WO2019093869A2 - Procédé de fabrication d'un matériau actif d'électrode positive et batterie secondaire - Google Patents

Procédé de fabrication d'un matériau actif d'électrode positive et batterie secondaire Download PDF

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WO2019093869A2
WO2019093869A2 PCT/KR2018/013852 KR2018013852W WO2019093869A2 WO 2019093869 A2 WO2019093869 A2 WO 2019093869A2 KR 2018013852 W KR2018013852 W KR 2018013852W WO 2019093869 A2 WO2019093869 A2 WO 2019093869A2
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active material
lithium
cathode active
material precursor
positive electrode
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PCT/KR2018/013852
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English (en)
Korean (ko)
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WO2019093869A3 (fr
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박성빈
정왕모
이동훈
김지혜
김동휘
조형만
한정민
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주식회사 엘지화학
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Priority to EP18875679.5A priority Critical patent/EP3683191B1/fr
Priority to US16/762,363 priority patent/US11508961B2/en
Priority to CN201880073121.5A priority patent/CN111344256B/zh
Priority to JP2020524757A priority patent/JP7098185B2/ja
Priority claimed from KR1020180139154A external-priority patent/KR102270119B1/ko
Publication of WO2019093869A2 publication Critical patent/WO2019093869A2/fr
Publication of WO2019093869A3 publication Critical patent/WO2019093869A3/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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a cathode active material for a secondary battery.
  • the lithium secondary battery has a structure in which an organic electrolyte or a polymer electrolyte is filled between a positive electrode and a negative electrode, which are made of an active material capable of intercalating and deintercalating lithium ions, and oxidized when lithium ions are inserted / And electrical energy is produced by the reduction reaction.
  • Lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), lithium manganese oxide (LiMnO 2 or LiMn 2 O 4, etc.) and lithium iron phosphate compound (LiFePO 4 ) were used as the cathode active material of the lithium secondary battery .
  • LiNiO 2 lithium nickel oxide
  • lithium iron phosphate compound LiFePO 4
  • LiFePO 4 lithium iron phosphate compound
  • the present invention relates to a method for producing a positive electrode active material of a high-content nickel-based lithium composite transition metal oxide containing 60 mol% or more of nickel (Ni) in order to secure a high capacity
  • the present invention provides a method for manufacturing a cathode active material for a secondary battery, which can improve the structural integrity and chemical stability of a cathode active material by improving the degree of completeness of plasticity by reducing the sensitivity.
  • the present invention provides a method of manufacturing a cathode active material, comprising: preparing a cathode active material precursor including nickel (Ni) and cobalt (Co) and including at least one selected from the group consisting of manganese (Mn) and aluminum (Al); And forming a lithium composite transition metal oxide by mixing and firing the cathode active material precursor and the lithium source, wherein the cathode active material precursor has a Ni content of at least 60 mol% Wherein the molar ratio (Li / M) of the lithium source to the total metal element (M) of the cathode active material precursor is greater than 1.1.
  • a cathode active material of a high-content nickel-based lithium composite transition metal oxide containing 60 mol% or more of nickel (Ni) for securing a high capacity a sintering temperature, So that the degree of plasticity can be easily increased without difficulty in control of severe firing conditions.
  • the cathode active material prepared according to the present invention can be controlled in crystal size, structural stability, and chemical stability even though it is a high-Ni-based lithium complex transition metal oxide.
  • the lithium secondary battery manufactured using the cathode active material according to the present invention can improve the initial capacity, efficiency, and lifetime characteristics.
  • FIG. 1 is a graph showing a characteristic evaluation between lithium secondary batteries using the cathode active material prepared according to Examples and Comparative Examples.
  • a cathode active material precursor comprising at least one selected from the group consisting of nickel (Ni), cobalt (Co), manganese (Mn) ; And (2) mixing and firing the cathode active material precursor and the lithium source to form a lithium composite transition metal oxide, wherein the cathode active material precursor has a Ni content of 60 mol% And the molar ratio (Li / M) of the lithium source (Li) to the total metal element (M) of the cathode active material precursor is greater than 1.1.
  • the present invention relates to a method for producing a positive electrode active material of a high-Ni-based lithium composite transition metal oxide containing 60 mol% or more of nickel (Ni) (Li / M) of lithium (Li) in the lithium source to be greater than 1.1, the sensitivity to the firing conditions such as the firing temperature and the firing atmosphere can be relaxed and the firing rate .
  • the crystal size can be controlled well, and structural stability and chemical stability can be improved even in the case of a high-content nickel-based lithium complex transition metal oxide.
  • the lithium secondary battery manufactured using the cathode active material according to the present invention can improve the initial capacity, efficiency, and lifetime characteristics.
  • the method for producing the cathode active material will be described step by step.
  • the cathode active material precursor includes at least one selected from the group consisting of nickel (Ni) and cobalt (Co), and manganese (Mn) and aluminum (Al).
  • the cathode active material precursor of the present invention is a high-Ni cathode active material precursor having a content of nickel (Ni) of 60 mol% or more among all metal elements. More preferably, the content of nickel (Ni) in the total metal elements may be 80 mol% or more.
  • the lithium complex transition metal oxide formed using a high-Ni cathode active material precursor having a nickel (Ni) content of 60 mol% or more among the entire metal elements may be able to secure a high capacity.
  • the cathode active material precursor may be represented by the following general formula (1).
  • M a is at least one element selected from the group consisting of Mn and Al and M b is at least one element selected from the group consisting of Zr, W, Mg, Al, Ce, Hf, Ta, La, Ti, Sr, Ba, Cr, 0 ⁇ x1? 0.4, 0 ⁇ y1? 0.4, 0? Z1? 0.1, and 0 ⁇ x1 + y1 + z1? 0.4.
  • Ni may be included in an amount corresponding to 1- (x1 + y1 + z1), for example, 0.6? 1- (x1 + y1 + z1) ⁇ 1.
  • the content of Ni in the cathode active material precursor of Formula 1 is 0.6 or more, sufficient amount of Ni is sufficient to contribute to charging and discharging, and high capacity can be achieved.
  • Ni may be included in the range of 0.8? 1 - (x1 + y1 + z1)? 0.99.
  • the positive electrode active material precursor used in the present invention is a high-content nickel (High-Ni) system in which nickel (Ni) is 60 mol% or more among all the metal elements and the sintering temperature, It is more important to control the firing conditions and increase the degree of plasticity because it is more difficult to form the cathode active material having the structural stability and chemical stability.
  • High-Ni high-content nickel
  • Co may be included in an amount corresponding to x1, that is, 0 ⁇ x1? 0.4. If the content of Co in the positive electrode active material precursor of Formula 1 exceeds 0.4, there is a fear of an increase in cost. Considering the remarkable effect of improving the capacity characteristics according to the presence of Co, the Co may be more specifically included in an amount of 0.05? X1? 0.2.
  • M a may be Mn or Al, or Mn and Al.
  • Such a metal element may improve the stability of the active material and, as a result, improve the stability of the battery.
  • the M a may be included in the content corresponding to y 1, that is, the content of 0 ⁇ y 1 ⁇ 0.4. If the y1 of the positive electrode active material precursor of Formula 1 is more than 0.4, the output characteristics and the capacity characteristics of the battery may be deteriorated.
  • the M a may be more specifically contained in an amount of 0.05? Y1? 0.2.
  • M b may be a doping element contained in the positive electrode active material precursor, and M b may include a content corresponding to z 1, that is, 0? Z 1? 0.1.
  • the cathode active material precursor used in the present invention may be an NCM compound including nickel (Ni), cobalt (Co), and manganese (Mn), or may be a nickel compound such as nickel (Ni), cobalt (Co) And may be a four component cathode active material precursor including four components of nickel (Ni), cobalt (Co), manganese (Mn) and aluminum (Al) as essential components. (Ni), cobalt (Co), manganese (Mn), and aluminum (Al), which contain nickel (Ni), cobalt (Co), and manganese A four-component cathode active material precursor including four components as essential components may be more preferable.
  • the cathode active material is prepared from the four-component cathode active material precursor, the stability of the cathode active material can be improved and the lifetime can be improved without deteriorating the output characteristics and the capacity characteristics of the NCM / NCA cathode active material.
  • the cathode active material precursor and the lithium source are mixed and fired to form a lithium complex transition metal oxide.
  • the molar ratio (Li / M) of the lithium source (Li) to the total metal element (M) of the cathode active material precursor is set to exceed 1.1.
  • the lithium source a lithium-containing sulfate, nitrate, acetate, carbonate, oxalate, citrate, halide, hydroxide or oxyhydroxide may be used, and it is not particularly limited as long as it can be dissolved in water.
  • the lithium source is Li 2 CO 3, LiNO 3, LiNO 2, LiOH, LiOH and H 2 O, LiH, LiF, LiCl, LiBr, LiI, CH 3 COOLi, Li 2 O, Li 2 SO 4, CH 3 COOLi, or Li 3 C 6 H 5 O 7 , and any one or a mixture of two or more of them may be used.
  • the molar ratio (Li / M) of the lithium source Li to the total metal element M of the cathode active material precursor is set to about 1.02 to 1.05.
  • the firing temperature and the firing conditions It is difficult to form nickel (Ni) having an initial oxidation number of 3+ due to the tendency of nickel (Ni) to be maintained as 2+, and if the firing condition is controlled or deviated a little, the crystal size increases sharply It was difficult to secure the degree of firing, and when the degree of firing was lowered, it was impossible to realize a sufficiently high capacity.
  • the present invention relates to a method for producing a positive electrode active material of a high-nickel-based lithium composite transition metal oxide containing 60 mol% or more of nickel (Ni) (Li / M) of the lithium source (Li) to the lithium source (M) exceeds 1.1, the sensitivity to the firing conditions such as the firing temperature and the firing atmosphere is relaxed and difficult control of the firing condition is difficult So that the completeness of the plasticity can be increased easily.
  • the crystal size can be well controlled, the structural stability and the chemical stability can be improved even in the case of a high-content nickel-based lithium composite transition metal oxide, It is confirmed that a cathode active material capable of realizing a high capacity can be produced.
  • the molar ratio (Li / M) of the lithium source to the total metal element (M) of the cathode active material precursor may be 1.105 to 1.30, and more preferably the molar ratio (Li / M) may be 1.13 to 1.20.
  • the sintering firing temperature may be performed at 700 ° C to 900 ° C, more preferably 750 to 850 ° C.
  • the firing temperature can be raised up to the firing temperature at a rate of 2 to 10 ° C / min, and more preferably, at a rate of 3 to 7 ° C / min.
  • the calcination may be performed in an oxygen atmosphere during the calcination, more specifically, calcining may be performed in the calcination temperature and oxygen atmosphere for 5 hours to 30 hours.
  • washing may be further performed to remove residual lithium by-products.
  • the washing step may be carried out, for example, by charging a lithium complex transition metal oxide into pure water and stirring the mixture.
  • a lithium complex transition metal oxide into pure water and stirring the mixture.
  • 30 to 300 parts by weight, more preferably 50 to 150 parts by weight, of pure water may be used per 100 parts by weight of the lithium-transition metal oxide.
  • the water-washing temperature may be 30 ° C or lower, preferably -10 ° C to 30 ° C, and the water-washing time may be 10 minutes to 1 hour.
  • the washing temperature and the washing time satisfy the above range, the lithium by-product can be effectively removed.
  • the lithium source Since the lithium source is charged so that the molar ratio (Li / M) of the lithium source (Li) to the total metal element (M) of the cathode active material precursor exceeds 1.1, the residual lithium by- However, if the washing process is performed in this way, the residual lithium by-product can be removed, which is not a problem.
  • the positive electrode active material of the lithium-based composite transition metal oxide produced according to the present invention is a high-nickel-based lithium composite transition metal oxide containing 60 mol% or more of nickel (Ni) Can be realized, and structural stability and chemical stability can be improved.
  • the lithium secondary battery manufactured using the cathode active material according to the present invention can improve the initial capacity, efficiency, and lifetime characteristics.
  • a positive electrode and a lithium secondary battery for a lithium secondary battery comprising the above-described positive electrode active material.
  • the positive electrode includes a positive electrode collector and a positive electrode active material layer formed on the positive electrode collector and including the positive electrode active material.
  • the cathode current collector is not particularly limited as long as it has conductivity without causing a chemical change in the battery, and for example, a metal such as stainless steel, aluminum, nickel, titanium, sintered carbon, , Nickel, titanium, silver, or the like may be used.
  • the cathode current collector may have a thickness of 3 to 500 ⁇ , and fine unevenness may be formed on the surface of the cathode current collector to increase the adhesive force of the cathode active material.
  • it can be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the cathode active material layer may include a conductive material and a binder together with the cathode active material described above.
  • the conductive material is used for imparting conductivity to the electrode.
  • the conductive material can be used without particular limitation as long as it has electron 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 whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; And polyphenylene derivatives. These may be used alone or in admixture of two or more.
  • the conductive material may be typically contained in an amount of 1 to 30% by weight based on the total weight of the cathode active material layer.
  • the binder serves to improve adhesion between the positive electrode active material particles and adhesion between the positive electrode active material and the positive electrode collector.
  • specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose ), Starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, and various copolymers thereof.
  • the binder may be included in an amount of 1 to 30% by weight 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 that the positive electrode active material described above is used. Specifically, the composition for forming a cathode active material layer containing the above-mentioned cathode active material and optionally a binder and a conductive material may be coated on the cathode current collector, followed by drying and rolling. At this time, the types and contents of the cathode active material, the binder, and the conductive material are as described above.
  • the solvent examples include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, and the like. Water and the like, and one kind or a mixture of two or more kinds can be used.
  • the amount of the solvent to be used is sufficient to dissolve or disperse the cathode active material, the conductive material and the binder in consideration of the coating thickness of the slurry and the yield of the slurry, and then to have a viscosity capable of exhibiting excellent thickness uniformity Do.
  • the positive electrode may be produced by casting the composition for forming the positive electrode active material layer on a separate support, then peeling off the support from the support, and laminating the obtained film on the positive electrode current collector.
  • an electrochemical device including the anode.
  • the electrochemical device may be specifically a battery or a capacitor, and more specifically, may be a lithium secondary battery.
  • the lithium secondary battery includes a positive electrode, a negative electrode disposed opposite to the positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, as described above.
  • the lithium secondary battery may further include a battery container for storing the positive electrode, the negative electrode and the electrode assembly of 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 disposed 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 changes in the battery.
  • the negative electrode current collector may be formed on the surface of copper, stainless steel, aluminum, nickel, titanium, sintered carbon, Carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like may be used.
  • the negative electrode collector may have a thickness of 3 to 500 ⁇ , and similarly to the positive electrode collector, fine unevenness may be formed on the surface of the collector to enhance the binding 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, and a nonwoven fabric.
  • the anode active material layer optionally includes a binder and a conductive material together with the anode active material.
  • the negative electrode active material layer may be formed by applying and drying a composition for forming a negative electrode including a negative electrode active material on the negative electrode collector and, optionally, a binder and a conductive material, or by casting the composition for forming a negative electrode on a separate support , And a film obtained by peeling from the support may be laminated on the negative electrode collector.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used.
  • Specific examples thereof include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber and amorphous carbon;
  • Metal 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 dedoping lithium such as SiO? (0 ⁇ ?
  • the carbon material may be both low-crystalline carbon and high-crystallinity carbon. Examples of the low-crystalline carbon include soft carbon and hard carbon.
  • Examples of the highly crystalline carbon include natural graphite, artificial graphite, artificial graphite or artificial graphite, Kish graphite graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar coke derived cokes).
  • binder and the conductive material may be the same as those described above for the anode.
  • the separator separates the negative electrode and the positive electrode and provides a moving path of lithium ions.
  • the separator can be used without any particular limitation as long as it is used as a separator in a lithium secondary battery. Particularly, It is preferable to have a low resistance and an excellent ability to impregnate the electrolyte.
  • porous polymer films such as porous polymer films made of polyolefin-based polymers such as ethylene homopolymers, propylene homopolymers, ethylene / butene copolymers, ethylene / hexene copolymers and ethylene / methacrylate copolymers, May be used.
  • a nonwoven fabric made of a conventional porous nonwoven fabric for example, glass fiber of high melting point, polyethylene terephthalate fiber, or the like may be used.
  • a coated separator containing a ceramic component or a polymer material may be used, 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-based liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, and a molten inorganic electrolyte that can be used in the production of a lithium secondary battery. It is not.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without limitation as long as it can act as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • examples of the organic solvent include ester solvents such as methyl acetate, ethyl acetate,? -Butyrolactone and?
  • Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethyl carbonate (DMC), diethylcarbonate (DEC), methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate PC) and the like; Alcohol solvents such as ethyl alcohol and isopropyl alcohol; R-CN (R is a straight, branched or cyclic hydrocarbon group of C2 to C20, which may contain a double bond aromatic ring or an ether bond); Amides such as dimethylformamide; Dioxolanes such as 1,3-dioxolane; Or sulfolane may be used.
  • Ether solvents such as dibutyl ether or tetrahydrofuran
  • Ketone solvents such as cyclohexanone
  • a carbonate-based solvent is preferable, and a cyclic carbonate (for example, ethylene carbonate or propylene carbonate) having a high ionic conductivity and a high dielectric constant, for example, such as ethylene carbonate or propylene carbonate, For example, ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate) is more preferable.
  • a cyclic carbonate for example, ethylene carbonate or propylene carbonate
  • ethylene carbonate or propylene carbonate for example, ethylene carbonate or propylene carbonate
  • ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate
  • the lithium salt can 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 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 Etc. may be used.
  • the concentration of the lithium salt is preferably in the range of 0.1 to 2.0 M. When the concentration of the lithium salt is within the above range, the electrolyte has an appropriate conductivity and viscosity, so that it can exhibit excellent electrolyte performance and the lithium ion can effectively move.
  • the electrolyte may contain, for example, a haloalkylene carbonate-based compound such as difluoroethylene carbonate or the like, pyridine, triethanolamine, or the like for the purpose of improving lifetime characteristics of the battery, Ethyl phosphite, triethanol amine, cyclic ether, ethylenediamine, glyme, hexametriamide, nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, At least one additive such as benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, The additive may be included in an amount of 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, it can be used in portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles hybrid electric vehicle (HEV)).
  • portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles hybrid electric vehicle (HEV)).
  • HEV hybrid electric vehicles hybrid electric vehicle
  • a battery module including the lithium secondary battery as a unit cell and a battery pack including the same.
  • the battery module or the battery pack may include a power tool; An electric vehicle including an electric vehicle (EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV); Or a power storage system, as shown in FIG.
  • a power tool including an electric vehicle (EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV); Or a power storage system, as shown in FIG.
  • EV electric vehicle
  • PHEV plug-in hybrid electric vehicle
  • Cathode active material precursor Ni 0 . 86 Co 0 . 1 Mn 0 . 02 Al 0 .02 (OH) mol ratio of lithium (Li) of the lithium source LiOH to the total metal elements of the 2 (M) (Li / M ) is introduced to a Henschel mixer (700L) to be 1.15, and from the center of 300rpm And mixed for 20 minutes.
  • a Henschel mixer 700L
  • the temperature was raised to 5 °C / min to prepare a lithium composite transition metal oxide by calcining for 10 hours in an oxygen (O 2) atmosphere at 790 °C.
  • Each of the cathode active material, the carbon black conductive material and the PVdF binder prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was mixed in a N-methylpyrrolidone solvent in a weight ratio of 95: 2.5: 2.5, (Viscosity: 5000 mPa ⁇ ⁇ ) was coated on one surface of the aluminum current collector, dried at 130 ⁇ ⁇ and rolled to prepare a positive electrode.
  • a negative electrode active material natural graphite, a carbon black conductive material and a PVdF binder were mixed in a N-methylpyrrolidone solvent in a weight ratio of 85: 10: 5 to prepare a composition for forming a negative electrode active material layer, To prepare a negative electrode.
  • a lithium secondary battery was prepared by preparing an electrode assembly between a positive electrode and a negative electrode manufactured as described above through a separator of porous polyethylene, positioning the electrode assembly inside a case, and then injecting an electrolyte into the case.
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Charging capacity (mAh / g) (0.2C) 230.1 231.2 230.7 228.4 229.3 229.6 221.2 Discharge capacity (mAh / g) (0.2C) 205.4 205.5 205.7 202.2 203.4 203.6 190.2 Efficiency (%) (0.2C) 89.3 88.9 89.2 88.5 88.7 88.7 86.0
  • the molar ratio of lithium (Li) and metal element (M) to lithium metal (M) was lower than that of Comparative Examples 1 to 4 in which the molar ratio (Li / M) (Li / M) exceeded 1.1 in Examples 1 to 3 exhibited somewhat superior initial capacity and efficiency.
  • Each of the lithium secondary battery cells thus prepared was charged at 45 ° C in a CCCV mode until it reached 0.5C and 4.25V, cut off under the condition of 0.55C, and 2.5V at a constant current of 1.0C , And the capacity retention (%) was measured while charging / discharging was performed 30 times. The results are shown in Fig.
  • the molar ratio (molar ratio) of lithium (Li) and metal element (M) to lithium (Li) and metal element (M) is smaller than that of Comparative Examples 1 to 4 in which the molar ratio Li / M) exceeded 1.1 in Examples 1 to 3, the capacity retention ratio according to the progress of the cycle is high. That is, it can be seen that the life characteristics of Examples 1 to 3 in which the molar ratio (Li / M) of lithium (Li) and metal element (M) exceeded 1.1 were greatly improved.

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

Abstract

La présente invention concerne un procédé de fabrication d'un matériau actif d'électrode positive pour une batterie secondaire, le procédé comprenant les étapes consistant à : préparer un précurseur de matériau actif d'électrode positive contenant du nickel (Ni), du cobalt (Co) et au moins un élément choisi dans le groupe constitué par le manganèse (Mn) et l'aluminium (Al); à mélanger et à fritter le précurseur de matériau actif d'électrode positive et une source de lithium pour former un oxyde de métal de transition composite de lithium. Dans le précurseur de matériau actif d'électrode positive, la teneur en nickel (Ni) dans les éléments métalliques globaux est supérieure ou égale à 60 % en moles et le rapport molaire (Li/M) du lithium (Li) de la source de lithium par rapport aux éléments métalliques globaux (M) est supérieur à 1,1.
PCT/KR2018/013852 2017-11-13 2018-11-13 Procédé de fabrication d'un matériau actif d'électrode positive et batterie secondaire WO2019093869A2 (fr)

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EP18875679.5A EP3683191B1 (fr) 2017-11-13 2018-11-13 Procédé de fabrication d'un matériau actif d'électrode positive et batterie secondaire
US16/762,363 US11508961B2 (en) 2017-11-13 2018-11-13 Method of preparing positive electrode active material for secondary battery
CN201880073121.5A CN111344256B (zh) 2017-11-13 2018-11-13 制备二次电池用正极活性材料的方法
JP2020524757A JP7098185B2 (ja) 2017-11-13 2018-11-13 二次電池用正極活物質の製造方法

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KR10-2017-0150535 2017-11-13
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KR1020180139154A KR102270119B1 (ko) 2017-11-13 2018-11-13 이차전지용 양극 활물질의 제조방법

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN113800574A (zh) * 2021-08-05 2021-12-17 广州大学 一种镍锰铁铝锂正极材料及其制备方法
CN114391189A (zh) * 2019-09-11 2022-04-22 株式会社Lg新能源 二次电池用正极材料及包含其的锂二次电池

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KR100944137B1 (ko) * 2005-11-02 2010-02-24 에이지씨 세이미 케미칼 가부시키가이샤 리튬 함유 복합 산화물 및 그 제조 방법
CN101443273B (zh) * 2006-02-17 2014-05-07 株式会社Lg化学 锂-金属复合氧化物的制备方法
KR20130059029A (ko) * 2011-11-28 2013-06-05 에스케이씨 주식회사 복합 금속 수산화물의 제조방법
WO2014010849A1 (fr) * 2012-07-09 2014-01-16 주식회사 엘지화학 Précurseur pour la préparation d'un oxyde de métal de transition composite de lithium
KR20160083616A (ko) * 2014-12-31 2016-07-12 삼성에스디아이 주식회사 리튬이차전지용 양극 활물질의 전구체, 그 제조방법, 리튬이차전지용 양극 활물질, 그 제조방법, 및 상기 양극 활물질을 포함하는 리튬이차전지

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114391189A (zh) * 2019-09-11 2022-04-22 株式会社Lg新能源 二次电池用正极材料及包含其的锂二次电池
CN113800574A (zh) * 2021-08-05 2021-12-17 广州大学 一种镍锰铁铝锂正极材料及其制备方法

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