WO2016122277A1 - Matériau actif positif pour batterie secondaire au lithium, son procédé de production et batterie secondaire au lithium comprenant celui-ci - Google Patents

Matériau actif positif pour batterie secondaire au lithium, son procédé de production et batterie secondaire au lithium comprenant celui-ci Download PDF

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WO2016122277A1
WO2016122277A1 PCT/KR2016/001073 KR2016001073W WO2016122277A1 WO 2016122277 A1 WO2016122277 A1 WO 2016122277A1 KR 2016001073 W KR2016001073 W KR 2016001073W WO 2016122277 A1 WO2016122277 A1 WO 2016122277A1
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Prior art keywords
lithium
active material
metal
coating layer
positive electrode
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PCT/KR2016/001073
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English (en)
Korean (ko)
Inventor
최수안
정호준
전상훈
양지운
신준호
정진성
정봉준
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주식회사 엘앤에프
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Priority claimed from KR1020160012168A external-priority patent/KR20160094338A/ko
Publication of WO2016122277A1 publication Critical patent/WO2016122277A1/fr

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    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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

  • It relates to a positive electrode active material for a lithium secondary battery, a manufacturing method thereof and a positive electrode active material for a lithium secondary battery.
  • a battery generates electric power by using an electrochemical reaction material for the positive electrode and the negative electrode.
  • a typical example of such a battery is a lithium secondary battery that generates electrical energy by a change in chemical potent al when lithium ions are intercalated / deintercalated at a positive electrode and a negative electrode.
  • the lithium secondary battery is prepared by using a material capable of reversible intercalation / deintercalation of lithium ions as a positive electrode and a negative electrode active material, and layering an organic electrolyte or a polymer electrolyte between the positive electrode and the negative electrode.
  • a lithium composite metal compound is used as a cathode active material of a lithium secondary battery, and composite metal oxides such as LiCo02, LiMn 2 O 4> LiNi0 2 , and LiMn0 2 have been studied.
  • Mn-based cathode active materials such as LiMn 2 0 4 and LiMn0 2 are easy to synthesize, are relatively inexpensive, have the best thermal stability compared to other active materials when overcharged, and have low environmental pollution and are attractive materials. Although it has a disadvantage, the capacity is small.
  • LiCo0 2 has a good electrical conductivity and a high battery voltage of about 3.7V, and also has excellent cycle life characteristics, stability, and discharge capacity. Thus, LiCo0 2 is a representative cathode active material commercially available and commercially available. However, since LiCo0 2 is expensive, it takes up more than 30% of the battery price, which leads to a problem of low price competitiveness.
  • LiNi0 2 exhibits the highest discharge capacity of battery characteristics among the cathode active materials mentioned above, but has a disadvantage in that it is difficult to synthesize. Also high of nickel The oxidized state causes deterioration of battery and electrode life, and causes severe self discharge and inferior reversibility. In addition, it is difficult to commercialize the stability is not perfect.
  • a cathode active material for a lithium secondary battery including various coating layers for improving battery characteristics has been provided.
  • the present invention provides a cathode active material for a lithium secondary battery having excellent high capacity, high efficiency, and lifespan, and provides a lithium secondary battery including a cathode including the cathode active material.
  • the metal M is at least one element selected from the group consisting of Ni, Co and Mn and M, is a group consisting of Zr ', Ti, Mg, Ca, V, Zn, W, Mo, Sn, Ga, B, and Al. At least one element selected from 0.90 ⁇ a ⁇ 1.10, 0.09 ⁇ b ⁇ 0.15,
  • It includes a coating layer located on at least a portion of the surface of the compound of Formula 1,
  • the coating layer includes Li 3 P0 4 , and the coating layer provides a cathode active material for a lithium secondary battery comprising a composite coating layer further comprising lithium metal oxide, metal oxide, or a combination thereof.
  • the metal M ⁇ may be at least one element selected from Mg, Ti, Zr, Al, and B. In Chemical Formula 1, The metal can be.
  • Li r i ch Li / M rat i o> 1.0
  • Li 3 PO 4 included in the composite coating layer, or lithium of lithium metal oxide is derived from Li contained in the compound capable of reversible intercalation and deintercalation of the lithium, or from a separate Li supply material Can be.
  • the metal in the lithium metal oxide, or metal oxide contained in the composite coating layer may be Na, K, Ca, Ni, Co, Ti, Al, Si, Sn, Mn, Cr, Fe, V, Zr, or a combination thereof. have.
  • the content of the composite coating layer relative to the total weight of the cathode active material is 0.2 to
  • the phosphorus source in a compound capable of reversible intercalation and deintercalation of lithium; And / or mixing a metal source to uniformly attach the phosphorus source to a surface of the compound capable of reversible intercalation and deintercalation of lithium; And
  • the phosphorus source or heat-treating a compound capable of reversible intercalation and deintercalation of lithium to which a metal source is attached, including Li 3 P0 4 , wherein the coating layer further comprises lithium metal oxide, metal oxide, or a combination thereof. It provides a method for producing a cathode active material for a lithium secondary battery comprising the step; obtaining; a compound capable of reversible intercalation and deintercalation of lithium comprising a composite coating layer. '
  • Metal M is at least one element selected from the group consisting of Ni, Co and Mn and M, is selected from the group consisting of Zr, Ti, Mg, Ca, V, Zn, W, Mo, Sn, Ga, B, and Al At least one element, and 0.90 ⁇ a ⁇ 1.10, 0.09 ⁇ b ⁇ 0.15.
  • the firing temperature may be 750 to 1,050 ° C.
  • the step of obtaining a compound capable of reversible intercalation and deintercalation of lithium comprising a composite coating layer further comprising; in the heat treatment temperature may be 650 to 950 ° C.
  • cathode active material having excellent battery characteristics and a lithium secondary battery including the same.
  • 1 is a schematic view of a lithium secondary battery. .
  • the metal M is at least one element selected from the group consisting of Ni, Co and Mn and M, is at least one selected from the group consisting of Zr, Ti, Mg, Ca, V, Zn, W, Mo, Sn, and Al. Elemental element, 0.90 ⁇ a ⁇ 1.10, 0.09 ⁇ b ⁇ 0.15
  • It includes a coating layer located on at least a portion of the surface of the compound of Formula 1,
  • the coating layer includes Li 3 PO 4 and the coating layer provides a cathode active material for a lithium secondary battery comprising a composite coating layer further comprising a lithium metal oxide, a metal oxide, or a combination thereof.
  • the metal may be at least one element selected from Mg, Ti, Zr, Al, and B.
  • Chemical Formula 1
  • the metal M ⁇ may be Mg. ...
  • the compound capable of reversible intercalation and deintercalation of lithium may be Li rich (Li / M ratio> 1.0) composition.
  • Li 3 P04 included in the composite coating layer, or lithium of lithium metal oxide may be derived from Li contained in the compound capable of reversible intercalation and deintercalation of the lithium, or may be derived from a separate Li supply material. .
  • the metal in the lithium metal oxide, or metal oxide contained in the composite coating layer may be Na, K, Ca, Ni, Co, Ti, Al, Si, Sn, Mn, Cr, Fe, V, Zr, or a combination thereof. have.
  • the content of the composite coating layer relative to the total weight of the positive electrode active material is 0.2 to Can be 2.0% by weight
  • Li 3 P0 4 Lithium metal oxide, a positive electrode active material including a composite coating layer further comprising a metal oxide or a combination thereof may improve battery characteristics of a lithium secondary battery. More specifically, it is possible to provide a cathode active material having a higher initial capacity, improved efficiency characteristics and excellent rate characteristics than conventional cathode active materials.
  • the metal compound including Li of the composite coating layer may serve to increase the diffusion degree of Li ions in the cathode active material to facilitate the movement of Li ions, thereby contributing to improvement of battery characteristics.
  • the above reversible intercalation and deintercalation compound of lithium may be particularly preferable for implementing battery characteristics by the coating layer if the specific doping element is excessively doped.
  • the LiM0 2 (M is Ni, Co, or Mn) composition system rock-salt structures can be formed on the surface of the anode material under the usual manufacturing conditions.
  • the rearrangement reaction (Rocksal t >> layered) occurs to control the structural defects and impurities formed on the surface.
  • LiM0 2 (M is Ni, Co, or Mn) when applying the composition Li 3 P0 4 is subject to the process is the Li shortage occurs battery characteristics, some degradation in the formed and also Li 3 in the composition that is not doped When the P0 4 coating is carried out, structural defects may be caused by the reduction reaction generated between P and the surface of the cathode material.
  • Li 3 P0 4 is applied when the coating treatment is applied to a compound having a composition of Li r ich (Li / M rat io> 1.0) and capable of reversible intercalation and deintercalation of a lithium that is excessively doped with a specific element.
  • Reversible intercalation of lithium represented by formula (1) Preparing a compound capable of deintercalation
  • Phosphorus source And / or preparing a metal source
  • Metal M is at least one element selected from the group consisting of Ni, Co and Mn and M, is selected from the group consisting of Zr, Ti, Mg, Ca, V, Zn, W, Mo, Sn, Ga, B, and Al At least one element, and 0.90 ⁇ a ⁇ L10 and 0.09 ⁇ b ⁇ 0.15.
  • the firing temperature may be between 750 and 1,050 ° C.
  • the phosphorus source or heat-treating a compound capable of reversible intercalation and deintercalation of lithium with a metal source attached thereto, comprising U3P04, wherein the coating layer comprises : Obtaining a compound capable of reversible intercalation and deintercalation of lithium, including a composite coating layer further comprising lithium metal oxide, metal oxide, or a combination thereof;
  • the heat treatment temperature may be 650 to 95CTC. Description of the rest of the configuration is the same as the embodiment of the present invention described above, so the description thereof will be omitted.
  • a lithium secondary battery comprising a positive electrode, a negative electrode and an electrolyte, the positive electrode includes a current collector and a positive electrode active material layer formed on the current collector, the positive electrode active material layer, It provides a lithium secondary battery comprising the positive electrode active material described above.
  • the positive electrode active material layer may include a binder and a conductive material.
  • the binder adheres positively to the positive electrode active material particles, and also serves to adhere the positive electrode active material to the current collector well, and representative examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose and diacetyl cellulose.
  • Polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyridone, polyureth, polytetraple ⁇ oethylene, polyvinylidene fluoride, Polyethylene, polypropylene, styrene-butadiene rubber, acrylic styrene-butadiene rubber epoxy resin, nylon, etc. may be used, but is not limited thereto.
  • the conductive material is used to impart conductivity to the electrode, and any battery can be used as long as it is an electronic conductive material without causing chemical change in the battery.
  • any battery can be used as long as it is an electronic conductive material without causing chemical change in the battery.
  • natural alum, artificial alum, carbon black, acetylene black, ketjen Carbon-based materials such as black and carbon fiber;
  • Metal materials such as metal powder or metal fibers such as copper, nickel, aluminum and silver; Conductive polymers such as polyphenylene and derivatives; Or an electroconductive material containing these mixture can be used.
  • the negative electrode includes a current collector and a negative electrode active material layer formed on the current collector, and the negative electrode active material layer includes a negative electrode active material.
  • the negative electrode active material includes a material capable of reversibly intercalating / deintercalating lithium ions, a lithium metal, an alloy of lithium metal, a material capable of doping and undoping lithium, or a transition metal oxide. .
  • a carbon-based negative electrode active material generally used in a lithium ion secondary battery may be used, and representative examples thereof include crystalline carbon, Amorphous carbon or these may be used together.
  • the crystalline carbon are amorphous, plate, Graphite, such as flakes, spherical or fibrous natural or artificial agglomerates.
  • the amorphous carbon include soft carbon (low temperature calcined carbon) or hard carbon, mesophase. Pitch carbide, calcined coke, and the like.
  • alloy of the lithium metal lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr,
  • Alloys of metals selected from the group consisting of Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al and Sn can be used.
  • Examples of a material capable of doping and undoping lithium include Si, SiO x (0 ⁇ x ⁇ 2), and Si-Y alloys (wherein Y is an alkali metal, an alkaline earth metal, a Group 13 element, and a Group 14 element transition metal. Element selected from the group consisting of ash earth elements and combinations thereof, not Si), Sn, Sn0 2 , Sn-Y (Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition rapid, an element selected from rare earth elements and combinations thereof, Sn and the like are not), and may also use at least one common and Si0 2 were combined of them.
  • transition metal oxide examples include vanadium oxide, lithium vanadium oxide, and the like.
  • the negative electrode active material layer also includes a binder, and may optionally further include a conductive material.
  • the binder adheres the negative electrode active material particles to each other well, and also adheres the negative electrode active material to the current collector, and typical examples thereof include polyvinyl alcohol, carboxymethyl salose, hydroxypropyl cellulose, poly H, and the like.
  • Nyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene Styrene ⁇ butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon and the like may be used, but is not limited thereto.
  • the conductive material is used to impart conductivity to the electrode
  • any electronic conductive material can be used without causing chemical change, and examples thereof include carbon-based materials such as natural alum, artificial alum, carbon black, acetylene black, ketjen black, and carbon fiber; Metal materials such as metal powder or metal fibers such as copper, nickel and aluminum silver; Conductive polymers such as polyphenylene derivatives; Or an electroconductive material containing these mixture can be used.
  • the current collector may be selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and combinations thereof. .
  • a 1 may be used as the current collector, but is not limited thereto.
  • the negative electrode and the positive electrode are prepared by mixing an active material, a conductive material and a binder in a solvent to prepare an active material composition, and applying the composition to a current collector. Since such an electrode manufacturing method is well known in the art, detailed description thereof will be omitted.
  • N-methylpyridone may be used as the solvent, but is not limited thereto.
  • the electrolyte contains a non-aqueous organic solvent and a lithium salt.
  • the non-aqueous organic solvent serves as a medium for transfer of silver involved in the electrochemical reaction of the battery.
  • a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, or aprotic solvent may be used as the non-aqueous organic solvent.
  • the carbonate-based solvent may be dimethyl carbonate (DMC) or diethyl carbonate ( DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), methyl ethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), etc.
  • the ester solvent may be methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, decanoide.
  • Valerolactone, mevalonolactone (meva l ono l actone), caprolactone (capro lactone), and the like can be used.
  • the ether solvent dibutyl ether, tetraglyme, diglyme, dimetheethane, 2—methyltetrahydrofuran, tetrahydrofuran, and the like may be used, and the ketone solvent may be cyclohexanone or the like. This can be used.
  • ethyl alcohol, isopropyl alcohol, etc. may be used as the alcohol solvent, and as the aprotic solvent, R-CN (R is carbon number).
  • Amides such as nitrile dimethylformamide such as a linear, branched or ring structure hydrocarbon group of 2 to 20, which may include a double bond aromatic ring or an ether bond), 1,3-dioxolane and the like ⁇ Dioxolanes and sulfolanes can be used.
  • the non-aqueous organic solvent may be used alone or in combination of one or more, and the mixing ratio in the case of using one or more in combination may be appropriately adjusted according to the desired battery performance, which is widely understood by those skilled in the art. Can be.
  • the carbonate solvent it is preferable to use cyclic carbonate and chain carbonate in combination.
  • the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of 1: 1 to 1: 9, so that the performance of the electrolyte may be excellent.
  • the non-aqueous organic solvent according to the embodiment of the present invention may further include an aromatic hydrocarbon organic solvent in the carbonate solvent.
  • the carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed in a volume ratio of 1: 1 to 30: 1.
  • an aromatic hydrocarbon compound of Formula 2 may be used as the aromatic hydrocarbon organic solvent.
  • the aromatic hydrocarbon organic solvent is benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene , 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2 , 4-trichlorobenzene, iodobenzene, 1,2-diodiodobenzene, 1,3-dioiobenzene, 1 ⁇ 4-dioiobenzene, 1,2,3-triiodobenzene, 1 ⁇ 2 , 4-triiodobenzene, toluene, fluorotoluene, 1,2-difluoroluene, 1,3-di Fluorolu
  • the non-aqueous electrolyte may further include vinylene carbonate or an ethylene carbonate compound of Formula 3 to improve battery life.
  • R 7 and 3 ⁇ 4 are each independently hydrogen, halogen group-cyano group (CN), nitro group ( ⁇ 0 2 ) or C1 to C5 fluoroalkyl group, at least one of R 7 and 3 ⁇ 4 is halogen Group, cyano group (CN), nitro group (N0 2 ) or C1 to C5 fluoroalkyl group.)
  • ethylene carbonate compound examples include difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate or fluoroethylene carbonate. Etc. can be mentioned. If such life improving additives are used further, their amount can be adjusted accordingly.
  • the lithium salt is a substance that dissolves in an organic solvent and acts as a source of lithium ions in the battery to enable operation of a basic lithium secondary battery and to promote the movement of lithium ions between the positive electrode and the negative electrode.
  • Representative examples of such lithium salts are LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 ( LiC 4 F 9 S0 3l LiC10 4 , LiA10 2 , .LiAlCl 4 , LiN (C x F 2x + 1 S0 2 ) (C y F 2y) +1 S0 2 ) (where x and y are natural numbers), LiCl, Li I and LiB (C 2 0 4 ) 2 (lithium bis (oxalato) borate (LiBOB) One or more selected ones are included as supporting electrolytic salts.
  • the concentration of salt is preferably used in the range of 0.01 to 2.0M.
  • concentration of the lithium salt is included in the above range, since the electrolyte has an appropriate conductivity and viscosity, it may exhibit excellent electrolyte performance, and lithium ions may move effectively.
  • a separator may exist between the positive electrode and the negative electrode.
  • the separator polyethylene, polypropylene, polyvinylidene fluoride or two or more multilayer films thereof may be used .
  • a mixed multilayer film such as polyethylene / polypropylene two-layer separator, polyethylene / polypropylene / polyethylene three-layer separator, polypropylene / polyethylene / polypropylene three-layer separator, and the like can be used.
  • Lithium secondary batteries may be classified into lithium ion batteries, lithium ion polymer batteries, and lithium polymer batteries according to the type of separator and electrolyte used, and may be classified into cylindrical, square, coin, and pouch types according to their type. It can be divided into bulk type and thin film type according to the size. The structure, structure, and manufacturing method of these batteries are well known in the art, and thus detailed descriptions thereof are omitted.
  • the lithium secondary battery 1 schematically shows a typical structure of a lithium secondary battery of the present invention.
  • the lithium secondary battery 1 includes a positive electrode 3, a negative electrode 2, and an electrolyte solution impregnated in a separator 4 existing between the positive electrode 3 and the negative electrode 2.
  • the container 5 and the sealing member 6 which encloses the said battery container 5 are included.
  • Li A positive electrode active material was prepared as possible.
  • Example 2 100 g of the prepared cathode active material and Zr (0H) 4 powder. 0. 172 g of dry powder of Si0 2 powder 0.054g and (NH 4 ) 2 HP0 4 powder 0,387g to prepare a mixture in which the powder is attached to the surface of the positive electrode active material body and then the mixture to 800 ° C. Heat treatment was performed for 6 hours to prepare a positive electrode active material.
  • Example 2 100 g of the prepared cathode active material and Zr (0H) 4 powder. 0. 172 g of dry powder of Si0 2 powder 0.054g and (NH 4 ) 2 HP0 4 powder 0,387g to prepare a mixture in which the powder is attached to the surface of the positive electrode active material body and then the mixture to 800 ° C. Heat treatment was performed for 6 hours to prepare a positive electrode active material.
  • Example 2 100 g of the prepared cathode active material and Zr (0H) 4 powder. 0. 172 g of dry powder of Si0 2 powder 0.054g and (NH 4 )
  • the LiNi 0 .6oCoo.2oMno.2o0 2 was used. Production of coin cell
  • a positive electrode slurry was prepared by adding to 5.0 wt%.
  • the positive electrode slurry was applied to a thin film of aluminum (A1), which is a positive electrode current collector having a thickness of 20 to 40, and vacuum dried, followed by roll press to prepare a positive electrode.
  • Li-metal was used as the negative electrode.
  • a half cell of a coin sal type was manufactured using 1.15M LiPF 6 EC: DMC (l: lvol3 ⁇ 4) as an electrolyte.
  • Table 1 below is 4.5V initial Formation, rate characteristic, lcyle, 20cycle, 30cycle capacity and life characteristic data of the above Examples and Comparative Examples.
  • Example 1 192.47 97.79 186.10 181.13 177.23 97.33 95.23 96.66
  • Example 2 191.72 97.43 184.91 180.09 176.34 97.39 95.37 96.71
  • Example 3 202.47 91.07 196.22 183.74 180.11 93.64 91.79 91.14
  • Comparative Example 1184.92 95 9 292 195 295 195 295 195 295 195 295 179.14 174.12 96.25 93.55 95.61
  • the positive electrode active material including the excessively doped composite coating layer includes the composite coating layer, but Comparative Example 2, which is not doped, is confirmed to have a difference in battery characteristics. Excess doping is found to be useful for high voltages.
  • the positive electrode active material having a different composition is also confirmed to improve characteristics.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne un matériau actif positif destiné à une batterie secondaire au lithium, ledit matériau étant un composé pouvant intercaler et désintercaler le lithium de manière réversible et représenté par la formule chimique 1 : [formule chimique 1] LiaM1-bM'bO2, dans laquelle le métal M est au moins un élément choisi dans le groupe constitué par Ni, Co et Mn ; M' est au moins un élément choisi dans le groupe constitué par Zr, Ti, Mg, Ca, V, Zn, W, Mo, Sn, Ga, B et Al ; 0,90 < a < 1,10 ; et 0,09 < b < 0,15, le composé de formule chimique 1 comprenant une couche de revêtement positionnée sur au moins une partie de la surface de celui-ci, ladite couche de revêtement comprenant du Li3PO4 et comprenant également une couche de revêtement composite comprenant en outre des oxydes métalliques de lithium, des oxydes métalliques, ou une combinaison de ceux-ci.
PCT/KR2016/001073 2015-01-30 2016-02-01 Matériau actif positif pour batterie secondaire au lithium, son procédé de production et batterie secondaire au lithium comprenant celui-ci WO2016122277A1 (fr)

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KR20150014641 2015-01-30
KR10-2015-0014641 2015-01-30
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KR1020160012168A KR20160094338A (ko) 2015-01-30 2016-02-01 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112635722A (zh) * 2019-10-09 2021-04-09 北京卫蓝新能源科技有限公司 一种锂离子电池复合正极材料及制备方法

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