high speed mixer in a ratio of 1.05: 1 and mixed uniformly for 5 minutes.
  • the mixture was placed in a kiln and the temperature was raised to 710 ° C at a temperature increase rate of 2 ° C / min, and maintained at 710 ° C for 10 hours.
  • Oxygen was passed continuously at a flow rate of 10 mL / min during elevated temperature and maintenance. After completion of the calcination, natural cooling was performed to room temperature, followed by grinding and classification to obtain a positive electrode active material LiNi 0.75 Co 0.15 Mn 0.1 O 2 .
  • a slurry was prepared by mixing the positive electrode active material, carbon black as a conductive material, and polyvinylidene fluoride (PVDF) as a binder at a weight ratio of 94: 3: 3.
  • the slurry was uniformly applied to an aluminum foil having a thickness of 15 ⁇ m, and vacuum dried at 130 ° C. to prepare a positive electrode for a lithium secondary battery.
  • a liquid electrolyte in which LiPF 6 is dissolved at a concentration of 1.0 M, a battery cell in the form of a coin half cell was manufactured according to a commonly known manufacturing process.
  • NiSO 4 , CoSO 4 and MnSO 4 were mixed in distilled water at a ratio of 0.75: 0.15: 0.10, respectively.
  • the solution in the reactor of 60 °C and NaOH and NH 3 to H 2 O as the positive electrode active material precursor by a coprecipitation reaction proceeds for 24 hours by using a zero rating precipitating agent and skill of 14 ⁇ m Ni 0.75 Co 0.15 Mn 0.1 ( OH) 2 Obtained.
  • the precursor obtained was dried at 80 ° C. for 12 hours and then re-dried at 110 ° C. for 12 hours.
  • cathode active material precursor a cathode active material and a secondary battery (battery cell) were manufactured in the same manner as in Example 1.
  • a positive electrode active material precursor, a positive electrode active material, and a secondary battery were prepared in the same manner as in Example 1 and Comparative Example 1, except that NiSO 4 , CoSO 4 , and MnSO 4 were respectively mixed at 0.80: 0.11: 0.09.
  • a positive electrode active material precursor, a positive electrode active material, and a secondary battery were prepared in the same manner as in Example 1 and Comparative Example 1, except that NiSO 4 , CoSO 4 , and MnSO 4 were respectively mixed at 0.88: 0.09: 0.03.
  • a positive electrode active material precursor, a positive electrode active material, and a secondary battery were prepared in the same manner as in Example 1 and Comparative Example 1, except that NiSO 4 , CoSO 4 , and MnSO 4 were respectively mixed at 0.92: 0.05: 0.03.
  • the positive electrode of Examples 5 and 6 in the same manner as in Example 2 except that NiSO 4 , CoSO 4 , MnSO 4 were mixed at 0.80: 0.09: 0.11, respectively, and the reaction temperature was adjusted to 50 ° C. and 60 ° C., respectively.
  • An active material precursor, a positive electrode active material, and a secondary battery were prepared.
  • the discharge capacity of the secondary batteries according to Examples and Comparative Examples was measured by charging (CC / CV 0.5C 4.3V 0.05CA CUT-OFF) and discharging (CC 1.0C 3.0V CUT-OFF).
  • the capacity retention rate was evaluated as a percentage of the value obtained by dividing the discharge capacity at 200 times by the discharge capacity at one time by repeating 200 cycles performed when the 1C discharge capacity was measured.
  • the positive electrode active material precursors of the embodiments satisfying at least one of A 101 / A 001 and I 101 / I 001 exhibited a capacity retention of 70% or more, but are comparative examples.
  • the retention was significantly reduced after 200 cycles at the same composition and capacity.
  • the long-term stability deteriorates rapidly as the content of Ni increases.
  • Example 6 in the case of Example 6, as the values of A 101 / A 001 and I 101 / I 001 are slightly increased, the capacity retention ratio is reduced compared to Example 5, but the predetermined A 101 / A 001 is reduced. And maintaining the I 101 / I 001 range, a significant dose reduction as in the comparative examples was avoided.

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Abstract

Selon des modes de réalisation, la présente invention concerne un précurseur de matériau actif de cathode qui comprend du nickel (Ni) et du cobalt (Co), le nickel étant contenu en une quantité excessive, le rapport de l'aire (A101) du pic de plan (101) sur l'aire (A001) du pic de plan (001), A101/A001, étant supérieur ou égal à 1 selon une analyse par diffraction des rayons X. Le précurseur de matériau actif de cathode peut être utilisé pour obtenir une cathode et un accumulateur au lithium présentant un excellent degré de cristallisation et une excellente stabilité à long terme.
PCT/KR2019/003624 2018-03-28 2019-03-28 Précurseur de matériau actif de cathode et accumulateur au lithium l'utilisant Ceased WO2019190217A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201980023350.0A CN112219297B (zh) 2018-03-28 2019-03-28 正极活性物质前体和使用其的锂二次电池
US17/041,959 US12512468B2 (en) 2018-03-28 2019-03-28 Cathode active material precursor and lithium secondary battery utilizing same

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KR20180035933 2018-03-28
KR10-2018-0035933 2018-03-28
KR10-2019-0033031 2019-03-22
KR1020190033031A KR102495992B1 (ko) 2018-03-28 2019-03-22 양극 활물질 전구체 및 이를 활용한 리튬 이차 전지

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Citations (5)

* Cited by examiner, † Cited by third party
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KR20110136002A (ko) * 2010-06-13 2011-12-21 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질 전구체 및 이를 이용한 리튬 이차 전지용 양극 활물질 및 양극 활물질을 포함하는 리튬 이차 전지
KR20150078672A (ko) * 2013-12-31 2015-07-08 삼성정밀화학 주식회사 리튬 이차 전지용 복합금속 전구체, 그 제조방법, 이로부터 형성된 리튬 이차전지용 양극 활물질 및 이를 포함하는 리튬 이차 전지
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WO2018020845A1 (fr) * 2016-07-29 2018-02-01 住友金属鉱山株式会社 Hydroxyde composite de nickel manganèse et son procédé de production, matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux et son procédé de production, et batterie secondaire à électrolyte non aqueux

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004119218A (ja) * 2002-09-26 2004-04-15 Seimi Chem Co Ltd リチウム二次電池用の正極活物質及びその製造方法
KR20110136002A (ko) * 2010-06-13 2011-12-21 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질 전구체 및 이를 이용한 리튬 이차 전지용 양극 활물질 및 양극 활물질을 포함하는 리튬 이차 전지
KR20150078672A (ko) * 2013-12-31 2015-07-08 삼성정밀화학 주식회사 리튬 이차 전지용 복합금속 전구체, 그 제조방법, 이로부터 형성된 리튬 이차전지용 양극 활물질 및 이를 포함하는 리튬 이차 전지
JP2017033669A (ja) * 2015-07-29 2017-02-09 ニッポン高度紙工業株式会社 電池正極用活物質、電池、電池正極用活物質の製造方法
WO2018020845A1 (fr) * 2016-07-29 2018-02-01 住友金属鉱山株式会社 Hydroxyde composite de nickel manganèse et son procédé de production, matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux et son procédé de production, et batterie secondaire à électrolyte non aqueux

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