WO2018084525A1 - Matériau actif de cathode pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant - Google Patents

Matériau actif de cathode pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant Download PDF

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WO2018084525A1
WO2018084525A1 PCT/KR2017/012143 KR2017012143W WO2018084525A1 WO 2018084525 A1 WO2018084525 A1 WO 2018084525A1 KR 2017012143 W KR2017012143 W KR 2017012143W WO 2018084525 A1 WO2018084525 A1 WO 2018084525A1
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active material
positive electrode
lithium secondary
electrode active
secondary battery
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PCT/KR2017/012143
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English (en)
Korean (ko)
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한규석
김상복
이기수
최윤영
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삼성에스디아이 주식회사
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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 cathode active material for a lithium secondary battery and a lithium secondary battery comprising the same.
  • lithium secondary batteries have been in the spotlight as power sources of portable small electronic devices.
  • the lithium secondary battery has a structure including a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, a separator located between the positive electrode and the negative electrode, and an electrolyte.
  • the negative electrode active material various types of carbon-based materials or Si-based active materials including artificial, natural graphite, and hard carbon capable of inserting / desorbing lithium are used.
  • the cathode active material is mainly composed of an oxide composed of lithium and a transition metal having a structure capable of intercalation of lithium ions such as LiCoO 2 , LiMn 2 O 4 , LiNi 1 - x Co x O 2 (0 ⁇ x ⁇ 1), and the like. Used.
  • Na is mainly included as an impurity in the raw material, and Na is known as a material that lowers the sintering of the positive electrode active material produced during heat treatment, thereby causing poor contact between particles and reducing conductivity. It was intended to reduce the Na content contained in the active material to less than 100 ppm.
  • Na x CoO 2 is first prepared, followed by solution reaction of Na x CoO 2 and a lithium raw material such as Li 2 CO 3 to ion-exchange Na and Li to form a layered structure. It may be prepared in a form in which a certain amount of Li and Na coexist in the Li site of.
  • the prepared active material is an active material having a prismatic structure that is not layered. This method can widen the Na content range, and as the charge and discharge are repeated, it can suppress the transition to the spinel structure to suppress the capacity decrease of the positive electrode active material. There is a problem that cannot be applied.
  • One embodiment of the present invention is to provide a positive electrode active material for a lithium secondary battery having excellent initial charge and discharge efficiency, excellent high voltage phase transition characteristics and high temperature standing cycle life retention.
  • Another embodiment is to provide a lithium secondary battery including the positive electrode active material.
  • One embodiment of the present invention provides a cathode active material for a lithium secondary battery including a compound represented by the following Chemical Formula 1.
  • y may be 0 ⁇ y ⁇ 0.006.
  • the positive electrode active material may be for a high voltage lithium secondary battery having an operating voltage of 4.3V or more, in another embodiment, 4.3V to 4.5V, and in another embodiment, 4.35V to 4.45V.
  • the positive electrode active material may be prepared by a solid phase method.
  • Another embodiment includes a cathode including the cathode active material; A negative electrode including a negative electrode active material; And it provides a lithium secondary battery comprising an electrolyte.
  • the cathode active material for a lithium secondary battery according to an embodiment may provide a lithium secondary battery having excellent initial charging and discharging efficiency, excellent high voltage phase transition characteristics, and high temperature standing life retention.
  • FIG. 1 is a view schematically showing the structure of a lithium secondary battery according to one embodiment of the present invention.
  • Figure 2 is a graph showing the X-ray diffraction measurement results of the positive electrode active material prepared in Examples 1 to 3 and Comparative Example 1.
  • FIG. 4 is a scanning electron micrograph according to primary firing (A) and secondary firing (B) of the positive electrode active material prepared according to Example 2.
  • FIG. 4 is a scanning electron micrograph according to primary firing (A) and secondary firing (B) of the positive electrode active material prepared according to Example 2.
  • FIG. 6 is a graph showing the rate characteristics of the half-cell containing the positive electrode active material of Examples 1 to 3 and Comparative Example 1.
  • FIG. 7 is a graph showing rate characteristics of a half cell including the positive electrode active materials of Example 2 and Comparative Example 2.
  • FIG. 8 is a graph showing room temperature cycle life characteristics of a half cell including the cathode active materials of Examples 1 to 3 and Comparative Examples 1 and 2.
  • FIG. 8 is a graph showing room temperature cycle life characteristics of a half cell including the cathode active materials of Examples 1 to 3 and Comparative Examples 1 and 2.
  • the cathode active material for a rechargeable lithium battery according to one embodiment of the present invention may include a compound represented by the following Formula 1.
  • the cathode active material is a compound in which a part of Li is substituted with Na, and a part of Co is substituted with Ti with Mg, optionally Mg.
  • x value may be 0 ⁇ x ⁇ 0.01, according to one embodiment may be 0 ⁇ x ⁇ 0.005, and according to another embodiment, 0.002 ⁇ x ⁇ 0.005.
  • the x value is included in the above range, so that the capacity may be maintained even at high C-rate, long life at room temperature, and high temperature life of 45 ° C.
  • the x value exceeds 0.01, a secondary phase other than the layered structure is produced, i.e., it cannot maintain a proper structure, and a large amount of Na can be precipitated to the cathode during charging and discharging, resulting in deterioration of the electrochemical properties. not.
  • the layer structure of the positive electrode active material may be improved, and electrical conductivity may be improved, and lifespan retention may be improved at a high voltage of 4.4 V or more. If Mg and, optionally, Mg and Ti replace Li together, the amount of active Li participating in the electrochemical reaction may be reduced, and the capacity and life may be reduced by blocking a channel through which Li diffuses.
  • the y value in the cathode active material may be 0 ⁇ y ⁇ 0.01, and according to one embodiment, 0 ⁇ y ⁇ 0.006.
  • the y value may have an advantage of improving the life characteristics by exerting the pillar effect of maintaining the structure of Li—O—Li at high voltage. If the value of y is 0 or exceeds 0.01, Mg may inadvertently enter the Li site and deteriorate the capacity and life characteristics.
  • a z value may be 0 ⁇ z ⁇ 0.01, and according to one embodiment, 0 ⁇ z ⁇ 0.005 .
  • Ti is included in the cathode active material together with Mg, the structure can be stabilized at a high voltage, and at the same time, the electrical conductivity is improved, thereby improving the service life and rate characteristics.
  • Such an effect can be effectively obtained when the z value is 0.01 at maximum, and if it exceeds 0.01, there may be a problem that TiO 2 is left without entering the Co site.
  • Such a positive electrode active material may be suitably used in a high voltage lithium secondary battery having an operating voltage of 4.3 V or higher, and according to one embodiment, the operating voltage is 4.3 V to 4.5 V, and according to another embodiment, the operating voltage is 4.3 V to 4.45. It can be suitably used for the high voltage lithium secondary battery which is V.
  • V the high voltage lithium secondary battery which is V.
  • x is a positive electrode active material of 0, y is 0 in a high-voltage lithium secondary battery of 4.4V or more, there may be a problem that the layer structure collapses during charging and discharging and capacity is greatly reduced at the beginning of the life cycle Not appropriate
  • Such a positive electrode active material may be manufactured by a solid phase method. This solid state method is explained below.
  • Lithium raw material, cobalt raw material, sodium raw material and magnesium raw material are mixed. At this time, the titanium raw material may be further added.
  • the lithium raw material may include lithium acetate, lithium nitrate, lithium hydroxide, lithium carbonate, lithium acetate, hydrates thereof, or a combination thereof.
  • the cobalt raw material may include cobalt nitrate, cobalt hydroxide, cobalt oxide, cobalt acetate, cobalt carbonate, hydrates thereof, or a combination thereof.
  • the sodium raw material may include sodium nitrate, sodium hydroxide, sodium carbonate, sodium oxide, sodium acetate, or a combination thereof.
  • the magnesium raw material may include magnesium nitrate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium acetate, or a combination thereof.
  • the titanium raw material may include titanium nitrate, titanium hydroxide, titanium carbonate, Titanium oxide, titanium acetate, or a combination thereof.
  • the mixing ratio of the lithium raw material, the cobalt raw material, the sodium raw material and the magnesium raw material, and optionally the titanium raw material may be properly adjusted to obtain the composition of Chemical Formula 1.
  • the resulting mixture is subjected to primary heat treatment.
  • the primary heat treatment process may be carried out at a temperature of 1000 °C to 1050 °C, wherein the heat treatment time may be 4 hours to 16 hours.
  • the heat treatment atmosphere may be an air atmosphere, an oxygen atmosphere, or a combination thereof.
  • a second heat treatment is performed on the first heat treatment product to prepare a cathode active material.
  • the secondary heat treatment process may be further subjected to a secondary heat treatment, a post heat treatment for 4 hours to 8 hours at a temperature of 900 °C to 1000 °C. If the secondary heat treatment process is not performed, Na may precipitate on the surface of the positive electrode active material, and in this case, since it becomes a secondary phase having a structure other than a layered structure, the standard capacity of the active material decreases, and electrical conductivity decreases, thereby improving the life characteristics. It can be adversely affected and not appropriate.
  • Another embodiment includes a cathode including the cathode active material; cathode; And it provides a lithium secondary battery comprising an electrolyte.
  • the positive electrode includes a current collector and a positive electrode active material formed on the current collector and including a positive electrode active material.
  • the content of the cathode active material may be 90% by weight to 98% by weight based on the total weight of the cathode active material layer.
  • the cathode active material layer may further include a binder and a conductive material. The binder and the conductive material may be included in amounts of 1 wt% to 5 wt% based on the total weight of the positive electrode active material layer.
  • the binder is polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, polyvinyl fluoride, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride , Polyethylene, polypropylene, styrene-butadiene rubber, acrylic styrene butadiene rubber, epoxy resin, nylon and the like can be used, but is not limited thereto.
  • the conductive material examples include carbonaceous materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fibers, metal powders such as copper, nickel, aluminum, and silver, and polyphenylene derivatives such as metallic fibers such as metal fibers.
  • a conductive material containing a conductive polymer or a mixture thereof can be used.
  • Al foil may be used as the current collector, but is not limited thereto.
  • the negative electrode includes a negative electrode active material layer including a current collector and a negative electrode active material formed on the current collector.
  • the anode active material includes a material capable of reversibly intercalating / deintercalating lithium ions, a lithium metal, an alloy of lithium metal, a material doped and undoped with lithium, or a transition metal oxide.
  • any 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 can be used together.
  • the crystalline carbon include graphite such as amorphous, plate, flake, spherical or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon include soft carbon or hard carbon ( hard carbon), mesophase pitch carbide, calcined coke, and the like.
  • alloy of the lithium metal examples include lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn. Alloys of the metals selected may be used.
  • Examples of materials that can be doped and undoped with lithium include Si, SiO x (0 ⁇ x ⁇ 2), and Si-Q alloys (wherein Q is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a Group 15 element, and 16).
  • Sn, SnO 2 , Sn-R alloys wherein R is an alkali metal, an alkaline earth metal, a Group 13 element, 14 element, an element selected from group 15 elements, group 16 elements, transition metals, rare earth elements and combinations thereof, Sn may be mentioned not
  • R is an alkali metal, an alkaline earth metal, a Group 13 element, 14 element, an element selected from group 15 elements, group 16 elements, transition metals, rare earth elements and combinations thereof, Sn may be mentioned not
  • the elements Q and R include Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge, P, As, Sb, Bi, One selected from the group consisting of S, Se, Te, Po, and a combination thereof can be used.
  • transition metal oxide examples include vanadium oxide, lithium vanadium oxide or lithium titanium oxide.
  • the content of the negative electrode active material in the negative electrode active material layer may be 95% by weight to 99% by weight with respect to the total weight of the negative electrode active material layer.
  • the negative electrode active material layer includes a binder, and optionally may further include a conductive material.
  • the content of the binder in the negative electrode active material layer may be 1% by weight to 5% by weight based on the total weight of the negative electrode active material layer.
  • 90 wt% to 98 wt% of the negative electrode active material, 1 wt% to 5 wt% of the binder, and 1 wt% to 5 wt% of the conductive material may be used.
  • the binder adheres the anode active material particles to each other well, and also serves to adhere the anode active material to the current collector well.
  • a non-aqueous binder, an aqueous binder, or a combination thereof may be used as the binder.
  • the non-aqueous binder may include polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers including ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride , Polyethylene, polypropylene, polyamideimide, polyimide, or a combination thereof.
  • the aqueous binder may include styrene-butadiene rubber, acrylated styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber, acrylic rubber, butyl rubber, fluorine rubber, ethylene propylene copolymer, polyepichlorohydrin , Polyphosphazene, polyacrylonitrile, polystyrene, ethylene propylene diene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, polyester resin, acrylic resin, phenol resin, epoxy resin, polyvinyl alcohol and combinations thereof It may be selected.
  • SBR acrylated styrene-butadiene rubber
  • SBR acrylated styrene-butadiene rubber
  • acrylonitrile-butadiene rubber acrylic rubber, butyl rubber, fluorine rubber, ethylene propylene copolymer, polyepichlorohydrin , Polyphosphazen
  • an aqueous binder When using an aqueous binder as the negative electrode binder, it may further include a cellulose-based compound that can impart viscosity as a thickener.
  • a cellulose-based compound that can impart viscosity as a thickener.
  • carboxymethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, these alkali metal salts, etc. can be used in mixture of 1 or more types. Na, K or Li may be used as the alkali metal.
  • the amount of the thickener used may be 0.1 parts by weight to 3 parts by weight based on 100 parts by weight of the negative electrode active material.
  • the conductive material examples include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen 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 derivatives; Or a conductive material containing a mixture thereof.
  • 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.
  • the electrolyte includes a non-aqueous organic solvent and a lithium salt.
  • the non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • non-aqueous organic solvent a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, or aprotic solvent may be used.
  • Examples of the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), and ethylene carbonate ( EC), propylene carbonate (PC), butylene carbonate (BC) and the like can be used.
  • the ester solvent may be methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, decanolide, mevalonolactone, and caprolactone. And the like can be used.
  • Dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, etc. may be used as the ether solvent.
  • cyclohexanone may be used as the ketone solvent.
  • ethyl alcohol, isopropyl alcohol, etc. may be used as the alcohol solvent, and the aprotic solvent may be R-CN (R is a straight-chain, branched, or cyclic hydrocarbon group having 2 to 20 carbon atoms. Nitriles such as a double bond aromatic ring or ether bond), amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolane, and the like can be used. .
  • the organic solvents may be used alone or in combination of one or more, and the mixing ratio in the case of mixing one or more may be appropriately adjusted according to the desired battery performance, which can be widely understood by those skilled in the art. have.
  • the carbonate solvent it is preferable to use a mixture of cyclic carbonate and chain carbonate.
  • 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 organic solvent may further include an aromatic hydrocarbon organic solvent in the carbonate solvent.
  • the carbonate solvent and the aromatic hydrocarbon organic solvent may be mixed in a volume ratio of 1: 1 to 30: 1.
  • an aromatic hydrocarbon compound of Formula 1 may be used as the aromatic hydrocarbon-based organic solvent.
  • R 1 to R 6 are the same as or different from each other and are selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group, and a combination thereof.
  • aromatic hydrocarbon organic solvent examples include benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-tri Fluorobenzene, 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-dioodobenzene, 1,3-dioiobenzene, 1,4-dioiobenzene, 1,2,3-triiodobenzene, 1, 2,4-triiodobenzene, toluene, fluorotoluene, 2,3-difluorotoluene, 2,4-difluorotol, to
  • the electrolyte may further include vinylene carbonate or an ethylene carbonate-based compound of Formula 2 as a life improving additive to improve battery life.
  • R 7 and R 8 are the same as or different from each other, and are selected from the group consisting of hydrogen, a halogen group, a cyano group (CN), a nitro group (NO 2 ), and an alkyl group having 1 to 5 fluorinated carbon atoms. At least one of R 7 and R 8 is selected from the group consisting of a halogen group, a cyano group (CN), a nitro group (NO 2 ) and a fluorinated C1-5 alkyl group, provided that both R 7 and R 8 are all Not hydrogen.
  • ethylene carbonate-based compound examples include difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate or fluoroethylene carbonate. Can be. In the case of further using such life improving additives, the amount thereof can be properly adjusted.
  • 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 the 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 , LiN (SO 2 C 2 F 5 ) 2 , Li (CF 3 SO 2 ) 2 N, LiN (SO 3 C 2 F 5 ) 2 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ), where x and y are natural numbers, for example Supporting one or more selected from the group consisting of LiCl, LiI and LiB (C 2 O 4 ) 2 (lithium bis (oxalato) borate (LiBOB)); It is preferable to
  • 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, and polyethylene / polypropylene two-layer separator, polyethylene / polypropylene / polyethylene three-layer separator, polypropylene / polyethylene / poly It goes without saying that a mixed multilayer film such as a propylene three-layer separator can be used.
  • FIG. 1 is an exploded perspective view of a rechargeable lithium battery according to one embodiment of the present invention.
  • a lithium secondary battery according to an embodiment is described as an example of being rectangular, the present invention is not limited thereto, and may be applied to various types of batteries, such as a cylindrical shape and a pouch type.
  • the lithium secondary battery 100 includes an electrode assembly 40 and an electrode assembly 40 interposed between the positive electrode 10 and the negative electrode 20 with a separator 30 interposed therebetween. It may include a case 50 is built.
  • the positive electrode 10, the negative electrode 20, and the separator 30 may be impregnated with an electrolyte (not shown).
  • Lithium carbonate (Li 2 CO 3 ), cobalt oxide (Co 3 O 4 ), magnesium oxide (MgO), titanium oxide (TiO 2 ) was added to Li 1 - x Na x Co 1 -y- z Mg y Ti z in the final product.
  • a positive electrode active material was prepared.
  • the lattice constant of the positive electrode active material was obtained by X-ray diffraction measurement using CuK ⁇ rays.
  • the measured a-axis length, c-axis length, and the distance ratio between the crystal axes (c / a axis ratio) are shown in Table 1 together.
  • V ( ⁇ 3 ) represents the volume of a unit cell.
  • Example 1 2.8166 2.8166 14.055 4.990 96.57
  • Example 1 2.8167 2.8167 14.057 4.991 96.58
  • Example 2 2.8169 2.8169 14.058 4.991 96.61
  • Example 3 2.8173 2.8173 14.062 4.991 96.67
  • Na doping of the cathode active material for lithium secondary batteries prepared in Examples 1 to 3 was additionally measured using a nuclear magnetic resonance device (NMR).
  • the magnetic resonance apparatus was 23 Na-NMR (Bruker Avance III), the results are shown in FIG.
  • NMR of sodium carbonate (Na 2 CO 3 ), which is a Na raw material was also measured, and the results are also shown in FIG. 3 (in FIG. 2, the y-axis is intensity).
  • the chemically active signal of Na did not appear in the cathode active material prepared in Comparative Example 1.
  • the positive electrode active materials prepared in Examples 1 to 3 showed a chemical shift at -8 ppm and 58 ppm, and were completely different from the spectrum of Na 2 CO 3 used as a raw material.
  • the two chemical signals in Examples 2 to 3 it can be seen that the relative strength gradually increases as the doping amount of Na increases.
  • Example 2 The results of Example 2 are shown in FIG. 4 (A: primary firing, B: secondary firing), and the results of Comparative Example 1 are shown in FIG. 4 (A: primary firing, B: secondary firing).
  • Example 2 Na was precipitated on the surface of the product when the primary firing was performed at 1025 ° C., but Na precipitates were formed on the surface of the cathode active material prepared by secondary firing at 950 ° C. It was confirmed that there was no.
  • the cathode active material slurry prepared by mixing the cathode active material, the carbon black conductive material, and the polyvinylidene fluoride binder prepared according to Examples 1 to 3 and Comparative Example 1 in an N-methyl pyrrolidone solvent at a weight ratio of 96: 2: 2. was prepared.
  • the prepared positive electrode active material slurry was uniformly coated on Al foil, and vacuum dried at 120 ° C. to prepare a positive electrode.
  • a coin cell was prepared.
  • the half-cell using the cathode active material of Comparative Example 1 which is not doped with Na, has a significantly reduced capacity at a current density of 2C or more.
  • the capacity does not significantly decrease under various current density conditions from 0.2C to 3C, that is, the high rate characteristics are excellent. It can be seen.
  • the half-cell using the positive electrode active material of Example 2 doped with 0.5 mol% of Na does not significantly reduce its capacity under various current density conditions from 0.2C to 3C, that is, excellent in high rate characteristics.
  • the half cell using the positive electrode active material of Comparative Example 2 is significantly reduced from 1C. From this result, when Mg and Ti are not doped, the capacity starts to decrease from the current density of 0.5C which is relatively low in the voltage range of 4.3V, and at 3C, the capacity almost does not work as 0. Therefore, Na It can be seen that even if doped, Mg and Ti are not included, the high rate characteristic is seriously degraded.
  • the half-cells prepared by using the positive electrode active materials prepared according to Examples 1 to 3 and Comparative Examples 1 and 2 were charged and discharged at 0.2C at room temperature (25 ° C.) for 40 times to measure the discharge capacity according to the cycle.
  • room temperature 25 ° C.
  • the cycle life characteristics are closely correlated with the amount of Na doping. That is, the battery using the positive electrode active material of Example 2 doped with Na 0.5 mol%, Example 3, the Na doping amount increased to 1.0 mol%, the Na doped amount reduced to 0.2 mol% using the positive electrode active material of Example 1 Compared to the cell, the result with the least capacity reduction up to 40 cycles was obtained.

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Abstract

La présente invention concerne un matériau actif de cathode pour une batterie secondaire au lithium et une batterie secondaire au lithium comprenant ledit matériau. Le matériau actif de cathode comprend un composé représenté par la formule 1 suivante : [Formule 1] Li1-xNaxCo1-y-zMgyTizO2 (où 0 < x ≤ 0,05, 0 < y ≤ 0,01, et 0 ≤ z ≤ 0,01).
PCT/KR2017/012143 2016-11-07 2017-10-31 Matériau actif de cathode pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant WO2018084525A1 (fr)

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KR10-2016-0147470 2016-11-07
KR1020160147470A KR20180050894A (ko) 2016-11-07 2016-11-07 리튬 이차 전지용 양극 활물질 및 이를 포함하는 리튬 이차 전지

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020175781A1 (fr) * 2019-02-28 2020-09-03 주식회사 에스엠랩 Matériau actif de cathode, son procédé de préparation, et batterie secondaire comprenant la cathode le comprenant
WO2022266799A1 (fr) * 2021-06-21 2022-12-29 宁德新能源科技有限公司 Dispositif électrochimique et dispositif électronique
CN116062797A (zh) * 2023-01-17 2023-05-05 珠海冠宇电池股份有限公司 一种正极材料及包含该正极材料的电池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010053328A2 (fr) * 2008-11-10 2010-05-14 주식회사 엘지화학 Matériau actif positif doté de caractéristiques de tension élevée améliorées
JP5100069B2 (ja) * 2006-09-15 2012-12-19 三洋電機株式会社 非水電解質二次電池およびその製造方法
US20130101893A1 (en) * 2011-10-25 2013-04-25 Apple Inc. High-voltage lithium-polymer batteries for portable electronic devices
KR20140040673A (ko) * 2010-10-20 2014-04-03 카운슬 오브 사이언티픽 앤드 인더스트리얼 리서치 양극 물질 및 이로부터의 리튬이온 배터리
KR20160059781A (ko) * 2014-11-19 2016-05-27 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5100069B2 (ja) * 2006-09-15 2012-12-19 三洋電機株式会社 非水電解質二次電池およびその製造方法
WO2010053328A2 (fr) * 2008-11-10 2010-05-14 주식회사 엘지화학 Matériau actif positif doté de caractéristiques de tension élevée améliorées
KR20140040673A (ko) * 2010-10-20 2014-04-03 카운슬 오브 사이언티픽 앤드 인더스트리얼 리서치 양극 물질 및 이로부터의 리튬이온 배터리
US20130101893A1 (en) * 2011-10-25 2013-04-25 Apple Inc. High-voltage lithium-polymer batteries for portable electronic devices
KR20160059781A (ko) * 2014-11-19 2016-05-27 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020175781A1 (fr) * 2019-02-28 2020-09-03 주식회사 에스엠랩 Matériau actif de cathode, son procédé de préparation, et batterie secondaire comprenant la cathode le comprenant
WO2022266799A1 (fr) * 2021-06-21 2022-12-29 宁德新能源科技有限公司 Dispositif électrochimique et dispositif électronique
CN116062797A (zh) * 2023-01-17 2023-05-05 珠海冠宇电池股份有限公司 一种正极材料及包含该正极材料的电池

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