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WO2019074305A2 - Matériau actif d'électrode positive pour batterie rechargeable au lithium, son procédé de préparation, électrode positive le comprenant pour batterie rechargeable au lithium et batterie rechargeable au lithium - Google Patents

Matériau actif d'électrode positive pour batterie rechargeable au lithium, son procédé de préparation, électrode positive le comprenant pour batterie rechargeable au lithium et batterie rechargeable au lithium Download PDF

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Publication number
WO2019074305A2
WO2019074305A2 PCT/KR2018/011984 KR2018011984W WO2019074305A2 WO 2019074305 A2 WO2019074305 A2 WO 2019074305A2 KR 2018011984 W KR2018011984 W KR 2018011984W WO 2019074305 A2 WO2019074305 A2 WO 2019074305A2
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Prior art keywords
lithium
nickel
active material
positive electrode
transition metal
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PCT/KR2018/011984
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English (en)
Korean (ko)
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WO2019074305A3 (fr
Inventor
김원태
신선식
윤여준
박홍규
강성훈
유종열
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020180120667A external-priority patent/KR102213174B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2019572655A priority Critical patent/JP7051184B2/ja
Priority to US16/630,720 priority patent/US11362332B2/en
Priority to CN201880047150.4A priority patent/CN110892565B/zh
Publication of WO2019074305A2 publication Critical patent/WO2019074305A2/fr
Publication of WO2019074305A3 publication Critical patent/WO2019074305A3/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/991—Boron carbide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 for a lithium secondary battery, a method for producing the positive electrode active material, a positive electrode for a lithium secondary battery including the positive electrode active material, and a lithium secondary battery.
  • lithium secondary batteries having a high energy density and voltage, a long cycle life, and a low self-discharge rate are commercially available and widely used.
  • Lithium transition metal complex oxides are used as the positive electrode active material of lithium secondary batteries, and lithium cobalt composite metal oxides such as LiCoO 2 having a high operating voltage and excellent capacity characteristics are mainly used.
  • LiCoO 2 has very poor thermal properties due to the destabilization of the crystal structure due to the depolymerization.
  • LiCoO 2 is expensive, it can not be used in large quantities as a power source for fields such as electric vehicles and the like.
  • Lithium manganese composite metal oxides such as LiMnO 2 or LiMn 2 O 4
  • lithium iron phosphate compounds such as LiFePO 4
  • lithium nickel composite metal oxides such as LiNiO 2
  • LiNiO 2 has a lower thermal stability than LiCoO 2
  • a lithium nickel cobalt metal oxide in which a part of Ni is substituted with Co and Mn or Al has been developed as a method for improving low thermal stability while maintaining excellent reversible capacity of LiNiO 2 .
  • the lithium nickel cobalt metal oxide containing lithium nickel cobalt metal oxide containing a high content of Ni exhibiting a high capacity characteristic is excellent in the structural stability of the lithium nickel cobalt metal oxide, and development of a cathode active material capable of producing a high capacity and high- .
  • a first technical object of the present invention is to provide a lithium transition metal oxide containing nickel in a high content, wherein a surface of the lithium transition metal oxide is coated using a specific raw material, And a method for producing a cathode active material having improved structural stability.
  • a second object of the present invention is to provide a cathode active material having a Co-containing coating material formed in a specific amount.
  • a third object of the present invention is to provide a positive electrode for a lithium secondary battery comprising the positive electrode active material.
  • a fourth aspect of the present invention is to provide a lithium secondary battery including the positive electrode for a lithium secondary battery.
  • the present invention relates to a process for preparing a nickel-containing lithium transition metal oxide by a first heat treatment of a nickel-containing hydroxide precursor and a lithium-raw material containing 65 mol% or more of nickel relative to the total number of moles of the transition metal; Mixing the B-containing and C-containing raw material and the Co-containing raw material with the nickel-containing lithium transition metal oxide to form a mixture; And a second heat treatment of the mixture to form a coating material containing B and Co on the surface of the lithium-transition metal oxide.
  • the present invention also relates to a nickel-containing lithium transition metal oxide comprising at least 65 mol% of nickel based on the total moles of transition metals except lithium; And a coating material distributed on the surface of the nickel-containing lithium-transition metal oxide, wherein the coating material comprises B and Co, and the coating material contains Co in an amount of 1,000 to 5,000 ppm. Thereby providing an active material.
  • a positive electrode for a lithium secondary battery comprising the positive electrode active material according to the present invention.
  • a lithium secondary battery comprising a positive electrode according to the present invention.
  • the present invention by forming a coating material containing B and Co using a specific raw material on the surface of a lithium transition metal oxide containing nickel in a high content, it is possible to prevent oxygen escape due to oxidation of Ni.
  • side reactions between the positive electrode active material and the electrolyte can be suppressed, and the structural stability of the positive electrode active material can be improved.
  • the secondary battery can be provided with improved output characteristics and lifetime characteristics in battery manufacturing.
  • FIG. 1 is a scanning electron micrograph of the cathode active material prepared in Example 1.
  • FIG. 2 is a scanning electron microscope (SEM) image of the cathode active material prepared in Comparative Example 1.
  • FIG. 3 is a scanning electron micrograph of the cathode active material prepared in Comparative Example 2.
  • Example 6 is a graph showing discharge capacities of a lithium secondary battery manufactured in Example 1 and Comparative Examples 1 and 3 to 4 under a condition of 1.0 C constant current discharge.
  • FIG. 7 is a graph showing the discharge capacities of the lithium secondary batteries manufactured in Example 1 and Comparative Examples 1 and 3 to 4 under a condition of 2.0 C constant current discharge.
  • the positive electrode active material according to the present invention is a nickel-containing lithium transition metal oxide containing at least 65 mol% of nickel based on the total moles of transition metals except lithium. And a coating material formed on the surface of the nickel-containing lithium transition metal oxide, wherein the coating material comprises B and Co, and the coating material contains Co in an amount of 1,000 to 5,000 ppm.
  • the cathode active material may include a nickel-containing lithium transition metal oxide containing at least 65 mol% of nickel based on the total moles of transition metals other than lithium, more preferably nickel -Containing lithium transition metal oxide.
  • Me is at least one selected from the group consisting of Mn and Al.
  • the nickel-containing lithium transition metal oxide may more preferably be LiNi a Co b Al 1 - (a + b) O 2 or LiNi a Co b Mn 1 - (a + b) O 2 , LiNi 0 . 65 Co 0 . 2 Al 0 . 15 O 2 , LiNi 0.7 Co 0.15 Al 0.15 O 2 , LiNi 0 . 8 Co 0 . 1 Al 0 . 1 O 2 , LiNi 0 . 9 Co 0 . 05 A1 0 . 05 O 2 , LiNi 0 . 65 Co 0 . 2 Mn 0 .
  • the nickel-containing lithium transition metal oxide having a nickel content of 65 mol% or more with respect to the total number of moles of transition metals other than lithium can be used to achieve high capacity of the battery during the production of the battery.
  • the positive electrode active material includes a coating material including Co element B and Co formed on the surface of the positive electrode active material. Since the contact between the positive electrode active material and the electrolyte contained in the lithium secondary battery is blocked by the coating material, occurrence of side reaction is suppressed, so that it is possible to improve the lifetime characteristics when applied to a battery and increase the filling density of the positive electrode active material have. Particularly, when B is contained as a coating element, it is possible to reduce the initial resistance and the rate of increase in resistance due to securing excellent electrical conductivity, achieve the effect of reducing lithium impurities remaining on the surface of the cathode material, The rate characteristics can be improved and the initial resistance and the rate of increase in resistance can be reduced due to securing excellent electrical conductivity.
  • the coating material may contain B in an amount of 100 ppm to 500 ppm, preferably 200 ppm to 300 ppm, and the Co may include 1,000 ppm to 5,000 ppm, preferably 2,000 ppm to 4,500 ppm.
  • B and Co are included in the above-mentioned coating material, the effect of suppressing the corrosion and side reaction on the surface of the cathode active material by hydrogen fluoride occurs more effectively, and the rate characteristics and lifetime characteristics when applied to a battery can be further improved.
  • the content of Co contained in the coating material can be measured using a transmission electron microscope and X-ray spectrometry.
  • the content of Co present in a coating material can be measured using electron dispersive X-ray spectroscopy (EDS) of a JEM-2010F transmission electron microscope (TEM).
  • EDS electron dispersive X-ray spectroscopy
  • TEM JEM-2010F transmission electron microscope
  • the content of B contained in the coating material can be measured by, for example, ICP mass spectrometry.
  • ICP mass spectrometry Optima 7000 dv, PerkinElmer
  • Optima 7000 dv PerkinElmer
  • Optima 7000 dv PerkinElmer
  • Optima 7000 dv PerkinElmer
  • 0.2 mL of internal STD is added to the dissolved sample and diluted to 20 mL with ultrapure water.
  • the coating material may be uniformly distributed over the entire surface of the cathode active material, or may be distributed in the form of partially coherent islands. Specifically, when the coating material uniformly forms a coating layer over the entire surface of the cathode active material, for example, the thickness of the coating layer may be 1 nm to 50 nm, preferably 7 nm to 25 nm. When the coating material is distributed on the surface of the cathode active material in the island shape, the coating material may be distributed to occupy 20% to 90% of the total surface area of the cathode active material. When the area of the coating material is less than 20% of the total surface area of the cathode active material, the effect of improving the structural stability due to the formation of the coating material may be insignificant. When the coating material is uniformly formed over the entire surface of the cathode active material, the structural stability of the cathode active material surface can be further improved.
  • the method for producing a positive electrode active material comprises mixing a nickel-containing hydroxide precursor containing at least 65 mol% of nickel relative to the total moles of transition metals and a lithium-source material and subjecting the mixture to a first heat treatment to form a nickel- Producing a metal oxide; Mixing the B-containing and C-containing raw material and the Co-containing raw material with the nickel-containing lithium transition metal oxide to form a mixture; And forming a coating material containing B and Co on the surface of the lithium-transition metal oxide by secondary heat treatment of the mixture.
  • a nickel-containing transition metal hydroxide precursor and a lithium-source material are mixed and subjected to a first heat treatment to prepare a nickel-containing lithium transition metal oxide.
  • the nickel-containing transition metal hydroxide precursor may have a nickel content of 65 mol% or more based on the total number of moles of the transition metal, and Ni a1 Co b1 Me 1 - (a 1 + b 1 ) OH 2 wherein 0.65? A1? , 0.05? B1? 0.2, 0.85? A1 + b1? 0.95, and Me is at least one selected from the group consisting of Mn and Al).
  • the nickel cobalt manganese hydroxide precursor is Ni 0 . 65 Co 0 . 2 Al 0 .15 (OH) 2 , Ni 0. 7 Co 0 . 15 Al 0 .15 (OH) 2 , Ni 0. 8 Co 0 .
  • the lithium-source material is not particularly limited as long as it is a compound containing a lithium source, but lithium carbonate (Li 2 CO 3 ), lithium hydroxide (LiOH), LiNO 3 , CH 3 COOLi and Li 2 COO) 2 may be used.
  • the nickel-containing transition metal hydroxide precursor and the lithium-source material are mixed so that the molar ratio of Li to metal (Li / metal ratio) is 1 to 1.3, preferably 1.05 to 1.1, more preferably 1.07 to 1.09 .
  • the nickel-containing transition metal hydroxide precursor and the lithium-source material are mixed in the above range, a cathode active material exhibiting excellent capacity characteristics can be produced.
  • a mixture of the nickel-containing transition metal hydroxide precursor and the lithium-source material is subjected to a first heat treatment to prepare a cathode active material containing a nickel-containing lithium transition metal oxide.
  • the primary heat treatment may be performed at a temperature of 700 ° C to 900 ° C.
  • the first heat treatment may be performed in an oxidizing atmosphere.
  • a residual lithium impurity to such an extent that a coating material can be sufficiently formed can be obtained, and a positive electrode nickel-containing lithium transition metal oxide having excellent crystal grains can be obtained.
  • the primary heat treatment is performed in an inactive atmosphere such as a nitrogen atmosphere, the amount of residual lithium impurities increases, so that metal oxides are not synthesized and formation of a coating material may be difficult.
  • the primary heat treatment may be carried out in an oxidizing atmosphere at 600 ° C to 800 ° C for 4 hours to 5 hours in one step and then at 800 ° C to 900 ° C for 8 hours to 10 hours in two steps.
  • the particle strength of the cathode active material can be improved.
  • the primary heat treatment temperature and time satisfy the above range, the raw material does not remain in the particles and the high-temperature stability of the battery can be improved. As a result, the bulk density and crystallinity are improved, The structural stability can be improved.
  • the nickel-containing lithium transition metal oxide is mixed with the B- and C-containing raw material and the Co-containing raw material to form a mixture.
  • the C- and B-containing source material B 4 C, (C 3 H 7 O) 3 B, (C 6 H 5 O) 3 B, [CH 3 (CH 2) 3 O] 3 B, And C 6 H 5 B (OH) 2 , and may be at least one of B 4 C, preferably B 4 C.
  • the B and C-containing raw materials are B 4 C
  • B 4 C since B 4 C has a high melting point, it is advantageous to apply it as a raw material for performing a high-temperature heat treatment.
  • the C included in the B and C-containing raw materials is easily oxidized by the strong reducing action, and oxidation of the coating raw material can be easily suppressed.
  • the B and C-containing raw material may be mixed in an amount of 0.02 parts by weight to 0.04 parts by weight based on 100 parts by weight of the nickel-containing lithium transition metal oxide.
  • the Co-containing raw material can be used without limitation as long as it can coat the surface of the lithium transition metal oxide particles and does not deteriorate the electrochemical performance.
  • Co (OH) 2 , Co 2 O 3 , Co 3 (PO 4) 2, CoF 3, CoOOH, Co (OCOCH 3) 2 ⁇ 4H 2 O, Co (NO 3) ⁇ 6H 2 O, Co 3 O 4, Co (SO 4) 2 ⁇ 7H 2 O and CoC at least one may be at least selected from the group consisting of 2 O 4.
  • Co (OH) 2 when used as the Co-containing raw material, its structural stability can be further improved when applied to a battery.
  • the Co (OH) 2 when the Co (OH) 2 is thermally treated in an oxidizing atmosphere at a temperature of 300 ° C or higher, it is oxidized to Co 3 O 4 to act as a resistance during electrochemical reaction, Thereby causing a problem that the resistance characteristic is poor.
  • the Co-containing raw material as well as the B and C-containing raw materials are included together as the coating material according to the present invention, the B and C-containing raw materials are generated during the dissociation process at high temperature heat treatment Carbon can act as a reducing agent. Accordingly, the Co (OH 2 ) can be prevented from being oxidized to the metal oxide, so that the Co content in the coating material is preferably about 1,000 to 5,000 ppm.
  • the Co-containing raw material may be mixed with 0.5 part by weight to 1.0 part by weight with respect to 100 parts by weight of the nickel-containing lithium transition metal oxide.
  • the mixture is subjected to a secondary heat treatment at 500 ° C to 750 ° C to form a coating material containing B and Co on the surface of the lithium transition metal oxide.
  • the secondary heat treatment may be performed at 500 ° C to 750 ° C for 3 hours to 8 hours, more preferably at 500 ° C to 650 ° C for 4 hours to 6 hours.
  • the secondary heat treatment temperature is in the above range, the surface of the cathode active material is easily modified due to the formation of the coating material without changing the surface of the cathode active material by forming the coating material at a high temperature, It is possible to produce a cathode active material having an excellent and high capacity.
  • capacity and lifetime characteristics may be reduced due to excessive lithium borate compound formation.
  • the cathode for a secondary battery includes a cathode current collector, a cathode active material layer formed on the cathode current collector, and the cathode active material layer includes the cathode active material according to the present invention.
  • cathode active material is the same as that described above, a detailed description thereof will be omitted and only the remaining constitution will be specifically described below.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • 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 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, optionally, a binder optionally together with the cathode active material.
  • the cathode active material may be contained in an amount of 80 to 99% by weight, more specifically 85 to 98.5% by weight based on the total weight of the cathode active material layer. When included in the above content range, excellent capacity characteristics can be exhibited.
  • the conductive material is used for imparting conductivity to the electrode.
  • the conductive material is not particularly limited 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 included in an amount of 0.1 to 15% by weight based on the total weight of the cathode active material layer.
  • the binder serves to improve the adhesion between the positive electrode active material particles and the adhesion between the positive electrode active material and the current collector.
  • Specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, 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 0.1 to 15% 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 cathode active material and optionally the binder and the conductive material may be dissolved or dispersed in a solvent to prepare a composition for forming a cathode active material layer, which is then applied onto the cathode current collector, followed by drying and rolling.
  • 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, and then laminating a film obtained by peeling from the support onto the positive electrode collector.
  • the present invention can produce an electrochemical device including the positive electrode.
  • the electrochemical device may be specifically a battery, a capacitor, or the like, and more specifically, it may be a lithium secondary battery.
  • the lithium secondary battery includes a positive electrode, a negative electrode disposed opposite to the positive electrode, and a separation membrane and an electrolyte interposed between the positive electrode and the negative electrode.
  • the positive electrode is the same as that described above, Only the remaining configuration will be described in detail below.
  • the lithium secondary battery may further include a battery container for housing the electrode assembly of the anode, the cathode, and the separator, and a sealing member for sealing the battery container.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer 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.
  • 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; SiO ⁇ (0 ⁇ ⁇ 2 ), SnO 2, vanadium oxide, which can dope and de-dope a lithium metal oxide such as lithium vanadium oxide;
  • a composite containing the metallic compound and the carbonaceous material such as Si-C composite or Sn-C composite, and any one or a mixture of two or more thereof may be used.
  • a metal lithium thin film may be used as the negative electrode active material.
  • 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).
  • the negative electrode active material may include 80% by weight to 99% by weight based on the total weight of the negative electrode active material layer.
  • the binder is a component for assisting the bonding between the conductive material, the active material and the current collector, and is usually added in an amount of 0.1% by weight to 10% by weight based on the total weight of the negative electrode active material layer.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • CMC carboxymethylcellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-butadiene rubber
  • fluorine rubber various copolymers thereof.
  • the conductive material may be added in an amount of 10 wt% or less, preferably 5 wt% or less, based on the total weight of the negative electrode active material layer, as a component for further improving the conductivity of the negative electrode active material.
  • a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, for example, graphite such as natural graphite or artificial graphite; Carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the negative electrode active material layer is prepared by applying and drying a composition for forming a negative electrode active material layer, which is prepared by dissolving or dispersing a negative electrode active material on a negative electrode current collector, and optionally a binder and a conductive material in a solvent, Casting a composition for forming an active material layer on a separate support, and then laminating a film obtained by peeling from the support onto a negative electrode current collector.
  • a composition for forming a negative electrode active material layer which is prepared by dissolving or dispersing a negative electrode active material on a negative electrode current collector, and optionally a binder and a conductive material in a solvent, Casting a composition for forming an active material layer on a separate support, and then laminating a film obtained by peeling from the support onto a negative electrode current collector.
  • the negative electrode active material layer may be formed by applying and drying a composition for forming a negative electrode active material layer prepared by dissolving or dispersing a negative electrode active material on a negative electrode collector and optionally a binder and a conductive material in a solvent, Casting the composition on a separate support, and then peeling the support from the support to laminate a film on the negative electrode current collector.
  • the separation membrane separates the cathode and the anode and provides a passage for lithium ion.
  • the separation membrane can be used without any particular limitation as long as it is used as a separation membrane 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 the separator may be selectively used as a single layer or a multilayer structure.
  • Examples of the electrolyte used in the present invention include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-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 linear, branched or cyclic hydrocarbon group having 2 to 20 carbon atoms, 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 cyclohex
  • 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 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 life characteristics, 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
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be a cylindrical shape, a square shape, a pouch shape, a coin shape, or the like using a can.
  • the lithium secondary battery according to the present invention can be used not only in a battery cell used as a power source of a small device but also as a unit cell in a middle- or large-sized battery module including a plurality of battery cells.
  • the cathode active material prepared above was pulverized using induction. 0.02 parts by weight and 0.8 parts by weight of B 4 C and Co (OH) 2 as coating element-containing raw materials were added to the crushed cathode active material, respectively, and mixed with 100 parts by weight of the cathode active material. Subsequently, heat treatment was performed at 600 ⁇ ⁇ for 5 hours in an air atmosphere. The heat treated powder was pulverized by induction and classified by using 325 mesh to prepare a cathode active material in which coating materials containing B and Co were distributed on the surface in an island shape.
  • a lithium secondary battery was prepared from the positive electrode active material by the same method as in Example 1.
  • the cathode active material was prepared in the same manner as in Example 1 above.
  • Example 1 the surface was relatively smooth as in Comparative Example 1 (see FIG. 2) in which a coating material was formed at a relatively low temperature.
  • Comparative Example 5 the surface was relatively smooth as in Example 1 and Comparative Example 1, but the Co content was small compared with Example 1 and Comparative Examples 1 and 2 It was because.
  • a lithium secondary battery was fabricated using the cathode active materials prepared in Examples 1 and 2 and Comparative Examples 1 and 3 to 5, respectively, and capacity characteristics were confirmed using the same.
  • the positive electrode active material, the carbon black conductive material, and the carbon black conductive material prepared in Examples 1 and 2 and Comparative Examples 1 and 3 to 5 were mixed at a weight ratio of 95: 2.5: 2.5, and the mixture was mixed in N-methylpyrrolidone solvent to prepare a composition for forming a positive electrode.
  • the composition for forming an anode was applied to an Al foil having a thickness of 20 ⁇ , dried, and rolled to produce a positive electrode.
  • a lithium metal electrode having a diameter of 16 pi was used as the negative electrode active material.
  • the positive electrode and the negative electrode prepared above were laminated together with a polypropylene separator to prepare an electrode assembly.
  • the electrode assembly was placed in a battery case, and 1 M of LiPF 6 was dissolved in a mixed solvent of ethyl methyl carbonate: ethylene carbonate in a ratio of 7: 3 And an electrolyte was injected thereinto to prepare lithium secondary batteries of Examples 1 and 2 and Comparative Examples 1 and 3 to 5.
  • Each of the lithium secondary batteries of Examples 1 and 2 and Comparative Examples 1 and 3 to 5 prepared above was charged to 4.3 V at a constant current of 0.1 C at 25 ⁇ and discharged at a constant current of 0.1 C until the voltage reached 3 V Charging and discharging characteristics were observed in the first cycle, and the results are shown in Table 1 and FIG. 5 below. Thereafter, discharge capacities at 1.0 C and 2.0 C were measured at different discharge conditions of 1.0 C and 2.0 C, respectively. These discharge capacities were shown in FIG. 6 and FIG. 7, respectively. The efficiency at 2.0 C is shown in Table 2 below.
  • the secondary batteries prepared in Examples 1 and 2 exhibited efficiencies of 90% or more at 1.0 C-rate, 89% at 2.0 C-rate Efficiency, and the discharge capacity was the most improved.
  • the lithium secondary batteries of Examples 1 to 2 and Comparative Examples 1 to 5 were charged at a constant current of 0.5 C at a temperature of 25 ⁇ until the voltage reached 4.3 V, allowed to stand for 20 minutes, and then become 3 V at a constant current of 1.0 C .
  • the charge and discharge behaviors were taken as one cycle. After repeating this cycle 50 times, the resistance increase rate according to this example and the comparative example was measured, and the results are shown in Table 3 below.
  • Example 3 As shown in Table 3, it was confirmed that the resistance of the secondary battery manufactured in Example 1 showed a resistance increase rate of less than 1.5% as compared with the initial resistance in the resistance measurement after 50 cycles. Meanwhile, it was confirmed that the secondary battery according to Example 2 had relatively low structural stability of the cathode active material as the Co content in the coating material was lowered, and that the resistance characteristic was improved when the battery was applied to the battery.
  • the B and C-containing raw materials may act as a reducing agent to prevent oxidation of the Co-containing raw material during the heat treatment after forming a coating material containing B and Co on the surface of the metal oxide.
  • Co is not reduced and remains in the coating material to achieve the effect of the present invention.

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

Abstract

La présente invention concerne un procédé de préparation d'un matériau actif d'électrode positive, le procédé comprenant les étapes consistant à : mélanger un précurseur d'hydroxyde contenant du nickel contenant 65 % en moles ou plus de nickel par rapport au nombre total de moles de métaux de transition et une matière première de lithium, puis effectuer un traitement thermique primaire, pour préparer un oxyde de métal de transition lithié contenant du nickel ; mélanger une matière première contenant du B et du C et une matière première contenant du Co à l'oxyde de métal de transition lithié contenant du nickel pour former un mélange ; et soumettre le mélange à un traitement thermique secondaire pour former un matériau de revêtement contenant du B et du Co sur une surface de l'oxyde de métal de transition lithié. L'invention concerne en outre un matériau actif d'électrode positive préparé par le procédé de préparation et ayant un matériau de revêtement contenant une teneur particulière de Co, une électrode positive, contenant le matériau actif d'électrode positive, pour une batterie rechargeable au lithium, et une batterie rechargeable au lithium.
PCT/KR2018/011984 2017-10-12 2018-10-11 Matériau actif d'électrode positive pour batterie rechargeable au lithium, son procédé de préparation, électrode positive le comprenant pour batterie rechargeable au lithium et batterie rechargeable au lithium Ceased WO2019074305A2 (fr)

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JP2019572655A JP7051184B2 (ja) 2017-10-12 2018-10-11 リチウム二次電池用正極活物質、その製造方法、それを含むリチウム二次電池用正極及びリチウム二次電池
US16/630,720 US11362332B2 (en) 2017-10-12 2018-10-11 Positive electrode active material for lithium secondary battery, method of preparing the same, and positive electrode for lithium secondary battery and lithium secondary battery which include the positive electrode active material
CN201880047150.4A CN110892565B (zh) 2017-10-12 2018-10-11 正极活性材料、其制备方法以及包含其的锂二次电池用正极和锂二次电池

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JP2021141066A (ja) * 2020-03-05 2021-09-16 三星エスディアイ株式会社Samsung SDI Co., Ltd. リチウム二次電池用複合正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池

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KR100437339B1 (ko) * 2002-05-13 2004-06-25 삼성에스디아이 주식회사 전지용 활물질의 제조방법 및 그로부터 제조되는 전지용활물질
KR101264364B1 (ko) * 2009-12-03 2013-05-14 주식회사 엘앤에프신소재 리튬 이차 전지용 양극 활물질 및 이를 이용한 리튬 이차 전지
JP6284542B2 (ja) * 2013-10-29 2018-02-28 エルジー・ケム・リミテッド 正極活物質の製造方法、及びこれによって製造されたリチウム二次電池用正極活物質
JP6524651B2 (ja) * 2013-12-13 2019-06-05 日亜化学工業株式会社 非水電解液二次電池用正極活物質及びその製造方法
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JP2021141066A (ja) * 2020-03-05 2021-09-16 三星エスディアイ株式会社Samsung SDI Co., Ltd. リチウム二次電池用複合正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池
JP7165769B2 (ja) 2020-03-05 2022-11-04 三星エスディアイ株式会社 リチウム二次電池用複合正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池
US12107268B2 (en) 2020-03-05 2024-10-01 Samsung Sdi Co., Ltd. Composite positive electrode active material for lithium secondary battery, preparation method thereof, and lithium secondary battery including positive electrode including the same
US12308430B2 (en) 2020-03-05 2025-05-20 Samsung Sdi Co., Ltd. Composite positive electrode active material for lithium secondary battery, preparation method thereof, and lithium secondary battery including positive electrode including the same

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