WO2018117634A1 - Matériau actif d'anode de haute tension dopé avec du métal - Google Patents

Matériau actif d'anode de haute tension dopé avec du métal Download PDF

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WO2018117634A1
WO2018117634A1 PCT/KR2017/015118 KR2017015118W WO2018117634A1 WO 2018117634 A1 WO2018117634 A1 WO 2018117634A1 KR 2017015118 W KR2017015118 W KR 2017015118W WO 2018117634 A1 WO2018117634 A1 WO 2018117634A1
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Prior art keywords
active material
positive electrode
electrode active
cobalt oxide
lithium cobalt
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PCT/KR2017/015118
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English (en)
Korean (ko)
Inventor
박성빈
박영욱
박지영
이보람
조치호
허혁
정왕모
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주식회사 엘지화학
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Priority claimed from KR1020170174513A external-priority patent/KR102147364B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780036217.XA priority Critical patent/CN109314238B/zh
Priority to EP17884634.1A priority patent/EP3447830A4/fr
Publication of WO2018117634A1 publication Critical patent/WO2018117634A1/fr
Priority to US16/242,712 priority patent/US11183691B2/en

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/89—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by mass-spectroscopy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
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    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a high voltage positive electrode active material and a method for manufacturing the same.
  • lithium secondary batteries exhibiting high energy density and operating potential, long cycle life, and low self discharge rate are commercially used.
  • LiCo0 2 As a cathode material having such a substituted cathode material or a coating.
  • structural stability is difficult to maintain, making it difficult to apply a high capacity secondary battery.
  • the positive electrode material having a coating layer formed on the surface of LiCo0 2 is a fact that the coating layer has a problem of preventing the movement of Li ions during charging and discharging or reducing the capacity of LiCo0 2 , but rather reducing the performance of a secondary battery. .
  • the present invention deteriorates even at high voltages of more than 4.5V. It is to provide a positive electrode active material and a method for manufacturing the same that can have structural stability without. In addition, the present invention provides a positive electrode including the positive electrode active material, and a lithium secondary battery that can exhibit excellent performance and life characteristics even under a high voltage of more than 4.5V.
  • the present invention is a lithium cobalt oxide of the charge weed represented by the formula (1).
  • a metal element (M) doped on the lithium cobalt oxide in an amount of 0.2 to 1 parts by weight based on 100 parts by weight of the lithium cobalt oxide.
  • a positive electrode active material in which the crystal structure is maintained in a range in which the positive electrode potential at full charge exceeds 4.5 V based on the Li potential:
  • M is at least one member selected from the group consisting of Al, Ti, Mg, Mn, Zr, Ba, Ca, Ta, Mo, Nb, and metals having an oxidation number of +2 or +3.
  • the present invention also includes a positive electrode comprising the positive electrode active material; cathode; And it provides a lithium secondary battery comprising an electrolyte.
  • the present invention dry mixing the cobalt salt, lithium precursor and the doping precursor; And firing the mixture at a temperature of 900 ° C. or higher.
  • a cathode active material and a method of manufacturing the same according to specific embodiments of the present invention will be described.
  • M is at least one member selected from the group consisting of Al, Ti, Mg, Mn, Zr, Ba, Ca, Ta, Mo, Nb, and metals having an oxidation number of +2 or +3.
  • lithium cobalt oxide of the formula (1) having a layered structure is doped with one or more metal elements to a predetermined content or more, it is determined even in a range exceeding 4.5V. Structural stability of the structure was improved to maintain a stable crystal structure, and found a high high voltage characteristic and came to complete the invention.
  • the metal element is "doped" to lithium cobalt oxide. Although it does not form a chemical bond with the constituent element, it may mean that at least a part of the metal element M is incorporated into the crystal lattice structure of the lithium cobalt oxide to have a physical / crystallographic state. At this time, at least a part of the metal element M incorporated into the crystal lattice structure of the lithium cobalt oxide is inserted into the empty crystal lattice structure of the lithium cobalt oxide, for example, without forming a chemical bond with the lithium cobalt oxide. It may have a physical / crystallographic connection. As such, as having a physical / crystallographic connection state without forming a chemical bond, the metal element M may be distributed more in a region close to the surface of the lithium cobalt oxide.
  • such "doping” is a metal element M forming the lithium cobalt oxide and the chemical bonding state, for example, the chemical bonds in the oxide by substituting cobalt part contained in the lithium cobalt oxide, the composite state with clearly in Can be distinguished.
  • the metal element M may be uniformly distributed over the entire region of the lithium cobalt oxide by the chemical bond and formation of the composite.
  • the cathode active material of one embodiment is based on lithium cobalt oxide of Chemical Formula 1.
  • it is composed of a structure doped with at least one metal element, and since a certain amount of dopant is introduced into and positioned in the crystal lattice of lithium cobalt oxide, the stability of the crystal structure or the particle surface is improved. Can be.
  • the positive electrode active material of one embodiment is at least a certain level, for example, 0.2 parts by weight or more, or 0.2 to 1.0 parts by weight, or 0.3 to 0.9 parts by weight, 4.3V or more, black 4.5V
  • the crystal structure of lithium cobalt oxide can be stabilized even under a high voltage, and it has been confirmed that it can be preferably applied as an active material exhibiting excellent capacity characteristics and life characteristics under such a high voltage.
  • the dopant content is more than 1.0 parts by weight
  • a complex by chemical bonding with lithium cobalt oxide eg, a complex in which a part of cobalt is substituted by a metal element M
  • the structural stability of the active material under high voltage is rather reduced, or such a substitution element or the coating layer hinders the movement of Li ions during charging and discharging, or the cobalt content is relatively reduced. Capacity characteristics of the 1-based active material may be lowered.
  • the metal element M is doped with lithium cobalt oxide and introduced into the crystal lattice.
  • the above-described active material may be TOF-SIMS (Time of Flight Secondary Ion Mass Spectrometry). ) Can be confirmed from the analysis results.
  • the metal element M is the above.
  • the metal source at least some of the lithium cobalt oxide and::: without forming a complex by a chemical bond, that doped in the lithium cobalt oxide You can check it.
  • the positive electrode active material is in excess of 4.5V
  • the crystal structure can be maintained in the charging range of 4.8V or less, and in detail, the stability of the crystal structure can be maintained in the charging range of more than 4.5V to 4.6V, and more specifically, ' 4.5V to 4.55.
  • the crystal structure and stability can be secured in the charging range below V.
  • Metal element M which is the above-mentioned dopant is Al, Ti, Mg, Mn, Zr, Ba, Ca, Ta ; It can be selected without particular limitation from the group of metal elements consisting of Mo, Nb, and a 'metal having an oxidation number of +2 or +3.
  • the surface side reaction with the electrolyte may also be AI or Mg, considering the effect of lowering the phase stability and phase stability at high voltage. In some cases, both AI and Mg may be used as dopants. .
  • the cathode active material of one embodiment may maintain the crystal structural stability even at high voltage charging, this stability can be confirmed by XRD analysis.
  • the positive electrode active material may have a peak intensity of the (003) plane at 4.55V at 30% or more of the (003) plane peak intensity at 4.50V on a 2 ⁇ scale of the XRD analysis result.
  • the peak intensity of the (003) plane at 4.55V It may be at least 40%, or 40 to 90% of the (003) plane peak intensity at 4.50V.
  • the crystal structure of the lithium cobalt oxide is maintained, in the case of the previous lithium cobalt oxide When charged up to 4.55V, the crystal structure collapsed and a significantly lower peak intensity was measured when compared to the peak of 4.5V. Therefore, it can be seen that when the lithium cobalt oxide is doped with a small amount or doped with a small amount of metal, the crystal structure collapses in a range exceeding 4.5V.
  • the positive electrode active material of one embodiment exhibits a peak intensity of (003) plane at 4.55V more than 30% with respect to the peak intensity at 4.5V by using a specific content and type of dopant, so that it is structural at high voltage. It can be seen that the stability is improved.
  • the capacity retention rate of the positive electrode active material in which the content (b) of the doped metal element (M) is 0.3 part by weight is a doped metal element.
  • the content of (M) may appear relatively low compared to the capacity retention rate of 0.1 parts by weight.
  • the capacity retention rate is lowered due to a large amount of dopant when the voltage at full charge is 4.5V. Therefore, in the case of the positive electrode active material of one embodiment, in order to exhibit a high capacity retention rate, not only the content of the doping metal is high, but also the charge voltage needs to be higher than at least 4.5V.
  • the capacity retention rate of the positive electrode active material having the Mg content of 0.3 parts by weight is the capacity of the positive electrode active material having the doped Mg content of 0.1 parts by weight when the charge and discharge cycle is 30 or more times. It may appear relatively low compared to retention.
  • Mg is doped into the lithium cobalt positive electrode active material, and the Mg content is 0.3 parts by weight, when the charge and discharge cycle is less than 30 times, it shows a higher capacity retention rate than when the content of Mg is 0.1 parts by weight, but more than 30 times In the case of Mg, the capacity retention rate is lower than 0.1 parts by weight.
  • the capacity retention rate of the positive electrode active material having a content of metal element M of 0.3 parts by weight may be relatively higher than that of the positive electrode active material having a content of doped metal element M of 0.1 part by weight.
  • the positive electrode active material of one embodiment requires more than a predetermined amount of dopant to exhibit high capacity retention at high voltages exceeding 4.5V.
  • the charging voltage is 4.5 V
  • the doping metal is Mg
  • the charge and discharge cycle is more than 30 cycles
  • 0.3 parts by weight of the doped part has a higher capacity retention rate than 0.1 parts by weight of the doped part.
  • the doping increases as the charge and discharge cycle increases.
  • the difference between the capacity retention rate of the positive electrode active material in which the metal content is 0.3 parts by weight and the capacity retention rate of the positive electrode active material in 0.1 parts by weight becomes larger.
  • the capacity retention rate at 50 charge / discharge cycles is 50% when the positive electrode potential of the full-scale display is 4.55V based on the Q potential. It may be 85% or more as a standard, and generally, when the content of the doped metal element is 0.1 parts by weight, it can be seen that the capacity retention rate in the same cycle is higher than that when it is less than 75%.
  • the cathode active material of the above-described embodiment further comprises a coating layer formed on the lithium cobalt oxide particles, the coating layer is a group consisting of Al 2 O 3 , MgO, ZrO, Li 2 Zr0 3 and Ti0 2 It may include one or more metal oxides selected from.
  • the structural stability of the lithium cobalt oxide particles may be further improved.
  • lithium cobalt oxide when used as a positive electrode active material at a high voltage, a large amount of lithium ions are released from the lithium cobalt oxide particles, and the concentration of Li ions on the surface is low so that Co is easily eluted. As the amount of Co eluted increases, the reversible capacity decreases, and the probability of Co precipitated on the surface of the cathode increases. It can be a factor to increase the cathode resistance. Therefore, when the metal oxide coating layer is further formed on the particles of lithium cobalt oxide, the metal element included in the coating layer preferentially reacts with HF to protect the cathode active material particles. As a result, the cycle characteristics of the secondary battery at high voltage can be effectively prevented from being lowered.
  • the content of the metal element included in the coating layer can be adjusted to 300 ppmw to 1,200 ppmw based on the content of lithium cobalt oxidation of Formula 1, the positive electrode when the amount of the metal element included in the coating layer is less than 300 ppmw If the structural stability of the active material is difficult to secure, and larger than 1,200 ppmw, the capacity and output characteristics of the battery are deteriorated, which is not preferable.
  • the method of producing a positive electrode active material of the above-described embodiment includes the steps of dry mixing a cobalt salt, a lithium precursor and a doping precursor; And calcining the mixture to a temperature of 900 ° C. or higher.
  • one embodiment of the active material doped with at least a part of the metal element M was prepared by dry mixing the respective precursors and solid-state burning.
  • the wet method such as coprecipitation method
  • the active material in the form of a composite in which the metal element M is chemically bonded with the formula (1) is obtained, and thus, the cathode active material in the form of one embodiment does not appear to be manufactured.
  • the firing temperature may be 900 ° C to 1,200 ° C, in detail may be 1,000 ° C to 1,100 ° C, the firing The time may be 4 hours to 20 hours, specifically 5 hours to 15 hours.
  • the calcination temperature is lower than 900 ° C, the structure of the lithium cobalt oxide is not formed smoothly, and if the calcination temperature is higher than 1,2003 ⁇ 4, it is not preferable because the capacity deterioration or the life deterioration may occur due to the overfiring of lithium cobalt oxide. .
  • the firing time is less than 4 hours may cause a problem that the doping is not enough, if more than 12 hours may change the physical and chemical properties of the lithium cobalt oxide may cause performance degradation. Therefore, it is not preferable.
  • the method may further include forming a coating layer on the surface of the M-doped lithium cobalt oxide, wherein the coating layer may include at least one selected from the group consisting of Al 2 O 3 , MgO, ZrO, Li 2 Zr0 3, and Ti0 2 . It may already include more than one metal oxide, as has already been appreciated.
  • a salt containing a metal element to be included in the coating layer may be mixed with the doped lithium cobalt oxide and calcined, and the salt containing the metal element may be sintered to the doped lithium cobalt.
  • the cobalt oxide used in the manufacturing method of the other embodiments described above is.
  • the type is not particularly limited, for example, the cobalt acid salt may be at least one selected from the group consisting of Co 3 O 4 , C0CO 3 , Co (N0 3 ) 2, and Co (OH) 2 , and in detail Co 3 0 4 , or Co (this H) 2 .
  • the lithium precursor may be one or more selected from the group consisting of Li 2 CO 3 , LiOH, L 1 NO 3 , CH 3 COOL 1, and Li 2 (COO) 2 , and specifically, may be UC) H, or Li 2 CO 3 .
  • the doping precursor is at least one metal, metal oxide, and metal salt selected from the group consisting of Al, Ti, Mg, Mn, Zr, Ba, Ca, Ta, Mo, Nb, and metals having an oxidation number of +2 or +3. It may be one or more selected from the group consisting of, in detail may be AI, and / or Mg.
  • a secondary battery positive electrode comprising a cathode active material for implementing the above-described example one.
  • the positive electrode may be manufactured by, for example, applying a positive electrode active material composed of positive electrode active material particles to a positive electrode current collector, a positive electrode mixture in which a conductive material and a binder are mixed, and further adding a filler to the positive electrode mixture as necessary. Can be added.
  • the positive electrode current collector is generally manufactured in a thickness of 3 ⁇ to 500 ⁇ , and is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • stainless steel, aluminum, nickel, Titanium, and carbon, nickel, titanium or 'One selected from surface treated with silver may be used, and in detail, aluminum may be used.
  • the current collector may form fine irregularities on its surface to increase the adhesion of the positive electrode active material, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • Examples of the conductive material include graphite such as natural or artificial graphite; Carbon blacks such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black and summer black; Conductive fibers such as carbon fibers and metal fibers; Powders such as carbon fluoride, aluminum and nickel powder; Organic whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the binder included in the positive electrode is a component that assists in bonding the active material, the conductive material, and the like to the current collector, and is generally added in an amount of 0.1 to 30 weight 0 / ° based on the total weight of the mixture including the positive electrode active material. .
  • binders examples include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyridone, tetrafluoroethylene polyethylene, Polypropylene, ethylene-propylene-diene ter : Polymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various co-polymers, and the like.
  • CMC carboxymethyl cellulose
  • EPDM sulfonated EPDM
  • styrene-butadiene rubber examples include fluorine rubber, various co-polymers, and the like.
  • a lithium secondary battery including the positive electrode, the negative electrode, and the electrolyte.
  • the type of the lithium secondary battery is not particularly limited, but for example, a lithium ion battery having a high energy density, a discharge voltage, an output stability, and the like may be included in the lithium ion polymer battery.
  • a lithium secondary battery is composed of a positive electrode, a negative electrode, a separator, and a lithium salt-containing nonaqueous electrolyte.
  • the negative electrode is manufactured by applying and drying a negative electrode active material on a negative electrode current collector, If necessary, the components as described above may optionally be further included.
  • the negative electrode current collector is generally made in a thickness of 3 ⁇ to 500 ⁇ .
  • Such a negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery, for example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon. ,. Copper or stainless steel surface i to the surface carbon, nickel, titanium in the steel is such a process: to, aluminum-cadmium alloys.
  • fine concavities and convexities may be formed on the surface to enhance the bonding force of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • carbon such as hardly graphitized carbon and an inferior carbon
  • Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1-x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me' : Metal composite oxides such as Al, B, P, Si, group 1, 2, 3, and halogen of the periodic table, 0 ⁇ x ⁇ 1, 1 ⁇ y ⁇ 3, 1 ⁇ z ⁇ 8)
  • Lithium metal Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, Sn0 2, PbO, Pb0 2, Pb 2 0 3 'Pb 3 0 4, Sb 2 0 3, Sb 2 0 4, Sb 2 0 5, GeO, Ge0 2, Bi 2 0 3, Bi 2 0 4, and metal oxide such as Bi 2 0 5
  • Conductive polymers such as polyacetylene; Li-Co-Ni-based
  • the separator is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used.
  • 2-methoxy ethanol, aluminum trichloride, or the like may be added.
  • a halogen-containing solvent such as carbon tetrachloride and ethylene trifluoride may be further included, or carbon dioxide gas may be further included to improve high temperature storage characteristics.
  • FEC Fluoro-Ethylene Carbonate
  • PRS Propene sultone
  • a battery pack including the secondary battery and a device including the battery pack are provided.
  • Such battery packs and devices are known in the art, and thus, Detailed description will be omitted.
  • the device may be, for example, a laptop computer, a netbook, a tablet PC, a mobile phone, an MP3, a wearable electronic device, a power tool, an electric vehicle (EV), a hybrid electric vehicle (HEV). , Plug-in hybrid H electric vehicles (PHEVs), electric bikes (E-bikes), electric scooters (E-scooters), electric golf carts, or power storage It may be a system for, but is not limited to these, of course.
  • PHEVs Plug-in hybrid H electric vehicles
  • E-bikes electric bikes
  • E-scooters electric golf carts
  • power storage It may be a system for, but is not limited to these, of course.
  • the cathode active material according to the present invention is a structure in which at least one metal element is doped into a lithium cobalt oxide having a layered structure, and at least a level of dopant is introduced into the crystal lattice of lithium cobalt oxide. Because of its location, it is possible to suppress the collapse of the crystal structure to ensure structural stability at high voltages higher than 4.5V.
  • lithium cobalt oxide has only a method of increasing the voltage to increase the capacity.
  • the cathode active material according to the present invention is used, stability problems at high voltage are solved, and thus high capacity and high cycle characteristics may be exhibited. have.
  • FIG. 2 is a graph showing capacity retention when the upper limit voltage is charged to 4.55 V for a half coin cell containing Mg of 1,000 ppm and 3,000 ppm doped lithium cobalt oxide, respectively;
  • FIG. 3 is a graph showing capacity retention when the upper limit voltage is charged to 4.5V for a half-coin cell containing 1,000 ppm and 3,000 ppm doped lithium cobalt oxide, respectively;
  • FIG. 5 is a view showing a time of flight secondary ion mass spectrometry (TOF-SIMS) analysis of the cathode active material of Example 1;
  • TOF-SIMS time of flight secondary ion mass spectrometry
  • FIG. 6 is an XRD graph showing peak intensities when the upper limit voltage is increased in steps of 0.01 V from 4.5 V to 4.54 V in the half coin cell including the positive electrode active materials of Example 1 and Comparative Example 1.
  • FIG. 6 is an XRD graph showing peak intensities when the upper limit voltage is increased in steps of 0.01 V from 4.5 V to 4.54 V in the half coin cell including the positive electrode active materials of Example 1 and Comparative Example 1.
  • 0.294 g of MgO, 80.27 g of Co 3 0 4 , and 36.94 g of Li 2 CO 3 are dry mixed so that Mg contains 3,000 ppm based on the total weight of the positive electrode active material, and then 10 hours at 1,050 ° C. in a furnace. Firing was performed to produce lithium cobalt oxide doped with Mg.
  • Mg determines the total weight of the positive electrode active material.
  • Mg-doped lithium cobalt oxide was prepared in the same manner as in Example 1 except that 1,000 ppm was included as a reference.
  • AI-doped lithium cobalt oxide was prepared in the same manner as in Example 2 except that AI was included in an amount of 1,000 ppm based on the total weight of the positive electrode active material.
  • Mg-doped lithium cobalt oxide was prepared in the same manner as in Example 1 except that Mg was included at 10,000 ppm based on the total weight of the positive electrode active material.
  • the half-coin cell manufactured as described above was charged at 0.5C at 25 ° C with an upper limit of 4.5V and 4.55V, respectively, and discharged at 1.0C to a lower limit of 3V as a cycle of 50 cycles. Dose retention was measured, and the results are shown in Table 1 and FIGS. 1 to 4.
  • Table 2 shows the initial capacity when charging to 4.5V and 4.55V, respectively.
  • Table 2 Referring to Table 1, Figures 1 to 4, and Table 2, as in Examples 1 and 2, when 3,000 ppm of Mg or AI were doped, respectively, the capacity retention rate when Mg or AI was charged and discharged at 50 V at 50 cycles was Mg. Alternatively, it can be seen that AI appears lower than Comparative Examples 1 and 2 doped with 1,000 ppm, respectively. In addition, in the case of using the positive electrode active material of Example 1 up to about 30 cycles, the capacity retention rate is higher than that of Comparative Example 1, but after 30 cycles, it is observed that the capacity retention rate of ⁇ rapidly decreases.
  • Example 2 where the doping amount of AII was 3,000 ppm, the capacity retention rate at 4.5V was lower than 4.55V, but the capacity retention rate was 4.5V when compared with Comparative Example 1 where the doping amount of AI was 1,000 ppm. Although this decreases, capacity retention increases at 4.55V.
  • the positive electrode active material undergoes reversible phase transition as charging and discharging proceeds.
  • the reversibility of the phase transition decreases, thereby decreasing capacity.
  • the irreversible phase transition can be minimized and the capacity retention rate can be prevented from being reduced.
  • the content of the doped metal is too small, as in Comparative Examples 1 and 2, it is difficult to exert the above effects, so that the charge retention is rapidly reduced when charging and discharging to 4.55V.
  • lithium cobalt oxide is doped in "certain content range of Mg or AI, by minimizing the phase change on the classic it can be seen that having a high capacity retention ratio.
  • the initial efficiency decreases above 4.5V, and it is expected that it will be easy to balance the balance between the positive electrode and the negative electrode when manufacturing the battery cell, and the amount of excess positive electrode active material is reduced, which helps to reduce the cost of the battery cell. It is expected to be. As a result, it is possible to design materials suitable for battery cell operating voltage conditions. In addition, it is expected that the battery cell can be greatly helped in implementing the performance required in the battery cell and reducing the cost.
  • Example 6 in which the coating charge is formed on the lithium cobalt oxide shown in FIG. 6, when charging and discharging was performed at 4.55V 50 times as compared with Example 1 without the coating layer, a higher capacity retention rate was shown.
  • the positive electrode active material according to the embodiment is at a high potential higher than 4.5V '. It can be seen that the improved life characteristics.
  • Example 2 The result of analyzing the active material obtained in Example 2 by Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS) is shown in FIG. 5.
  • TOF-SIMS Time of Flight Secondary Ion Mass Spectrometry
  • a doped metal element A1 is on the lithium cobalt oxide: search the distribution is confirmed, in particular, to the surface of the lithium cobalt oxide containing minute at a higher concentration in the near region is confirmed. From the analysis result, it can be seen that A1 does not form a complex by chemical bonding with lithium cobalt oxide, and the lithium cobalt oxide phase is doped to form a physical / crystallographic connection structure.
  • the peak of the (003) plane was observed within the range of 23 degrees to 24 degrees in the case of 4.40 V to 4.55 V, and 24 degrees in the case of 4.55 V. Peaks are also observed within the range of 25 to 25 degrees.
  • the charging potential of the positive electrode active material is 4.54 V or more
  • phase transition proceeds to a phase in which the crystal structure is different, and in the case of 4.55 V, a new peak indicating the crystal structure after the phase transition is observed in the range of 24 to 25 degrees.
  • phase transition is reversible in that the peak of the (003) plane appears continuously to some extent, and thus, a certain capacity retention rate can be maintained even when charging and discharging proceeds.
  • Figure 6 shows the peaks before and after the phase transition by the magnitude of the voltage, the peak intensity of the (003) plane at 4.55V is at least 30% of the (003) plane peak intensity at 4.50V It can be seen that the metal doped lithium cobalt oxide shows a high capacity retention by minimizing the phase transition, it can exhibit a significantly improved life characteristics.

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Abstract

La présente invention porte sur un matériau actif d'anode de haute tension dopé avec un élément métallique et sur un procédé de fabrication correspondant, le matériau actif d'anode pouvant être un matériau comprenant : de l'oxyde de cobalt et de lithium présentant une structure en couches ; et un élément métallique (M) dopé sur l'oxyde de cobalt et de lithium en une quantité de 0,2 à 1 partie en poids pour 100 parties en poids de l'oxyde de cobalt et de lithium, et dans lequel une structure cristalline peut être maintenue dans une plage où, entièrement chargée, la tension anodique dépasse 4,5 V sur la base du potentiel de Li.
PCT/KR2017/015118 2016-12-21 2017-12-20 Matériau actif d'anode de haute tension dopé avec du métal WO2018117634A1 (fr)

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