WO2019093653A1 - Matériau actif d'électrode positive pour accumulateur au lithium et accumulateur au lithium le comprenant - Google Patents

Matériau actif d'électrode positive pour accumulateur au lithium et accumulateur au lithium le comprenant Download PDF

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WO2019093653A1
WO2019093653A1 PCT/KR2018/011096 KR2018011096W WO2019093653A1 WO 2019093653 A1 WO2019093653 A1 WO 2019093653A1 KR 2018011096 W KR2018011096 W KR 2018011096W WO 2019093653 A1 WO2019093653 A1 WO 2019093653A1
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Prior art keywords
secondary battery
lithium secondary
active material
positive electrode
electrode active
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PCT/KR2018/011096
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English (en)
Korean (ko)
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김도유
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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 disclosure relates to a cathode active material for a lithium secondary battery and a lithium secondary battery including the same.
  • a cathode including a cathode active material As a core material of the lithium secondary battery, there are a cathode including a cathode active material, a cathode including a cathode active material, an electrolyte, and a separator.
  • the present disclosure aims at providing a positive electrode active material for a lithium secondary battery having a high capacity and an excellent thermal stability and a lithium secondary battery comprising the same.
  • the present disclosure provides a cathode active material for a lithium secondary battery comprising a compound represented by the following formula (1).
  • M is at least one or more elements selected from the group consisting of Cr, Fe, La, Ce, Sr, V, Ti, Mo, Zr, B, Rb and Y.
  • the present disclosure provides a lithium secondary battery comprising a positive electrode, a negative electrode, and an electrolyte solution, wherein the positive electrode includes the positive electrode active material for a lithium secondary battery according to an embodiment.
  • the positive electrode active material for a lithium secondary battery according to an embodiment of the present disclosure is applied to a lithium secondary battery, a lithium secondary battery having a remarkably improved thermal stability and excellent capacity characteristics can be realized.
  • FIG. 1 schematically shows a structure of a lithium secondary battery according to an embodiment of the present invention.
  • the cathode active material for a lithium secondary battery may include a compound represented by the following general formula (1).
  • M is at least one or more elements selected from the group consisting of Cr, Fe, La, Ce, Sr, V, Ti, Mo, Zr, B, Rb and Y.
  • the compound represented by the formula (1) may be, for example, a nickel-based oxide doped with Al and Mg, optionally doped with M and at the same time, a molar ratio of Ni of at least 0.8.
  • the role of a dopant is very important for improving the thermal stability of a lithium secondary battery using a nickel-based oxide having a molar ratio of Ni of at least 0.8 and securing a high capacity characteristic.
  • the lifetime of the lithium secondary battery can be improved and the heat generation starting temperature can be increased, so that the thermal stability can also be improved.
  • Mg the heat generation amount can be lowered, and at the same time, the heat generation starting temperature can be increased, so that the thermal stability of the secondary battery can be improved.
  • Al and Mg are doped in an appropriate amount, since the lithium secondary battery has excellent capacity and can realize the same effect as described above, Al and Mg are doped so as to satisfy the ranges of b and c described in the above formula It is appropriate. Further, besides Al and Mg, M can be further doped, which in this case can exhibit better high temperature cycle life characteristics.
  • two kinds of elements such as Al and Mg are doped in the amounts corresponding to the ranges of b and c, or Al and Mg are selectively doped with three or more elements of M by b, c and d, and when the Al is doped in an amount larger than Mg, the structural stability of the crystal structure of the nickel oxide particles can be improved even under a high temperature environment, The thermal stability can be further improved.
  • x may satisfy 0.9? X ⁇ 1.
  • Ni content increases, a high capacity lithium secondary battery can be realized, which is very advantageous.
  • b may be 0.001 ⁇ b? 0.02, for example 0.01? B? 0.02.
  • c may be 0 ⁇ c ⁇ 0.02, for example 0.01 ⁇ c ⁇ 0.015.
  • d may be 0? D ⁇ 0.005, for example, 0? D ⁇ 0.0025.
  • b and c may be 0.2? B / c? 3.0, for example, 0.25? B / c? 2.0, more specifically 0.6? B / c? 2.0.
  • the compound represented by Formula 1 may be, for example, Li 1.03 Ni 0.9 Co 0.05 Mn 0.025 Al 0.015 Mg 0.01 O 2 , Li 1.03 Ni 0.9 Co 0.05 Mn 0.025 Al 0.018 Mg 0.007 O 2 , and Li 1.03 Ni 0.9 Co 0.05 Mn 0.02 Al 0.02 Mg 0.01 O 2 .
  • a lithium secondary battery according to an embodiment of the present disclosure includes a cathode, a cathode, and an electrolyte.
  • FIG. 1 schematically shows a lithium secondary battery according to an embodiment of the present invention.
  • a lithium secondary battery 100 includes an electrode assembly 10, a casing member 20 for accommodating the electrode assembly 10, And includes a terminal 40 and a cathode terminal 50.
  • the electrode assembly 10 includes a positive electrode 11, a negative electrode 12, a separator 13 interposed between the positive electrode 11 and the negative electrode 12, and a positive electrode 11, a negative electrode 12, and a separator 13 (Not shown) for impregnating the electrolyte membrane.
  • a positive electrode comprising the positive electrode active material for a lithium secondary battery according to the present invention described above as the positive electrode 11 can be used.
  • the positive electrode 11 includes a positive electrode active material layer positioned on the positive electrode collector.
  • the positive electrode active material layer may include a positive electrode active material, and the positive electrode active material may include the positive electrode active material for a lithium secondary battery according to one embodiment described above.
  • the content of the cathode active material may be 90 wt% to 98 wt% with respect to the total weight of the cathode active material layer.
  • the cathode active material layer may further include a binder and a conductive material.
  • the content of the binder and the conductive material may be 1 wt% to 5 wt% with respect to the total weight of the cathode active material layer.
  • the binder serves to adhere the positive electrode active materials to each other and to adhere the positive electrode active material to the current collector.
  • Representative examples of the binder include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymer containing ethylene oxide, polyvinyl pyrrolidone But are not limited to, water, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin and nylon .
  • the conductive material is used for imparting conductivity to the electrode. Any conductive material may be used for the battery without causing any chemical change. Examples of the conductive material include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black and carbon fiber; Metal powders such as copper, nickel, aluminum, and silver, or metal-based materials such as metal fibers; Conductive polymers such as polyphenylene derivatives; Or a mixture thereof.
  • the cathode current collector may be an aluminum foil, a nickel foil or a combination thereof, but is not limited thereto.
  • the negative electrode 12 includes a negative electrode collector and a negative electrode active material layer disposed on the current collector.
  • the negative electrode active material layer includes a negative electrode active material.
  • the negative electrode active material a material capable of reversibly intercalating / deintercalating lithium ions, a lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, or a transition metal oxide may be used.
  • Examples of the material capable of reversibly intercalating / deintercalating lithium ions include a carbonaceous material, that is, a carbonaceous anode active material generally used in a lithium secondary battery.
  • Representative examples of the carbon-based negative electrode active material include crystalline carbon, amorphous carbon, or a combination thereof.
  • Examples of the crystalline carbon include graphite such as natural graphite or artificial graphite in an amorphous, plate-like, flake, spherical or fibrous form.
  • Examples of the amorphous carbon include soft carbon or hard carbon carbon, mesophase pitch carbide, fired coke, and the like.
  • lithium metal alloy examples include lithium and a group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, May be used.
  • a silicon-based material such as Si, SiO x (0 ⁇ x ⁇ 2), Si-Q alloy (Q is an alkali metal, an alkali earth metal, a Group 13 element, (Si), Sn, SnO 2 , Sn-R (wherein R is an element selected from the group consisting of a Group 15 element, a Group 16 element, a transition metal, a rare earth element, An element selected from the group consisting of an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a Group 15 element, a Group 16 element, a transition metal, a rare earth element and combinations thereof; , And at least one of them may be mixed with SiO 2 .
  • the element Q and the element R may be at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Pb, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof.
  • lithium titanium oxide may be used.
  • the content of the negative electrode active material in the negative electrode active material layer may be 95 wt% to 99 wt% with respect to the total weight of the negative electrode active material layer.
  • the negative electrode active material layer includes a negative electrode active material and a binder, and may further include a conductive material.
  • the content of the negative electrode active material in the negative electrode active material layer may be 95 wt% to 99 wt% with respect to the total weight of the negative electrode active material layer.
  • the content of the binder in the negative electrode active material layer may be 1 wt% to 5 wt% with respect to the total weight of the negative electrode active material layer.
  • the negative electrode active material may be used in an amount of 90 to 98 wt%
  • the binder may be used in an amount of 1 to 5 wt%
  • the conductive material may be used in an amount of 1 to 5 wt%.
  • the binder serves to adhere the anode active material particles to each other and to adhere the anode active material to the current collector.
  • a water-insoluble binder, a water-soluble binder, or a combination thereof may be used as the binder.
  • water-insoluble binder examples include polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, a polymer containing ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride , Polyethylene, polypropylene, polyamideimide, polyimide, or a combination thereof.
  • water-soluble binder examples include styrene-butadiene rubber, acrylated styrene-butadiene rubber, polyvinyl alcohol, sodium polyacrylate, propylene and olefin copolymers having 2 to 8 carbon atoms, (meth) acrylic acid and (meth) Copolymers or combinations thereof.
  • a cellulose-based compound capable of imparting viscosity may be further contained as a thickener.
  • a cellulose-based compound capable of imparting viscosity may be further contained as a thickener.
  • alkali metal Na, K or Li can be used.
  • the content of the thickener may be 0.1 part by weight to 3 parts by weight based on 100 parts by weight of the negative electrode active material.
  • the conductive material is used for imparting conductivity to the electrode. Any conductive material may be used for the battery without causing any chemical change. Examples of the conductive material include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, denka black and carbon fiber; Metal powders such as copper, nickel, aluminum, and silver, or metal-based materials such as metal fibers; Conductive polymers such as polyphenylene derivatives; Or a mixture thereof.
  • the anode current collector may be selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foil, polymer substrate coated with a conductive metal, and combinations thereof .
  • the electrode assembly 10 can be made of a flat structure after the separator 13 is wound between the strip-shaped anode 11 and the cathode 12 and then wound.
  • a structure in which a plurality of positive electrodes and negative electrodes of a sheet shape are alternately stacked with a separator interposed therebetween may be formed.
  • the positive electrode 11, the negative electrode 12 and the separator 13 may be impregnated with an electrolytic solution.
  • the separator 13 separates the positive electrode 11 and the negative electrode 12 and provides a passage for lithium ion. Any separator 13 may be used as long as it is commonly used in a lithium secondary battery. That is, it is possible to use an electrolyte having a low resistance to ion movement and an excellent ability to impregnate an electrolyte.
  • the separator 13 may be selected from, for example, glass fiber, polyester, polyethylene, polypropylene, polytetrafluoroethylene, or a combination thereof, and may be in the form of a nonwoven fabric or a woven fabric.
  • a polyolefin-based polymer separator such as polyethylene, polypropylene and the like may be mainly used for the lithium secondary battery, and a separator coated with a composition containing a ceramic component or a polymeric substance may be used for heat resistance or mechanical strength, May be used as a single layer or a multilayer structure.
  • the electrolytic solution 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 cell can move.
  • a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based or aprotic solvent may be used.
  • the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), methyl ethyl carbonate (MEC) EC), propylene carbonate (PC), and butylene carbonate (BC) may be used.
  • ester solvent methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate , gamma -butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, and the like can be used.
  • ether solvent include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, and tetrahydrofuran.
  • ketone solvent cyclohexanone may be used have.
  • alcoholic solvent ethyl alcohol, isopropyl alcohol and the like
  • aprotic solvent R-CN (R is a linear, branched or cyclic hydrocarbon group having 2 to 20 carbon atoms, , A double bond aromatic ring or an ether bond), amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolanes, and the like can be used .
  • the non-aqueous organic solvent may be used singly or in combination of one or more thereof.
  • the mixing ratio may be suitably adjusted in accordance with the performance of the desired battery, which is widely understood by those skilled in the art .
  • a carbonate-based solvent it is preferable to use a mixture of a cyclic carbonate and a chain carbonate.
  • the cyclic carbonate and the chain carbonate are mixed in a volume ratio of 1: 1 to 1: 9, the performance of the electrolytic solution may be excellent.
  • the non-aqueous organic solvent of the present invention may further include an aromatic hydrocarbon-based organic solvent in the carbonate-based 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.
  • the aromatic hydrocarbon-based organic solvent may be an aromatic hydrocarbon-based compound represented by the following formula (3).
  • R 1 to R 6 are the same or different from each other and selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group, and combinations thereof.
  • aromatic hydrocarbon organic solvent examples include benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3- Dichlorobenzene, 1,2-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2-dichlorobenzene, 1,2-dichlorobenzene, 2,4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2 , 4-triiodobenzene, toluene, fluorotoluene, 2,3-difluorotoluene, 2,4-difluorotoluene, 2,5-difluorotoluene, 2,3,4
  • the non-aqueous electrolyte may further include vinylene carbonate or an ethylene carbonate-based compound represented by the following formula (4) to improve battery life.
  • R 7 and R 8 are the same or different and 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 an alkyl group having 1 to 5 fluorinated carbon atoms, provided that R 7 and R 8 are both hydrogen no.
  • ethylene carbonate-based compound examples include difluoroethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate or fluoroethylene carbonate. have. When such a life improving additive is further used, its amount can be appropriately adjusted.
  • the lithium salt is dissolved in an organic solvent to act as a source of lithium ions in the cell to enable the operation of a basic lithium secondary battery and to promote the movement of lithium ions between the anode and the cathode.
  • the lithium salt Representative examples 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 from 1 to 20 ), LiCl, LiI and LiB (C 2 O 4 ) 2 (lithiumbis (oxalato) borate (LiBOB)) as a supporting electrolyte salt.
  • the concentration of the lithium salt is preferably in the range of 0.1 M to 2.0 M.
  • the electrolyte has an appropriate conductivity and viscosity, and therefore can exhibit excellent electrolyte performance, Can be moved.
  • the separator 13 interposed between the anode 11 and the cathode 12 may be a polymer membrane.
  • the separator for example, polyethylene, polypropylene, polyvinylidene fluoride or a multilayer film of two or more thereof may be used.
  • the separator may be a polyethylene / polypropylene double layer separator, a polyethylene / polypropylene / polyethylene triple layer separator, / Polyethylene / polypropylene three-layer separator, or the like can be used.
  • the casing member 20 may be composed of a lower casing member 22 and an upper casing member 21 and the electrode assembly 10 is accommodated in an inner space 221 of the lower casing member 22.
  • the sealing member is applied to the sealing member 222 located at the rim of the lower casing member 22 to seal the upper casing member 21 and the lower casing member 22.
  • the durability of the lithium secondary battery 100 can be improved by wrapping the insulating member 60 in a portion where the positive electrode terminal 40 and the negative electrode terminal 50 are in contact with the case 20.
  • the operating voltage of the lithium secondary battery according to the present embodiment may be in the range of, for example, 4.2V to 4.55V, more specifically, 4.25V to 4.5V.
  • the operating voltage of a lithium secondary battery is based on a half-coin cell.
  • the present invention includes the cathode active material according to one embodiment, the lithium secondary battery to which the present invention is applied can remarkably improve the thermal stability while having a high capacity.
  • the lithium secondary battery according to one embodiment may be provided in an apparatus including at least one of the lithium secondary batteries.
  • Such devices include, for example, any one selected from the group consisting of a cell phone, a tablet computer, a notebook computer, a power tool, a wearable electronic device, an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, Lt; / RTI > Since devices employing the lithium secondary battery are well known in the art, a detailed description thereof will be omitted herein.
  • Li (1.03) Ni (0.9 ) Co (0.05) Mn (0.025) Al (0.015) Mg (0.01) O 2 prepared the positive electrode active material Respectively.
  • the positive electrode active material composition was applied to an aluminum current collector to prepare a positive electrode.
  • a coin-shaped half-cell having a nominal capacity of 190 mAh was produced by a conventional method using the positive electrode prepared in accordance with the above-mentioned method (1), the lithium metal counter electrode and the electrolyte solution.
  • a mixed solvent of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) (30:40:30 by volume) in which 1.3 M LiPF 6 was dissolved was used as the electrolyte solution.
  • the positive electrode and negative electrode according to Examples 2 to 3 and Comparative Examples 1 to 8 were prepared in the same manner as in Example 1 except that the contents of the respective elements constituting the positive electrode active material were mixed so as to be as shown in Table 1 below, Thereby preparing a lithium secondary battery.
  • DSC Differential scanning calorimeter
  • the lithium secondary batteries prepared in Examples 1 to 3 and Comparative Examples 1 to 8 were charged at 100% to 0.1 V and 4.3 V, and then the battery was disassembled to separate the positive electrode plates.
  • the scan rate was 5 ° C / min.
  • the calculated calorific value (numerical value obtained by integrating the numerical value of the exothermic numerical curve on the DSC with respect to temperature) is shown in Table 2, and the maximum exothermic peak and the maximum peak temperature value and the total calorific value are shown in Table 2 below.
  • Example 1 192.34 238.5 19.8 46.16
  • Example 2 192.61 237.9 19.7 45.29
  • Example 3 193.11 239.1 20.1 45.99 Comparative Example 1 201.13 221.2 121.3 20.07 Comparative Example 2 192.12 246.9 10.9 54.78 Comparative Example 3 172.4 220.8 113.8 48.4 Comparative Example 4 206.3 223.7 78.2 17.4 Comparative Example 5 136.5 231.5 11.47 95 Comparative Example 6 196.77 224.4 21.5 27.63 Comparative Example 7 177.67 221.2 18.5 43.53 Comparative Example 8 170.12 221.2 17.2 51.08
  • the lithium secondary battery prepared according to Examples 1 to 3 is a case where a cathode active material having a molar ratio of Al and Mg satisfying the range of the formula 1 and a molar ratio of Al larger than Mg is applied as in the embodiment.
  • a cathode active material having a molar ratio of Al and Mg satisfying the range of the formula 1 and a molar ratio of Al larger than Mg is applied as in the embodiment.
  • Table 2 it can be seen that the lithium secondary battery produced according to Examples 1 to 3 has a maximum peak temperature and a difference in heat generation starting temperature of 30 ° C or more, so that heat generation is not explosive. It was also found that the heat-start temperature of 185 DEG C or higher, the maximum peak temperature of 230 DEG C or higher, and the maximum heat flow of 30 W / g or lower were all satisfied, and thus the lithium secondary batteries produced according to Examples 1 to 3 were excellent in thermal stability Able to know.
  • the lithium secondary battery manufactured according to Comparative Example 1 using the cathode active material containing no Al and Mg had a difference in maximum peak temperature and heat generation initiation temperature of less than 30 ° C, resulting in explosion of heat generation and poor thermal stability .
  • the lithium secondary battery according to Comparative Example 4 using the positive electrode active material containing Mg alone had a difference in maximum peak temperature and heat generation initiation temperature of less than 30 ° C., a maximum heat flow exceeding 30 W / g, Can be found.
  • Example 1 The lithium secondary battery produced in Example 1 and Comparative Examples 1 to 8 was charged with 0.1 C and 4.3 V cut-off at a constant current and a constant voltage, and the battery was stopped for 10 minutes and discharged at 0.1 C and 2.7 V cut- , And the charge / discharge cycle was stopped once for 10 minutes.
  • the lithium secondary battery manufactured according to Examples 1 to 3 has a high charge / discharge capacity and a high C-Rate and excellent electrochemical characteristics.
  • the lithium secondary batteries manufactured according to Comparative Examples 1 to 8 have low charge / discharge capacities and poor charge-discharge characteristics, and the electrochemical characteristics are inferior to those of Examples.

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Abstract

La présente invention concerne un matériau actif de cathode pour accumulateur au lithium et un accumulateur au lithium le comprenant. Un matériau actif d'électrode positive pour accumulateur au lithium selon un mode de réalisation peut contenir un composé représenté par la formule chimique 1 ci-dessous. [Formule chimique 1] Lia(NixCoyMnzAlbMgcMd)O2, dans laquelle 0,96 < a < 1,04, 0,8 ≤ x < 1, 0 < y ≤ 0,075, 0 < z ≤ 0,025, 0,001 < b ≤ 0,02, 0 < c < 0,02, 0 ≤ d < 0,005, b > c, x + y + z + b + c + d = 1, et M représente au moins un élément choisi dans le groupe constitué de Cr, Fe, La, Ce, Sr, V, Ti, Mo, Zr, B, Rb et Y.
PCT/KR2018/011096 2017-11-10 2018-09-20 Matériau actif d'électrode positive pour accumulateur au lithium et accumulateur au lithium le comprenant WO2019093653A1 (fr)

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