WO2019059655A2 - Électrode positive pour batterie secondaire et batterie secondaire comprenant celle-ci - Google Patents

Électrode positive pour batterie secondaire et batterie secondaire comprenant celle-ci Download PDF

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Publication number
WO2019059655A2
WO2019059655A2 PCT/KR2018/011082 KR2018011082W WO2019059655A2 WO 2019059655 A2 WO2019059655 A2 WO 2019059655A2 KR 2018011082 W KR2018011082 W KR 2018011082W WO 2019059655 A2 WO2019059655 A2 WO 2019059655A2
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WO
WIPO (PCT)
Prior art keywords
positive electrode
mixture layer
material mixture
secondary battery
active material
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PCT/KR2018/011082
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English (en)
Korean (ko)
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WO2019059655A3 (fr
Inventor
이동훈
전혜림
이상욱
노은솔
정왕모
강민석
백소라
박지영
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180111643A external-priority patent/KR102465819B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/647,935 priority Critical patent/US11569501B2/en
Priority to CN201880059198.7A priority patent/CN111095612B/zh
Priority to JP2020515873A priority patent/JP7062161B2/ja
Priority to EP18859067.3A priority patent/EP3671909B1/fr
Priority to PL18859067T priority patent/PL3671909T3/pl
Publication of WO2019059655A2 publication Critical patent/WO2019059655A2/fr
Publication of WO2019059655A3 publication Critical patent/WO2019059655A3/fr

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Classifications

    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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
    • 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
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode for a secondary battery and a secondary battery including the same.
  • lithium secondary batteries having a high energy density and voltage, a long cycle life, and a low self-discharge rate are commercially available and widely used.
  • overcharge phenomenon In the case of a lithium secondary battery, it can be overcharged beyond a normal charging region, and this phenomenon is referred to as overcharge phenomenon.
  • the lithium secondary battery When the lithium secondary battery is overcharged at a normal operating voltage or higher, heat is generated due to electrical resistance in the battery, and the temperature gradually rises. At this time, excessive lithium is discharged from the anode in the normal charging state, More lithium than is possible to enter, excess lithium is deposited on the cathode surface in the form of lithium metal. Also, when overcharging occurs, the structure collapses at the anode to provide not only thermal energy but also oxygen. When the separator is melted by the heat rapidly generated at the anode and the cathode, the anode and the cathode may develop into an inter short state have. When this condition is reached, the battery becomes extremely dangerous and can even explode.
  • An object of the present invention is to provide a positive electrode for a secondary battery that can prevent a battery from being exploded or heated by heat accumulated in the battery before reaching an overcharge reference voltage (about 8V to 10V).
  • the present invention provides a positive electrode current collector comprising: a first positive electrode mixture layer formed on a positive electrode collector; And a second positive electrode material mixture layer formed on the first positive electrode material mixture layer, wherein the first positive electrode material mixture layer has an operating voltage of 4.25 to 6.0 V, and includes an overcharging active material which generates lithium and gas upon charging A positive electrode for a secondary battery is provided.
  • a method of manufacturing a positive electrode collector comprising: forming a first positive electrode mixture layer on a positive electrode collector; And forming a second positive electrode material mixture layer on the first positive electrode material mixture layer, wherein the first positive electrode material mixture layer has an operating voltage of 4.25 to 6.0 V, A method for manufacturing a positive electrode for a secondary battery including an active material is provided.
  • the present invention also provides a secondary battery comprising the positive electrode for the secondary battery.
  • the positive electrode for a secondary battery according to the present invention includes a mixed layer including an overcharge active material which generates lithium and gas when the battery is driven and charged at an overcharge voltage level higher than an operating voltage of a general lithium secondary battery. Therefore, the resistance and the voltage of the battery rapidly increase before the battery is damaged or exploded due to the residual heat accumulated in the battery during the overcharge of the secondary battery and the explosion of the battery, so that the life characteristics and safety of the battery can be improved.
  • an overcharging active material layer capable of generating lithium and gas in a range lower than a voltage at which a battery is driven and a range in which an electrolyte undergo oxidative decomposition at the time of overcharging can be lowered is stacked on one surface of a positive electrode Respectively. Accordingly, when the battery is charged in the voltage range, gas is generated, and the resistance rapidly increases, and the voltage can be rapidly increased so as to be proportional thereto.
  • the resistance of the positive electrode active material is increased due to the reaction of the positive electrode active material before the exothermic reaction occurs,
  • a positive electrode for a secondary battery capable of preventing a heat generation or an explosion due to an oxidative decomposition reaction of an electrolyte to reach a voltage range corresponding to a voltage of a termination condition due to a sudden rise in the voltage of the positive electrode, Thereby providing a secondary battery.
  • a positive electrode for a secondary battery comprises: a first positive electrode material mixture layer formed on a positive electrode current collector; And a second positive electrode material mixture layer formed on the first positive electrode material mixture layer, wherein the first positive electrode material mixture layer has an operating voltage of 4.25 to 6.0 V, and includes an overcharging active material which generates lithium and gas upon charging do.
  • the cathode current collector is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, and for example, a cathode may be formed on the surface of stainless steel, aluminum, nickel, titanium, , Nickel, titanium, silver, or the like may be used.
  • the cathode current collector may have a thickness of 3 to 500 ⁇ , and fine unevenness may be formed on the surface of the current collector to increase the adhesive force of the cathode active material.
  • it can be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the first positive electrode material mixture layer formed on the positive electrode collector may include an overcharging active material having an operating voltage of 4.25 to 6.0 V and generating lithium and gas upon charging.
  • the operating voltage means a voltage range in which the overcharge-generating active material generates lithium and gas when the voltage reaches the above-mentioned range.
  • the operating voltage is not necessarily limited to the above range, But it can be regarded as the operating voltage range of the first positive electrode mixture layer if the voltage is lower than the voltage at which the reaction heat generated by oxidative decomposition of the electrolyte is generated.
  • the supercharging active material may include at least one element selected from the group consisting of a carbon element and a nitrogen element.
  • the overcharging active material contains the carbon element and / or the nitrogen element, it generates carbon dioxide (CO) and / or carbon monoxide (CO 2 ) within the operating voltage range and is vaporized.
  • the overchargeable active material contained in the first positive electrode material mixture layer generates gas and is vaporized, and at the same time, a part of the positive electrode is lost, so that the positive electrode resistance rapidly increases. Accordingly, the voltage of the anode also rises in proportion to the anode resistance, so that the supply of the voltage is stopped before the electrolyte is oxidized and decomposed to generate heat in the secondary battery.
  • the overcharging active material is selected from the group consisting of Li 2 C 2 O 4 , Li 2 C 4 O 4 , Li 2 C 3 O 5 , Li 2 C 4 O 6, and LiN 3
  • the material which is highly sensitive to the reaction within the specific operating voltage range more preferably, the overcharging active material may be Li 2 C 2 O 4 .
  • the overcharging active material may be contained in an amount of 60 to 99.9% by weight, preferably 65 to 99.8% by weight, and more preferably 70 to 99.8% by weight based on the total weight of the first cathode mix layer.
  • the overchargeable active material when included within the above range, when a voltage within the operating voltage range is applied to the battery, lithium and gas are sufficiently generated and the resistance and voltage may rise to a certain level or more.
  • the overcharge-capable active material is included in the above range, the capacity of the battery can be relatively increased. Therefore, it is preferable that the overcharging active material is contained within the above range.
  • the thickness of the first positive electrode material mixture layer is 0.1 to 30 ⁇ , more preferably 0.2 to 10 ⁇ .
  • the thickness of the first anodic coalescing layer is thinner than the above range, even if the voltage supplied to the battery reaches the voltage of the operating range and lithium and gas are generated, the amount of generated gas is small and the resistance rises accordingly The voltage of the anode is not likely to rise sharply.
  • the first positive electrode material mixture layer is formed to a thickness exceeding the above range, the charge / discharge performance of the electrode may be deteriorated.
  • the first positive electrode material mixture layer may further include a binder and a conductive material together with the above-described overchargeable active material.
  • the binder serves to improve the adhesion between the positive electrode active material particles and the adhesion between the positive electrode active material and the current collector.
  • Specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose ), Starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, and various copolymers thereof.
  • PVDF polyvinylidene fluoride
  • PVDF-co-HFP vinylidene fluoride-hexafluoropropylene copolymer
  • PVDF-co-HFP polyvinyl
  • the binder may be contained in an amount of 0.1 to 40% by weight, preferably 0.1 to 35% by weight, more preferably 0.1 to 30% by weight based on the total weight of the first cathode mix layer.
  • the binder is contained in the range below the above range, the adhesion between the first positive electrode mixture layer and the positive electrode collector is weak and the life characteristics of the battery may be deteriorated.
  • the binder is contained in the range exceeding the above range, The materials constituting the first positive electrode mixture layer may be aggregated and the first positive electrode material mixture layer may not be uniformly formed and the lifetime characteristics of the battery may be deteriorated, Is preferably included within the above range.
  • the conductive material is used for imparting conductivity to the electrode.
  • the conductive material is not particularly limited as long as it has electron conductivity without causing chemical change. Specific examples thereof include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black and carbon fiber; Metal powder or metal fibers such as copper, nickel, aluminum and silver; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; And polyphenylene derivatives. These may be used alone or in admixture of two or more.
  • the conductive material may be included in an amount of 0.1 to 40% by weight, preferably 0.1 to 35% by weight, and more preferably 0.1 to 30% by weight based on the total weight of the cathode active material layer.
  • a conductivity of a certain level or higher can be given to the electrode.
  • it is contained in the range below the above range it is difficult to impart a certain level of conductivity to the electrode. If it exceeds the above range, coagulation phenomenon occurs between the conductive materials and the first positive electrode material mixture layer is not uniformly formed, It is preferable that the conductive material is contained within the above range.
  • the second positive electrode material mixture layer is a layer formed on the first positive electrode material mixture layer and contains lithium transition metal oxide as the positive electrode active material.
  • the second positive electrode material mixture layer may further include a binder and a conductive material
  • the binder and the conductive material used for the second positive electrode material mixture layer may include a binder and a conductive material used for the first positive electrode material mixture layer
  • the types of the binder and the conductive material are the same as those described above.
  • the lithium-transition metal oxide when the lithium-transition metal oxide, the binder and the conductive material are included, the lithium-transition metal oxide is 80 to 99.9% by weight based on the total weight of the second positive electrode material mixture layer, 85 to 99.8% by weight, and more preferably 90 to 99.8% by weight.
  • the binder may contain 0.1 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.1 to 10% by weight based on the total weight of the second positive electrode material mixture layer.
  • the conductive material may include 0.1 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.1 to 10% by weight based on the total weight of the second cathode mix layer.
  • the lithium transition metal oxide is contained in the range below the range, lithium ions may not be sufficiently supplied to the cathode. If the lithium transition metal oxide is contained in the range exceeding the above range, the performance of the battery may deteriorate due to the conductivity and adhesion of the electrode. Therefore, it is more preferable that the lithium transition metal oxide is included within the above range in consideration of the capacity and life performance of the battery.
  • the second positive electrode material mixture layer when the binder and the conductive material are contained within the above range, the adhesion between the first positive electrode material mixture layer and the second positive electrode material mixture layer can be improved and the conductivity can be maintained to a certain level or more.
  • the binder when the binder is included in the range below the above range, the adhesion between the second positive electrode material mixture layer and the first positive electrode material mixture layer may be deteriorated, and when the conductive material is contained in the range below the second positive electrode material mixture layer, Can also be lowered.
  • the binder and the conductive material are included in the amount exceeding the above range, aggregation phenomenon occurs between the materials forming the second positive electrode material mixture layer, resulting in deterioration in adhesion to the first positive electrode material mixture layer, and battery life characteristics are deteriorated . Therefore, it is more preferable that the binder and the conductive material are included within the above range.
  • the thickness of the second positive electrode material mixture layer is 20 to 500 mu m, more preferably 50 to 300 mu m.
  • the thickness of the second positive electrode material mixture layer is less than the above range, lithium ions may not be sufficiently supplied into the battery.
  • the thickness exceeds the above range, the total thickness of the positive electrode increases, It is more preferable that the thickness of the second positive electrode material mixture layer is within the above range.
  • the thickness ratio of the first positive electrode material mixture layer and the second positive electrode material mixture layer is 1: 1 to 1: 300, more preferably 1:50 to 1: 200.
  • the first positive electrode material mixture layer may be formed so as to abruptly increase the resistance and the voltage, so that the lifetime performance and stability of the battery may be improved , Lithium ions are sufficiently supplied and the battery capacity can be improved.
  • the electrical contact between the positive electrode collector and the second positive electrode mixture layer by the breakage of the first positive electrode mixture layer Can be blocked.
  • a method for producing a battery pack comprising the steps of (1) forming a first positive electrode mixture layer on a positive electrode collector, and (2) forming a second positive electrode mixture layer on the first positive electrode mixture layer,
  • the positive electrode material mixture layer has an operating voltage of 4.25 to 6.0 V and includes an overcharging active material which generates lithium and gas upon charging.
  • the method of forming the first positive electrode material mixture layer containing the overcharge-capable active material is not particularly limited.
  • the step of forming the first anode mixture layer comprises: mixing the overcharging active material with a conductive material and a binder to form a first anode formation composition; And applying the composition for forming an anode on the positive electrode current collector.
  • the overcharge-capable active material, the conductive material and the binder may be dissolved or dispersed in a solvent to prepare a composition for forming a first anode.
  • the types and contents of the overcharging active material, the conductive material and the binder are as described above.
  • the solvent for forming the first anode forming composition may be a solvent commonly used in the art, and examples thereof include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpiperazine (NMP), acetone, or water, and either one of them alone or a mixture of two or more of them may be used.
  • the amount of the solvent used is sufficient to dissolve or disperse the overchargeable active material, the conductive material and the binder in consideration of the application thickness of the slurry and the yield of the slurry, and then to have a viscosity capable of exhibiting excellent thickness uniformity Do.
  • the first positive electrode composition composition may be coated on the positive electrode collector, followed by drying and rolling to form the first positive electrode mixture layer.
  • the anode may be produced by casting the first composition for forming an anode on a separate support, then peeling the support from the support, and laminating the film on the cathode current collector.
  • the second positive electrode material mixture layer is formed on the first positive electrode material mixture layer, and the method of forming the second positive electrode material mixture layer is not particularly limited.
  • the second positive electrode mixture layer may be formed by mixing the lithium transition metal oxide with a conductive material and a binder to form a second positive electrode composition; And applying the second composition for forming an anode on the first positive electrode material mixture layer.
  • the type and content of the lithium transition metal oxide, the binder, the conductive material, and the solvent for forming the second positive electrode material mixture composition are as described above.
  • the lithium secondary battery according to the present invention includes a positive electrode, a negative electrode disposed opposite to the positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte.
  • the lithium secondary battery may further include a battery container for storing the positive electrode, the negative electrode and the electrode assembly of the separator, and a sealing member for sealing the battery container.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
  • the negative electrode current collector may be formed on the surface of copper, stainless steel, aluminum, nickel, titanium, sintered carbon, Carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like may be used.
  • the negative electrode collector may have a thickness of 3 to 500 ⁇ , and similarly to the positive electrode collector, fine unevenness may be formed on the surface of the collector to enhance the binding force of the negative electrode active material.
  • it can be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the anode active material layer optionally includes a binder and a conductive material together with the anode active material.
  • the negative electrode active material layer may be formed by applying and drying a composition for forming a negative electrode including a negative electrode active material on the negative electrode collector and, optionally, a binder and a conductive material, or by casting the composition for forming a negative electrode on a separate support , And a film obtained by peeling from the support may be laminated on the negative electrode collector.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used.
  • Specific examples thereof include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber and amorphous carbon;
  • Metal compounds capable of alloying with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys or Al alloys;
  • Metal oxides such as SiOx (0 ⁇ x ⁇ 2), SnO2, vanadium oxide, lithium vanadium oxide and the like capable of doping and dedoping lithium;
  • a composite containing the metallic compound and the carbonaceous material such as Si-C composite or Sn-C composite, and any one or a mixture of two or more thereof may be used.
  • a metal lithium thin film may be used as the negative electrode active material.
  • the carbon material may be both low-crystalline carbon and high-crystallinity carbon.
  • Examples of the low-crystalline carbon include soft carbon and hard carbon.
  • Examples of the highly crystalline carbon include natural graphite, artificial graphite, artificial graphite or artificial graphite, Kish graphite graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar coke derived cokes).
  • the binder and the conductive material are the same as those described above for the anode.
  • the separator separates the negative electrode and the positive electrode and provides a moving path of lithium ions.
  • the separator can be used without limitation, as long as it is used as a separator in a lithium secondary battery. Particularly, It is preferable to have a low resistance and an excellent ability to impregnate the electrolyte.
  • porous polymer films such as porous polymer films made of polyolefin-based polymers such as ethylene homopolymers, propylene homopolymers, ethylene / butene copolymers, ethylene / hexene copolymers and ethylene / methacrylate copolymers, May be used.
  • a nonwoven fabric made of a conventional porous nonwoven fabric for example, glass fiber of high melting point, polyethylene terephthalate fiber, or the like may be used.
  • a coated separator containing a ceramic component or a polymer material may be used, and may be optionally used as a single layer or a multilayer structure.
  • Examples of the electrolyte used in the present invention include an organic-based liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, and a molten inorganic electrolyte that can be used in the production of a lithium secondary battery. It is not.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without limitation as long as it can act as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • examples of the organic solvent include ester solvents such as methyl acetate, ethyl acetate,? -Butyrolactone and?
  • Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethyl carbonate (DMC), diethylcarbonate (DEC), methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate PC) and the like; Alcohol solvents such as ethyl alcohol and isopropyl alcohol; R-CN (R is a straight, branched or cyclic hydrocarbon group of C2 to C20, which may contain a double bond aromatic ring or an ether bond); Amides such as dimethylformamide; Dioxolanes such as 1,3-dioxolane; Or sulfolane may be used.
  • Ether solvents such as dibutyl ether or tetrahydrofuran
  • Ketone solvents such as cyclohexanone
  • a carbonate-based solvent is more preferable, and a cyclic carbonate (for example, ethylene carbonate or propylene carbonate) having a high ionic conductivity and a high dielectric constant, such as ethylene carbonate or propylene carbonate, which can increase the charge- (For example, ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate, etc.).
  • a cyclic carbonate for example, ethylene carbonate or propylene carbonate
  • ethylene carbonate or propylene carbonate having a high ionic conductivity and a high dielectric constant, such as ethylene carbonate or propylene carbonate, which can increase the charge- (For example, ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate, etc.).
  • the cyclic carbonate and the chain carbonate are mixed in a volume ratio of about 1: 1 to about 1: 9, the performance of the electrolytic solution may be excellent.
  • the lithium salt can be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt LiPF 6, LiClO 4, LiAsF 6, LiBF 4, LiSbF 6, LiAl0 4, LiAlCl 4, LiCF 3 SO 3, LiC 4 F 9 SO 3, LiN (C 2 F 5 SO 3) 2 , LiN (C 2 F 5 SO 2) 2, LiN (CF 3 SO 2) 2.
  • LiCl, LiI, or LiB (C 2 O 4 ) 2 may be used.
  • the concentration of the lithium salt is preferably in the range of 0.1 to 2.0 M. When the concentration of the lithium salt is within the above range, the electrolyte has an appropriate conductivity and viscosity, so that it can exhibit excellent electrolyte performance and the lithium ion can effectively move.
  • the electrolyte may contain, for example, a haloalkylene carbonate-based compound such as difluoroethylene carbonate or the like, pyridine, triethanolamine, or the like for the purpose of improving lifetime characteristics of the battery, Ethyl phosphite, triethanol amine, cyclic ether, ethylenediamine, glyme, hexametriamide, nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, At least one additive such as benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, The additive may be included in an amount of 0.1 to 5% by weight based on the total weight of the electrolyte.
  • the lithium secondary battery including the positive electrode according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention ratio, and thus can be applied to portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles electric vehicle (HEV), and the like.
  • portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles electric vehicle (HEV), and the like.
  • Li 2 C 2 O 4 , a conductive material (denka black KF1100), and a PVDF binder were mixed in a weight ratio of 90: 5: 5 and NMP as a solvent.
  • the resultant mixture was subjected to dispersion treatment for 30 minutes using a disperser (Paste mixer or homo disperse) to prepare a composition for forming a first positive electrode material mixture layer (solid content: about 70% by weight).
  • the composition for forming the first positive electrode material mixture layer was coated on the aluminum current collector, dried at 120 ° C, and rolled to form a first positive electrode material mixture layer on the aluminum current collector.
  • the resultant mixture was subjected to dispersion treatment for 30 minutes using a disperser (Paste mixer or homo disperse) to prepare a composition for forming a second positive electrode material mixture layer (solid content: about 75% by weight)
  • the composition for forming the positive electrode material mixture layer was coated on the first positive electrode material mixture layer, dried at 120 ⁇ and rolled to prepare a positive electrode.
  • a positive electrode was prepared in the same manner as in Example 1 except that LiN 3 was used instead of Li 2 C 2 O 4 in the preparation of the first positive electrode material mixture composition.
  • Example 1 Except that the first positive electrode material mixture layer was not formed in Example 1 and the composition for forming the second positive electrode material mixture layer was immediately applied to the aluminum current collector and dried at 120 ⁇ and then rolled, .
  • LiNi 0 . 6 Co 0 . 2 Mn 0 . 2 O 2 a conductive material (denka black KF1100) and a PVDF binder in a weight ratio of 96: 2: 2, and mixed using NMP as a solvent. Further, 3 wt% of Li 2 C 2 O 4 was added and mixed.
  • the resultant mixture was subjected to dispersion treatment for 30 minutes using a disperser (Paste mixer or homo disperse) to prepare a composition for forming a positive electrode material mixture layer (solid content: about 70% by weight)
  • the composition for forming a layer was applied to an aluminum current collector, dried at 120 ⁇ , and rolled to form a positive electrode mixture layer on the aluminum current collector.
  • a lithium secondary battery was prepared using the positive electrodes prepared in Examples 1 to 3 and Comparative Examples 1 to 3, respectively. More specifically, it is as follows.
  • the negative electrode active material slurry was prepared by mixing natural graphite, a carbon black conductive material, carboxymethyl cellulose (CMC) and a styrene butadiene rubber (SBR) binder in a weight ratio of 96: 1: 1: 2 and using H 2 O as a solvent .
  • the negative electrode active material slurry was applied to a copper current collector, followed by drying and rolling to prepare a negative electrode.
  • An electrode assembly was manufactured through a separator made of porous polyethylene between each of the positive electrodes and the negative electrodes prepared in Examples 1 to 3 and Comparative Examples 1 to 3, the electrode assembly was placed inside the case, An electrolyte was injected to prepare a lithium secondary battery.
  • the lithium secondary batteries produced using the positive electrodes of Examples 1 to 3 and Comparative Examples 1 to 3 were charged under the charging conditions shown in Table 1 below to determine the voltage at the time of generation of the gas (the operating voltage of the first positive electrode material mixture layer (V)) was measured. The operating voltages measured at this time are shown in Table 1 below.
  • the lithium secondary battery prepared using the positive electrodes of Examples 1 to 3 and Comparative Examples 1 to 3 was subjected to stability test while being charged at 1.0 C in SOC 100 for one hour. At this time, when the voltage of the lithium secondary battery reaches 8.4 V without heat or explosion, it is evaluated as Pass. When the secondary battery fails to reach the voltage and the secondary battery is heated or exploded, it is evaluated as Fail.
  • the experimental results are shown in Table 2 below.

Abstract

L'invention concerne une électrode positive pour une batterie secondaire, comprenant une première couche de mélange d'électrode positive formée sur un collecteur de courant d'électrode positive ; et une seconde couche de mélange d'électrode positive formée sur la première couche de mélange d'électrode positive, la première couche de mélange d'électrode positive ayant une tension de travail de 4,25 à 6,0 V et comprenant un matériau actif de surcharge qui génère du lithium et du gaz pendant la charge, et une batterie secondaire au lithium comprenant l'électrode positive.
PCT/KR2018/011082 2017-09-19 2018-09-19 Électrode positive pour batterie secondaire et batterie secondaire comprenant celle-ci WO2019059655A2 (fr)

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US16/647,935 US11569501B2 (en) 2017-09-19 2018-09-19 Positive electrode for secondary battery and secondary battery including the same
CN201880059198.7A CN111095612B (zh) 2017-09-19 2018-09-19 二次电池用正极和包含其的二次电池
JP2020515873A JP7062161B2 (ja) 2017-09-19 2018-09-19 二次電池用正極及びこれを含む二次電池
EP18859067.3A EP3671909B1 (fr) 2017-09-19 2018-09-19 Électrode positive pour batterie secondaire et batterie secondaire la comprenant
PL18859067T PL3671909T3 (pl) 2017-09-19 2018-09-19 Elektroda dodatnia dla akumulatora i zawierający ją akumulator

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