WO2016108382A1 - Matériau actif de cathode pour batterie rechargeable au lithium, son procédé de fabrication, et batterie rechargeable au lithium comprenant celui-ci - Google Patents

Matériau actif de cathode pour batterie rechargeable au lithium, son procédé de fabrication, et batterie rechargeable au lithium comprenant celui-ci Download PDF

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WO2016108382A1
WO2016108382A1 PCT/KR2015/008730 KR2015008730W WO2016108382A1 WO 2016108382 A1 WO2016108382 A1 WO 2016108382A1 KR 2015008730 W KR2015008730 W KR 2015008730W WO 2016108382 A1 WO2016108382 A1 WO 2016108382A1
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active material
lithium
secondary battery
lithium secondary
nickel
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PCT/KR2015/008730
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English (en)
Korean (ko)
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김종민
장동규
김지윤
이미선
채영주
김동한
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삼성에스디아이 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • H01M4/50—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
    • 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
    • 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 cathode active material for a lithium secondary battery, a method of manufacturing the same, and a lithium secondary battery including the same. More specifically, the initial efficiency, capacity, and lifespan of a battery are included by including a nickel-based lithium transition metal oxide having reduced nickel mobility.
  • the present invention relates to a cathode active material for a lithium secondary battery capable of improving characteristics, a method of manufacturing the same, and a lithium secondary battery including the same.
  • the electronics and telecommunications industry is rapidly developing through the portable, miniaturized, lightweight, and high performance electronic devices, and the demand for lithium secondary batteries that can realize high capacity and high performance as a power source for these electronic devices is rapidly increasing. Further, as electric vehicles (EVs) and hybrid electric vehicles (HEVs) are put into practical use, research on lithium secondary batteries having high capacity and output and excellent stability is being actively conducted.
  • EVs electric vehicles
  • HEVs hybrid electric vehicles
  • Lithium secondary batteries are manufactured by using a material capable of intercalation and disintercalation of lithium ions as a negative electrode and a positive electrode, and filling an organic or polymer electrolyte between a negative electrode and a positive electrode, and lithium ions are inserted in the positive and negative electrodes. And electrical energy is generated by the oxidation reaction and the reduction reaction at the time of detachment.
  • the cathode material plays an important role in determining the capacity and performance of the battery in the battery.
  • Lithium cobalt oxide (LiCoO 2 ) is the first commercially available cathode material, which is still widely used as a cathode material due to its relatively good structural stability and ease of mass production compared to other lithium transition metal oxides. Due to its limitations, the price is expensive and harmful to the human body.
  • Ni-rich (Ni-rich) -based positive electrode active material containing a lot of nickel (Ni) of the lithium metal oxide having a layered structure exhibits a high capacity of more than 200mAh / g is considered as the next-generation electric vehicle and power storage cathode material have.
  • nickel (Ni) has been researched in a lot of interest because it is less toxic to human body and cheaper than cobalt (Co) (Non-Patent Document 1).
  • nickel tends to prefer divalent rather than trivalent valence, it is an empty space of a lithium layer in which lithium deficiency occurs due to volatilization of a raw material lithium salt at high temperature firing, and nickel having a divalent valence similar in lithium ion to an ion radius.
  • ions (Ni + 2) results in the incorporation, there is a problem that a non-stoichiometric lithium nickel oxide of the following composition are prepared.
  • Non-chemical lithium nickel oxide of stoichiometric composition, the Ni 2 + incorporated into the lithium layers, as well as interfere with the diffusion of lithium ions there is a problem of reducing the reversible capacity to significantly increase non-reversible.
  • Patent Document 1 Korean Patent Application Laid-Open No. 2013-0084361 discloses a metal cation having an ion radius larger than that of the Ni cation to prevent Ni cation mixing in the Li layer. Is disclosed in the positive electrode active material contained in the Li cation site or the empty space in the crystal lattice. According to this method, the movement path of Ni 2+ may be partially blocked, but the metal cations may interfere with the diffusion of lithium ions (Li + ), thereby lowering the electrochemical properties of the cathode active material.
  • the present inventors have a diffraction peak in the region where the diffraction angle 2 ⁇ is 20 ° to 25 ° in the X-ray diffraction analysis using a Cu target, and the peak peak is located between 21.8 ° and 22.5 °.
  • the present invention was completed by confirming that the mobility of nickel around lithium is reduced and the generation of nickel oxide-related heterogeneous phases, which may degrade the performance of the active material, is suppressed.
  • Patent Document 1 KR2013-0084361 A
  • Non-Patent Document 1 Sang-Yoon Lee, Study on Substitution and Surface Modification of Heterogeneous Elements for Structural Stability Improvement of Ni-rich Cathode Active Materials for Lithium Secondary Batteries, Master's Thesis, graduate School of Korea University (2013.2)
  • the diffraction peak is present in the region where the diffraction angle 2 ⁇ is 20 ° ⁇ 25 ° in the X-ray diffraction analysis using a Cu target, the peak peak is 22.5 ° to 22.5
  • a nickel-based lithium transition metal oxide located between ° to reduce the mobility of nickel around the lithium has excellent conductivity, to provide a positive electrode active material that can improve the initial efficiency, capacity and life characteristics of the battery.
  • Another object of the present invention is to provide a lithium secondary battery including the cathode active material.
  • the present invention includes a nickel-based lithium transition metal oxide having a layered structure represented by the following formula (1), X-ray diffraction using a copper target (Cu Target) of the lithium transition metal oxide
  • the present invention provides a cathode active material for a lithium secondary battery, characterized in that a diffraction peak exists in a region having a diffraction angle 2 ⁇ of 20 ° to 25 °, and the peak of the peak is located between 21.8 ° and 22.5 °.
  • a peak does not appear in a region having a diffraction angle 2 ⁇ of 20 ° to 21.8 °, and a peak height appearing between 21.8 ° and 22.5 ° is the lithium transition metal oxide.
  • it is preferably in the range of 0.05% to 2% of the peak height appearing near the diffraction angle 2 ⁇ 18 °.
  • the present invention provides a method for producing the cathode active material and a lithium secondary battery comprising the cathode active material.
  • the method for preparing the cathode active material may include mixing a precursor represented by Chemical Formula 2 and a lithium source in an equivalent ratio satisfying the condition of Equation 1 below; And heat-treating the mixture at 800 to 1000 ° C.
  • Equation 1 M is the x + y + z value of the formula (2).
  • the present invention by reducing the mobility of lithium surrounding nickel in the nickel-based lithium transition metal oxide, it is possible to suppress the occurrence of nickel oxide-related heterogeneous phases, which may reduce the performance of the active material, and provide additional mobile sites to the lithium to provide It can improve conductivity and improve structural stability during overcharging.
  • the cathode active material containing the nickel-based lithium transition metal oxide it is possible to provide a lithium secondary battery having excellent initial efficiency, capacity, and lifespan.
  • Figure 1 shows a comparison of the X-ray diffraction spectrum of the positive electrode active material prepared according to Example 1 and Comparative Example 1.
  • Figure 2 shows a comparison of the X-ray diffraction spectrum of the positive electrode active material prepared according to Examples 1 and 2.
  • Figure 3 shows a comparison of the X-ray diffraction spectrum of the positive electrode active material prepared according to Example 1 and Comparative Example 2.
  • Figure 4 is a graph showing the charge and discharge test results of the lithium secondary battery prepared using the positive electrode active material of Example 1 and Comparative Example 1.
  • Example 5 is a graph showing the life characteristics of the lithium secondary battery prepared using the positive electrode active material of Example 1 and Comparative Example 1.
  • Figure 6 is a graph showing the comparison of the conductivity according to the pressure of the positive electrode active material prepared according to Example 1 and Comparative Example 1.
  • the present invention includes a nickel-based lithium transition metal oxide having a layered structure represented by Formula 1 below, and the diffraction angle 2 ⁇ is 20 ° to X-ray diffraction analysis of the lithium transition metal oxide using a copper target (Cu Target).
  • the diffraction peak exists in the area
  • the lithium transition metal oxide according to the present invention is a nickel-rich (Ni-rich) lithium transition metal oxide containing nickel (Ni) more than cobalt (Co) and manganese (Mn).
  • Ni-rich (Ni-rich) type lithium transition metal oxide was having difficulty in commercialization due to the structural instability which it is possible to express a high capacity although the spotlight as materials for the next generation of electrodes storage, essentially Ni 3 + is present .
  • the nickel-based lithium transition metal oxide according to the present invention has a structure in which a part of lithium is arranged in a layered structure, the structural stability of nickel can be achieved.
  • the present inventors found that the nickel-based lithium transition metal oxide having the above structure has the highest peak among the peaks present in the region where the diffraction angle 2 ⁇ is 20 ° to 25 ° in the X-ray diffraction analysis, between 21.8 ° and 22.5 °. appears, which resulted in the completion of the in this case the present invention to determine the lithium surrounding nickel that the mobility of the drop being the generation (the Ni 2 + incorporated in, for example, Li layer) nickel oxide-related yijongsang that can degrade the active material performance suppressed because of .
  • the occurrence of nickel oxide-related heterophages is suppressed, it is possible to provide a lithium secondary battery having improved initial conductivity, battery capacity, and lifespan by providing additional moving sites to lithium, thereby improving conductivity. have.
  • the peak height appearing between 21.8 ° and 22.5 ° is preferably in the range of 0.05% to 2% of the peak height of the diffraction angle 2 ⁇ at around 18 ° in the X-ray diffraction analysis of the nickel-based lithium transition metal oxide.
  • the peak height appearing in the region of the diffraction angle 2 ⁇ is in the range of 21.8 ° ⁇ 22.5 ° falls within the above range it is preferable because the effect of reducing the mobility of nickel is the most excellent and the effect of improving the conductivity of the active material to the maximum.
  • the lithium manganese oxide lithium is surrounded by a metal element having a tetravalent valence such as manganese.
  • the lithium transition metal oxide of the layer structure according to the present invention is prepared by adding an excessive amount of lithium, metal elements around lithium have a trivalent valence on average. That is, even if lithium is introduced at a ratio greater than the total amount of transition metals (Ni, Co, and Mn) in the manufacturing step, a heterogeneous Li 2 MnO 3 formed of lithium and manganese is not formed, but part of lithium is partially added to the layered structure. Because of the structure that exists in the arrangement, the metallic elements around lithium have an average valence of trivalent rather than tetravalent.
  • a peak does not appear in a region having a diffraction angle 2 ⁇ of 20 ° to 21.8 °.
  • the 20 ° to 21.8 ° region is a section in which diffraction peaks originating from the Li 2 MnO 3 phase appear, and in the presence of the Li 2 MnO 3 phase, a strong peak near 21 ° and a shoulder peak between 21 ° and 21.8 ° are observed.
  • the peak of the lithium transition metal oxide of Comparative Example 2 including the Li 2 MnO 3 phase was found in the 20 ° ⁇ 21.8 ° region.
  • the present invention provides a method for producing a cathode active material including the nickel-based lithium transition metal oxide.
  • the method of manufacturing the positive electrode active material comprises the steps of mixing the precursor represented by the formula (2) and the lithium source in an equivalent ratio that satisfies the conditions of the following formula (1); And heat-treating the mixture at 800 to 1000 ° C.
  • Equation 1 M is the x + y + z value of the formula (2).
  • the number of moles of Li / M may be 1.01 to 1.05.
  • a positive electrode active material including a Li 2 MnO 3 phase having peaks in a region having a diffraction angle 2 ⁇ of 20 ° to 21.8 ° may be formed.
  • a positive electrode active material including a Li 2 MnO 3 phase having a peak in a region where 2 ⁇ is 20 ° to 21.8 ° may be formed. Particle size may increase too much and battery characteristics may decrease.
  • the present invention provides a lithium secondary battery including the cathode active material.
  • the lithium secondary battery may include a cathode including the cathode active material, a cathode including an anode active material, a separator, and a nonaqueous electrolyte.
  • the structure and manufacturing method of the lithium secondary battery are known in the technical field of the present invention, and may be appropriately selected without departing from the scope of the present invention.
  • the positive electrode is manufactured by applying a composition for forming a positive electrode active material including the positive electrode active material and the binder according to the present invention to a positive electrode current collector, and then drying and rolling.
  • the binder serves to fix the bonding between the positive electrode active material and the current collector, and any binder used in the art may be used without limitation, and preferably, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl It may be at least one selected from chloride, polyvinylpyrrolidone, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, polyethylene, polypropylene, styrene butyrene rubber, fluorine rubber.
  • any binder used in the art may be used without limitation, and preferably, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl It may be at least one selected from chloride, polyvinylpyrrolidone, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, polyethylene, polypropylene, styrene butyrene rubber, fluorine rubber.
  • the composition for forming the positive electrode active material may include a solvent such as N-Methyl-2-pyrrolidone (NMP) and an olefinic polymer such as polyethylene and polypropylene, optionally for the positive electrode active material and the binder; It may be prepared by further adding a filler made of a fibrous material such as glass fiber, carbon fiber and the like. In addition, it may further include a conductive agent known in the art, such as hard carbon, graphite and carbon fiber.
  • NMP N-Methyl-2-pyrrolidone
  • an olefinic polymer such as polyethylene and polypropylene
  • the positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery, and examples thereof include copper, stainless steel, aluminum, nickel, titanium, calcined carbon; Surface-treated with carbon, nickel, titanium, silver or the like on the surface of copper and stainless steel; Aluminum-cadmium alloys, and the like, and various forms such as films, sheets, foils, nets, porous bodies, foaming agents, and nonwoven fabrics are also possible.
  • the negative electrode may be prepared by coating a composition for forming a negative electrode active material including a negative electrode active material on a negative electrode current collector and then drying and rolling it, or lithium metal.
  • the negative electrode active material composition may further include the binder and the conductive material.
  • the negative electrode active material may be a carbonaceous material such as artificial graphite, natural graphite, graphitized carbon fiber, amorphous carbon, lithium and silicon (Si), aluminum (Al), tin (Sn), lead (Pb), zinc (Zn), Alloyable metal compounds such as bismuth (Bi), indium (In), manganese (Mg), gallium (Ga), cadmium (Cd), silicon alloys, tin alloys, aluminum alloys, and the like and carbonaceous materials It may be a composite including a.
  • Alloyable metal compounds such as bismuth (Bi), indium (In), manganese (Mg), gallium (Ga), cadmium (Cd), silicon alloys, tin alloys, aluminum alloys, and the like and carbonaceous materials It may be a composite including a.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery, and examples thereof include copper, stainless steel, aluminum, nickel, titanium, calcined carbon; Surface-treated with carbon, nickel, titanium, silver or the like on the surface of copper and stainless steel; Aluminum-cadmium alloys, and the like, and various forms such as films, sheets, foils, nets, porous bodies, foaming agents, and nonwoven fabrics are also possible.
  • the separator is disposed between the negative electrode and the positive electrode, and conventional porous polymer films used as conventional separators, such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate Porous polymer films made of polyolefin-based polymers such as copolymers may be used alone or in a stack of these. It is also possible to use conventional porous nonwoven fabrics such as nonwoven fabrics of high melting point glass fibers, polyethylene terephthalate fibers and the like.
  • the non-aqueous electrolyte solution is composed of an electrolyte solution and a lithium salt, but the non-aqueous organic solvent, an organic solid electrolyte, an inorganic solid electrolyte, and the like are used as the electrolyte solution, but are not limited thereto.
  • non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and gamma Butyl lactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxorone, formamide, dimethylformamide, dioxolon , Acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbo Aprotic organic solvents such as nate derivatives, tetrahydrofuran derivatives, ethers, methyl pyroionate and ethyl propionate can be
  • organic solid electrolytes examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyagitation lysine, polyester sulfides, polyvinyl alcohol, polyvinylidene fluoride, Polymerizers containing ionic dissociating groups and the like can be used.
  • Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates and the like of Li, such as Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 S-SiS 2 , and the like, may be used.
  • the lithium salt is a good material to be dissolved in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide.
  • the secondary battery may be divided into a coin type, a square shape, a cylindrical shape, a pouch type, and the like. Since the structure and manufacturing method of these batteries are known in the art, detailed description thereof will be omitted.
  • Ni 0 . 6 Co 0 . 2 Mn 0 .2 (OH) 1 2 precursor and LiOH: then a solution of an equivalent ratio (Li mole number / M 1.01) of 1.01, and heat treated at a temperature of 850 °C LiNi 0. 6 Co 0 . 2 Mn 0 .
  • a cathode active material having a composition of 2 O 2 was prepared.
  • Ni 0 . 5 Co 0 . 2 Mn 0 .3 (OH) 1 2 precursor and LiOH: then a solution of an equivalent ratio (Li mole number / M 1.02) of 1.02, and heat treated at a temperature of 850 °C LiNi 0. 5 Co 0 . 2 Mn 0 .
  • a cathode active material having a composition of 3 O 2 was prepared.
  • a cathode active material having a composition of 2 O 2 was prepared.
  • Ni 0 . 2 Co 0 . 2 Mn 0 .6 (OH) 2 precursor and LiOH 1: After mixing in 1.4 equivalent ratio (Li mole number / M 1.40), the heat-treated at a temperature of 700 °C Li 1. 17 Ni 0 . 17 Co 0 . 17 Mn 0 . A cathode active material having a 5 O 2 composition was prepared.
  • FIG. 1 which compares the X-ray diffraction spectra of the cathode active materials prepared according to Example 1 and Comparative Example 1, the diffraction peaks in the region where the diffraction angle 2 ⁇ is 20 ° to 25 ° for the cathode active material of Example 1 Is present, the peak of the peak is located between 21.8 ° to 22.5 °, whereas the positive electrode active material of Comparative Example 1 has the same composition as the positive electrode active material of Example 1 but the peak or peak of the peak is not located in the region Do not.
  • FIG. 2 which compares the X-ray diffraction spectrums of the cathode active materials prepared according to Examples 1 and 2, as the nickel content is increased, the peaks appearing in the region where the diffraction angle 2 ⁇ is 21.8 ° to 22.5 °. As the size increases, the peak is different from the peak appearing in the cathode active material of Comparative Example 2 and the relative size is different.
  • FIG. 3 which compares the X-ray diffraction spectra of the cathode active materials prepared according to Example 1 and Comparative Example 2, in the X-ray diffraction spectrum of the cathode active material according to Comparative Example 2, a strong peak near 21 °. And a shoulder peak between 21 ° and 21.8 ° is observed, whereas in the X-ray diffraction spectrum of Example 1, there is no peak at 20 ° to 21.8 °.
  • the positive electrode active material of Comparative Example 2 as a peak derived from the Li 2 MnO 3 is a does not include the cathode active material of Example 1 while containing Li 2 MnO 3 is a.
  • the aluminum foil was prepared by mixing the positive electrode active material prepared in Example 1 and Comparative Example 1, the conductive agent DenkaBlack, and the binder polyvinylidene fluoride (PVDF) at a ratio of 92: 4: 4 (w / w). Coating over to produce a positive electrode plate.
  • the initial efficiency (%) (discharge capacity / charge capacity at 1 st cycle of the 1 st cycle)
  • the formed cell was charged and discharged with a current of 1.0 C, and repeated 50 cycles.
  • the capacity retention ratio was calculated according to Equation (2) below, and evaluated as life characteristics. The results are shown in Table 1 below.
  • Capacity retention rate (%) (discharge capacity at 50 th cycle / discharge capacity at 1 st cycle)
  • the lithium secondary battery manufactured using the positive electrode active material of Example 1 the initial charge and discharge capacity, initial efficiency and life characteristics compared to the lithium secondary battery manufactured using the positive electrode active material of Comparative Example 1 It can be confirmed that it is excellent.

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Abstract

La présente invention concerne un matériau actif de cathode pour une batterie rechargeable au lithium dans lequel le matériau actif de cathode comprend un métal de transition au lithium à base de nickel ayant une structure en couches d'oxyde représenté par la formule LiaNibCocMndO2 (dans laquelle 1 < a < 1,14, b > c, b > d, 0,4 ≤ b ≤ 0,9, 0 < c < 0,4, et 0 ≤ d < 0,4), et dans lequel le pic le plus élevé parmi les pics présentés au sein d'un angle de diffusion 2θ compris entre 20° et 25° est montré entre 21,8° et 22,5° lors d'une mesure à l'aide d'une analyse de diffraction des rayons X; un procédé de préparation de celui-ci; et une batterie rechargeable au lithium le comprenant. Selon la présente invention, la mobilité d'un nickel adjacent au lithium au sein d'un oxyde de métal de transition au lithium est réduite, ce qui permet d'inhiber la génération de phase hétérogène relative à l'oxyde de nickel qui pourrait dégrader les performances d'un matériau actif, et en conséquence, la présente invention peut proposer une batterie rechargeable au lithium qui présente d'excellentes efficacité initiale, capacité et caractéristiques de durée de vie.
PCT/KR2015/008730 2014-12-29 2015-08-21 Matériau actif de cathode pour batterie rechargeable au lithium, son procédé de fabrication, et batterie rechargeable au lithium comprenant celui-ci WO2016108382A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100109605A (ko) * 2009-04-01 2010-10-11 주식회사 엘지화학 리튬 이차전지용 양극 활물질
KR20100130522A (ko) * 2009-06-03 2010-12-13 주식회사 엘지화학 리튬 이차전지용 전극 활물질
KR20130125124A (ko) * 2012-05-08 2013-11-18 한국과학기술연구원 리튬이차전지용 나노복합체 양극 활물질을 제조하는 방법
WO2014007358A1 (fr) * 2012-07-06 2014-01-09 住友化学株式会社 Oxyde métallique composite de lithium, matériau actif d'électrode positive, électrode positive et batterie secondaire à électrolyte non-aqueux
WO2014058068A1 (fr) * 2012-10-12 2014-04-17 日産自動車株式会社 Substance active d'électrode positive pour pile secondaire à électrolyte non aqueux, procédé de production de substance active d'électrode positive pour pile secondaire à électrolyte non aqueux, et pile secondaire à électrolyte non aqueux

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101469436B1 (ko) 2012-01-17 2014-12-08 주식회사 엘지화학 양극 활물질 및 이를 포함하고 불순물 혹은 스웰링 제어를 위한 리튬 이차전지와 생산성이 향상된 양극 활물질의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100109605A (ko) * 2009-04-01 2010-10-11 주식회사 엘지화학 리튬 이차전지용 양극 활물질
KR20100130522A (ko) * 2009-06-03 2010-12-13 주식회사 엘지화학 리튬 이차전지용 전극 활물질
KR20130125124A (ko) * 2012-05-08 2013-11-18 한국과학기술연구원 리튬이차전지용 나노복합체 양극 활물질을 제조하는 방법
WO2014007358A1 (fr) * 2012-07-06 2014-01-09 住友化学株式会社 Oxyde métallique composite de lithium, matériau actif d'électrode positive, électrode positive et batterie secondaire à électrolyte non-aqueux
WO2014058068A1 (fr) * 2012-10-12 2014-04-17 日産自動車株式会社 Substance active d'électrode positive pour pile secondaire à électrolyte non aqueux, procédé de production de substance active d'électrode positive pour pile secondaire à électrolyte non aqueux, et pile secondaire à électrolyte non aqueux

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