WO2017145888A1 - Particules de matière active d'électrode positive pour batterie rechargeable à électrolyte non aqueux, son procédé de production, et batterie rechargeable à électrolyte non aqueux - Google Patents

Particules de matière active d'électrode positive pour batterie rechargeable à électrolyte non aqueux, son procédé de production, et batterie rechargeable à électrolyte non aqueux Download PDF

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WO2017145888A1
WO2017145888A1 PCT/JP2017/005446 JP2017005446W WO2017145888A1 WO 2017145888 A1 WO2017145888 A1 WO 2017145888A1 JP 2017005446 W JP2017005446 W JP 2017005446W WO 2017145888 A1 WO2017145888 A1 WO 2017145888A1
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positive electrode
active material
electrode active
material particles
secondary battery
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PCT/JP2017/005446
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English (en)
Japanese (ja)
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貴幸 山村
徹也 鹿島
竜太 正木
一路 古賀
修 佐々木
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Ｂａｓｆ戸田バッテリーマテリアルズ合同会社
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Priority to CN201780008852.7A priority Critical patent/CN108604680A/zh
Publication of WO2017145888A1 publication Critical patent/WO2017145888A1/fr

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    • 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
    • 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
    • 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

Definitions

  • the present invention relates to positive electrode active material particles for a non-aqueous electrolyte secondary battery having a layered rock salt structure exhibiting high stability, a method for producing the same, and a non-aqueous electrolyte secondary battery.
  • LiCoO 2 is excellent in that it has a high voltage and a high capacity, but includes a problem of high manufacturing cost due to a small supply amount of cobalt raw material and a problem of environmental safety of a discarded battery.
  • a ternary positive electrode active material particle having a layered rock salt structure that is a solid solution of Ni, Co and Mn having excellent versatility (basic composition: Li (Ni x Co y Mn z ) O 2 -the same is the same)
  • the ternary positive electrode active material particles having a layered rock salt structure are prepared by mixing a Ni compound, a Co compound, a Mn compound and a Li compound at a predetermined ratio, for example, firing in a temperature range of about 700 ° C. to 1000 ° C. Can be obtained.
  • lithium ion secondary batteries using ternary positive electrode active material particles materials that can suppress deterioration of charge / discharge capacity due to repeated charge / discharge and improve battery safety are currently most demanded. .
  • the ternary positive electrode active material particles reduce the amount of oxygen generated in a high voltage region, have excellent filling properties, and have an appropriate size. It has been considered important to suppress instability of the crystal structure.
  • a method of controlling the composition balance, crystallite size and particle size distribution of Li, Ni, Co, and Mn compounds used in the ternary positive electrode active material particles, a method of obtaining powder by controlling the firing temperature, a different element A method for strengthening the bonding strength of crystals by adding selenium, a method for achieving the target by surface treatment, and the like are performed.
  • Patent Document 1 a material which is a high crystal of LiNi 0.33 Co 0.33 Mn 0.33 O 2 is known. Further, a material having high characteristic stability having a feature that a change in lattice volume due to a charge / discharge cycle is small is also known (Patent Document 2). Furthermore, a material that is intended to activate a safety valve of a battery by generating an appropriate gas by adding Ca is also known (Patent Document 3).
  • Patent Document 1 discloses a highly crystalline LiNi 0.33 Co 0.33 Mn 0.33 O 2 , and although there is an explanation thereof, the stability is still insufficient from a practical point of view. There is no sufficient improvement in battery safety.
  • Patent Document 2 the characteristic stability obtained by the small change in the lattice volume due to the charge / discharge cycle is emphasized, but the safety of the battery is not particularly described, and the safety of the battery is sufficiently improved. I doubt it can be improved.
  • security of a battery by taking out gas intentionally is taken, it lacks stability as positive electrode active material itself, and is still insufficient practically. .
  • the present invention has been made in view of the above problems, and an object of the present invention is to obtain positive active material particles for a non-aqueous electrolyte secondary battery having high safety, and such a positive active material.
  • the object is to obtain a highly safe non-aqueous electrolyte secondary battery using particles.
  • the positive electrode active material particles are mainly composed of at least Li, Ni, Co and Mn, and the molar ratio of Li / (Ni + Co + Mn) is 1.09 or more and 1.15 or less.
  • the lithium composite oxide was used.
  • the positive electrode active material particles for a non-aqueous electrolyte secondary battery according to the present invention have a layered rock salt structure and are composed of a lithium composite oxide containing at least Li, Ni, Co, and Mn as main components. It is a material particle, and a molar ratio of Li / (Ni + Co + Mn) is 1.09 or more and 1.15 or less, and the positive electrode active material particle is used for a positive electrode and a nonaqueous electrolyte secondary battery is assembled using Li as a negative electrode.
  • initial charge was performed at a current density of 16 mA / g up to 4.6 V in an environment of 60 ° C.
  • the horizontal axis represents voltage
  • the vertical axis represents dQ / dV which is a value obtained by differentiating the initial charge capacity with voltage.
  • the peak height in the voltage range of 4.3 V to 4.5 V is 100 mAh / g / V to 200 mAh / g / V.
  • the positive electrode active material particles according to the present invention have high stability by having the above-described configuration, and can be used for manufacturing a highly safe battery.
  • the stability of the crystal lattice of the ternary complex oxide, domains of Li 2 MnO 3 is believed to be important, when the Li content is less than the above range, the domain of Li 2 MnO 3 The amount becomes smaller and the stability becomes lower.
  • Li when the composite oxide to Li 2 MnO 3 larger amount when charged to a high voltage such as higher 4.5V, thereby to generate oxygen by decomposition large amount of Li 2 MnO 3.
  • the inside of the battery may be filled with oxygen gas, and the battery may explode due to heat generated by a high voltage.
  • the present inventors have recently assembled a coin cell in which the Li composite oxide having the above-described structure is used as the active material for the positive electrode and the negative electrode is Li, and the 0.2C rate up to 4.6 V in a 60 ° C. environment ( When the initial charge is performed at a current density of 16 mA / g), Li 2 MnO 3 is present in the positive electrode active material in the dQ / dV curve while containing Li in the above molar ratio. We found that the peak value appears very low. That is, the positive electrode active material particle according to the present invention is an active material having high stability in which generation of oxygen from the positive electrode active material is suppressed even when charged to a high voltage. A battery with high performance can be obtained.
  • the positive electrode active material particles according to the present invention have a crystallite size of 400 nm to 1000 nm obtained by Rietveld analysis of X-ray diffraction (XRD diffraction), and an average secondary particle diameter (D50) of 3 ⁇ m to 7 ⁇ m. And (D90-D10) / D50 is preferably in the range of 0.54 to 0.60.
  • the filling property can be improved without reducing the stability of the particles themselves.
  • the method for producing positive electrode active material particles for a non-aqueous electrolyte secondary battery according to the present invention uses a composite compound containing Ni, Co, and Mn as main components as a precursor, and a lithium compound Li / (Ni + Co + Mn) as the precursor.
  • positive electrode active material particles having high stability as described above can be obtained.
  • the precursor has a molar ratio of Ni, Co, and Mn of 1: 1: 1, Ni is mainly present in the state of nickel hydroxide, and Co is It is preferable that it can be confirmed that it exists in the state of cobalt oxyhydroxide or cobalt oxide and, in addition, NiMn 2 O 4 spinel.
  • the precursor preferably has an average secondary particle diameter D50 in the range of 3.5 ⁇ m to 6.5 ⁇ m and a tap density of 1.65 g / ml or more. .
  • the non-aqueous electrolyte secondary battery according to the present invention is characterized by using the positive electrode active material particles for the non-aqueous electrolyte secondary battery described above.
  • the safety can be improved as described above.
  • the positive electrode active material particles for a non-aqueous electrolyte secondary battery according to the present invention are suitable as a positive electrode active material for a non-aqueous electrolyte secondary battery because of high safety.
  • the positive electrode active material particles according to the present embodiment have a layered rock salt structure and are composed of a composite oxide containing at least Li, Ni, Co, and Mn.
  • the molar ratio represented by Li / (Ni + Co + Mn) is 1.09 to 1.15. It is considered that the domain of Li 2 MnO 3 is important for the stability of the crystal lattice of the Li composite oxide. However, when the Li content is less than the above range, the Li composite oxide is randomly included in the Li composite oxide. The amount of Li 2 MnO 3 present is reduced. As a result, since the stability of the Li composite oxide is lowered, the characteristics of the positive electrode active material particles are deteriorated.
  • the molar ratio represented by Li / (Ni + Co + Mn) is 1.10 to 1.15.
  • the positive electrode active material particles are used as a positive electrode, and a nonaqueous electrolyte secondary battery is assembled using Li as a negative electrode.
  • a current density of g a voltage is generated on the horizontal axis, and a graph (dQ / dV curve) indicating dQ / dV, which is a value obtained by differentiating the initial charge capacity with the voltage on the vertical axis.
  • the peak height in the range of 4.3 V to 4.5 V is 100 mAh / g / V to 200 mAh / g / V.
  • the way of viewing the graph means that the battery capacity appears in the voltage range where the peak exists.
  • the present inventors have found that there is a peak between 4.3V and 4.5V in the dQ / dV curve of the above coin cell in various experiments between 4.3V and 4.5V. It was found that Li 2 MnO 3 was suggested to exist in the crystal lattice in the positive electrode active material. That is, it was found that the amount of Li 2 MnO 3 can be quantified by a dQ / dV curve.
  • Li 2 MnO 3 decomposes when charged to a high voltage of 4.5 V or more when the battery is made of Li as the negative electrode. Oxygen is generated. As a result, the inside of the battery is filled with oxygen gas, and the battery may explode due to the heat generation of the positive electrode due to the high voltage.
  • the molar ratio represented by Li / (Ni + Co + Mn) is increased and Li 2 MnO 3 is easily formed, but in the range of 4.3 V to 4.5 V. This means that the dQ / dV peak can be reduced. It is considered that this is because Li 2 MnO 3 having a stacking fault is present in a randomly existing state and crystallinity is increased, resulting in inactivation. By inactivating the activity of Li 2 MnO 3 , it is considered that the generation of oxygen can be suppressed even when a high voltage is applied, and as a result, the possibility of explosion when used as a battery can be minimized.
  • Li 2 MnO 3 by obtaining a positive electrode active material by performing firing at high temperature of 950 ° C. ⁇ 1050 ° C.
  • the present invention is Li 2 MnO 3 was the inactivated It is considered that the layered compound is present in the hexagonal crystal at random so as to provide a pillar effect on the domain of the layered rock salt compound and to be a positive electrode active material capable of exhibiting high stability.
  • the maximum value of the peak appearing between 4.3 V and 4.5 V in the dQ / dV curve is preferably 100 mAh ⁇ g in the positive electrode active material particles according to the present invention.
  • a -1 ⁇ V -1 ⁇ 200mAh ⁇ g -1 ⁇ V -1 more preferably from 120mAh ⁇ g -1 ⁇ V -1 ⁇ 190mAh ⁇ g -1 ⁇ V -1, even more preferably 120 mAh ⁇ g ⁇ 1 ⁇ V ⁇ 1 to 180 mAh ⁇ g ⁇ 1 ⁇ V ⁇ 1 .
  • the positive electrode active material particles in the present embodiment include metal elements such as Mg, Al, Ti, V, Fe, Ga, Sr, Y, Zr, Nb, Mo, Ru, In, Sn, Ta, W, and Bi.
  • metal elements such as Mg, Al, Ti, V, Fe, Ga, Sr, Y, Zr, Nb, Mo, Ru, In, Sn, Ta, W, and Bi.
  • it may be contained in the form of a dope or a coating.
  • the crystallite size obtained by Rietveld analysis of XRD diffraction is preferably 400 nm to 1000 nm. If it is smaller than 400 nm, the crystal growth is insufficient and the safety is deteriorated. If it exceeds 1000 nm, the primary particles become large, cracks and the like enter and become unstable. More preferably, it is 500 nm to 950 nm.
  • the average secondary particle diameter (D50) is 3 ⁇ m to 7 ⁇ m, and (D90-D10) / D50 is in the range of 0.54 to 0.60.
  • (D90-D10) / D50 is an index of the spread of the particle size distribution and indicates the degree of variation in the particle size distribution.
  • the average secondary particle diameter is smaller than 3 ⁇ m, the battery becomes unstable when the electrode active material is used as a battery as aggregated particles.
  • the range of (D90-D10) / D50 is preferably 0.55 to 0.58. It is.
  • a precursor which is a composite compound mainly composed of Ni, Co, and Mn, and a lithium compound are mixed with Li / ( Mixing is performed so that the molar ratio represented by (Ni + Co + Mn) is in the range of 1.09 to 1.15. Thereafter, the mixture is fired at 950 ° C. to 1050 ° C. in an oxidizing atmosphere, whereby a Li composite oxide containing Li, Ni, Co, and Mn can be obtained.
  • the composite compound as a precursor containing at least Ni, Co, and Mn in the present invention can be obtained by coprecipitation of a wet reaction or the like. Specifically, Ni sulfate, Co sulfate, and Mn sulfate are 1.5 mol%.
  • the solution was dissolved so as to become 0.3 mol% of caustic soda, and 0.1 mol of ammonia solution was added dropwise at the same time to cause coprecipitation reaction, and the reaction product was obtained by overflowing, and then washed with water and dried. Obtained.
  • the residual S content was 0.18 wt% or less
  • the Na content was 300 ppm or less
  • the total amount of impurities including moisture was 0.35 wt% or less. If the amount of impurities is large, it may be difficult to synthesize when making a Li composite compound, or the safety may be impaired when making a battery.
  • the precursor is preferably dried to such an extent that NiMnO 3 is not generated.
  • Co may be cobalt oxyhydroxide or cobalt oxide.
  • a spinel compound such as NiMn 2 O 4 may be present.
  • the added metal element may be present in the hydroxide particles or may be present at the outer edge of the hydroxide particles.
  • the metal element that can be added include Mg, Al, Ti, V, Fe, Ga, Sr, Y, Zr, Nb, Mo, Ru, In, Sn, Ta, W, and Bi.
  • the precursor obtained by the wet process preferably has an average secondary particle diameter (D50) in the range of 3.5 ⁇ m to 6.5 ⁇ m and a tap density of 1.65 g / cm 3 or more.
  • D50 average secondary particle diameter
  • the Li compound reacts with the firing step, it can react firmly to the center, and the high crystalline domains of Li 2 MnO 3 can be present at random.
  • positive electrode active material particles having a sufficiently high density can be obtained when the tap density is reacted with a Li compound.
  • the lithium compound used in the present invention is not particularly limited, and various lithium salts can be used.
  • examples thereof include lithium, lithium citrate, lithium fluoride, lithium iodide, lithium lactate, lithium oxalate, lithium phosphate, lithium pyruvate, lithium sulfate, and lithium oxide.
  • lithium carbonate is preferable.
  • the secondary battery manufactured using the positive electrode containing the positive electrode active material particles according to the present embodiment includes the positive electrode, the negative electrode, and an electrolyte.
  • a conductive agent and a binder are added to and mixed with the positive electrode active material particles according to a conventional method.
  • the conductive agent acetylene black, carbon black, graphite, and the like are preferable
  • the binder polytetrafluoroethylene, polyvinylidene fluoride, and the like are preferable.
  • lithium metal lithium / aluminum alloy, lithium / tin alloy, graphite, graphite or the like can be used as the negative electrode active material.
  • the solvent of the electrolytic solution includes at least carbonates such as propylene carbonate (PC) and dimethyl carbonate (DMC), and ethers such as dimethoxyethane.
  • carbonates such as propylene carbonate (PC) and dimethyl carbonate (DMC)
  • ethers such as dimethoxyethane.
  • One kind of organic solvent can be used.
  • At least one lithium salt such as lithium perchlorate (LiClO) or lithium tetrafluoroborate (LiBF 4 ) is dissolved in the above solvent.
  • LiPF 6 lithium hexafluorophosphate
  • LiClO lithium perchlorate
  • LiBF 4 lithium tetrafluoroborate
  • the nonaqueous electrolyte secondary battery manufactured using the positive electrode containing the positive electrode active material particles according to the present embodiment has a high peak of 4.3 V to 4.5 V when an overcharge test is performed by an evaluation method described later. Is 100 mAh ⁇ g ⁇ 1 ⁇ V ⁇ 1 to 200 mAh ⁇ g ⁇ 1 ⁇ V ⁇ 1 .
  • the positive electrode active material particles according to the present invention When the positive electrode active material particles according to the present invention are used, the high crystal domains of Li 2 MnO 3 are randomly present in the crystal lattice of the positive electrode active material by entering the peak height, and the layered rock salt compound In addition, the oxygen release from Li 2 MnO 3 can be significantly reduced, and safety can be ensured.
  • a typical embodiment of the present invention is as follows.
  • composition of the positive electrode active material particles was prepared by dissolving 1.0 g of a sample in 25 ml of a 20% hydrochloric acid solution by heating, transferring to a 100 ml volumetric flask after cooling, preparing pure water by adding pure water, and measuring the ICAP [Optima 8300. Each element was quantified and determined using Perkin Elmer Co., Ltd.].
  • the tap density of the precursor of the positive electrode active material particles 40 g of the sample is weighed, put into a 50 ml measuring cylinder, and the tap density is calculated based on the volume when tapped 1200 times with a tap denser (manufactured by Seishin Enterprise Co., Ltd.) did.
  • Identification of the compound phase of the positive electrode active material particles is performed by an X-ray diffractometer [SmartLab Co., Ltd. manufactured by Rigaku] in a range of 2 ⁇ / ⁇ of 10 ° to 90 ° and 1.2 ° in increments of 0.02 °. / min step scan.
  • the average secondary particle size (D50) and (D90-D10) / D50 values are the volume-based averages measured by the wet laser method using a laser type particle size distribution analyzer Microtrac HRA [manufactured by Nikkiso Co., Ltd.] The particle size.
  • the crystallite size of the positive electrode active material particles was calculated using an X-ray diffractometer [SmartLab (manufactured by Rigaku Corporation)] with a slit of 2/3 degrees and a range of 2 ⁇ / ⁇ of 10 ° to 90 °, 0 Performed at a step of 1.2 ° / min in increments of .02 °. Thereafter, the crystallite size was calculated by performing Rietveld analysis using text data.
  • the coin cell concerning battery evaluation it produced as follows. First, 90% by weight of a composite oxide as a positive electrode active material particle powder according to each of Examples and Comparative Examples described later, 3% by weight of acetylene black as a conductive material, 3% by weight of graphite, and N-methylpyrrolidone as a binder After being mixed with 4% by weight of polyvinylidene fluoride dissolved in, it was applied to an Al metal foil and dried at 120 ° C. This sheet was punched out to 14 mm ⁇ , and then pressure-bonded at 1.5 t / cm 2 was used as the positive electrode.
  • a 2032 type coin cell was manufactured using a solution in which EC and DMC mixed with 1 mol / L LiPF 6 dissolved in a volume ratio of 1: 2 were used as the negative electrode made of metallic lithium having a thickness of 500 ⁇ m punched to 16 mm ⁇ .
  • a graph (dQ / dV curve) showing the dQ / dV which is a value obtained by differentiating the voltage on the horizontal axis and the initial charge capacity on the vertical axis is 4.
  • Initial charge is performed at a charge density of 0.2 C rate (current density 16 mA / g) up to 6 V, and the voltage at that time is plotted on the horizontal axis and dQ / dV which is a value obtained by differentiating the initial charge capacity by voltage is used on the vertical axis.
  • a graph with a voltage ranging from 4.2 V to 4.6 V was created.
  • the composite oxide particles (precursor) were obtained by washing with water and drying (Ni 0.33 Co 0.33 Mn 0.33 ).
  • the precursor has an average secondary particle size of 4.8 ⁇ m, a residual S content of 0.13 wt%, a residual Na content of 187 ppm, a total impurity content of 0.25 wt%, and a tap density of 1.83 g / ml. Met.
  • the precursor and lithium carbonate are mixed in a mortar for 1 hour so that the molar ratio of Li / (Ni + Co + Mn) is 1.11. Obtained. Positive electrode active material particles in which 50 g of the obtained mixture is put in an alumina crucible and kept at 980 ° C. for 5 hours in an oxidizing atmosphere to become Li 1.11 (Ni 0.33 Co 0.33 Mn 0.33 ) O 2. Got.
  • Example 2 Using the precursor of the composite compound synthesized in Example 1 above, the precursor and lithium carbonate were mixed for 1 hour in a mortar so that the Li / (Ni + Co + Mn) molar ratio was 1.12. A mixture was obtained. 50 g of the obtained mixture was put in an alumina crucible, and positive electrode active material particles that became Li 1.12 (Ni 0.33 Co 0.33 Mn 0.33 ) O 2 by holding at 980 ° C. for 5 hours in an air atmosphere were obtained. Obtained.
  • Example 3 Using the precursor of the composite compound synthesized in Example 1 above, the precursor and lithium carbonate were mixed for 1 hour in a mortar so that the Li / (Ni + Co + Mn) molar ratio was 1.14. A mixture was obtained. 50 g of the obtained mixture was placed in an alumina crucible, and positive electrode active material particles that became Li 1.14 (Ni 0.33 Co 0.33 Mn 0.33 ) O 2 by holding at 1000 ° C. for 5 hours in an air atmosphere were obtained. Obtained.
  • Example 4 Using the precursor of the composite compound synthesized in Example 1 above, the precursor and lithium carbonate were mixed for 1 hour in a mortar so that the Li / (Ni + Co + Mn) molar ratio was 1.12. A mixture was obtained. 50 g of the obtained mixture was put in an alumina crucible and held at 990 ° C. for 5 hours in an air atmosphere to obtain positive electrode active material particles that became Li 1.12 (Ni 0.33 Co 0.33 Mn 0.33 ) O 2. Obtained.
  • Example 5 Using the precursor of the composite compound synthesized in Example 1 above, the precursor and lithium carbonate were mixed for 1 hour in a mortar so that the Li / (Ni + Co + Mn) molar ratio was 1.10. A mixture was obtained. 50 g of the obtained mixture was put in an alumina crucible and held at 950 ° C. for 5 hours in an air atmosphere to obtain positive electrode active material particles that became Li 1.10 (Ni 0.33 Co 0.33 Mn 0.33 ) O 2. Obtained.
  • Example 6 Using the precursor of the composite compound synthesized in Example 1 above, the precursor and lithium carbonate were mixed for 1 hour in a mortar so that the Li / (Ni + Co + Mn) molar ratio was 1.13. A mixture was obtained. 50 g of the obtained mixture was put in an alumina crucible and held at 1020 ° C. for 5 hours in an air atmosphere, whereby positive electrode active material particles that became Li 1.13 (Ni 0.33 Co 0.33 Mn 0.33 ) O 2 were obtained. Obtained.
  • Example 7 Using the precursor of the composite compound synthesized in Example 1 above, the precursor and lithium carbonate were mixed for 1 hour in a mortar so that the Li / (Ni + Co + Mn) molar ratio was 1.10. A mixture was obtained. 50 g of the obtained mixture was put in an alumina crucible and kept at 970 ° C. in an air atmosphere for 5 hours to obtain positive electrode active material particles that became Li 1.10 (Ni 0.33 Co 0.33 Mn 0.33 ) O 2. Obtained.
  • Example 8 Using the precursor of the composite compound synthesized in Example 1 above, the precursor and lithium carbonate were mixed for 1 hour in a mortar so that the Li / (Ni + Co + Mn) molar ratio was 1.12. A mixture was obtained. 50 g of the obtained mixture was put in an alumina crucible, and positive electrode active material particles that became Li 1.12 (Ni 0.33 Co 0.33 Mn 0.33 ) O 2 by holding at 950 ° C. for 5 hours in an air atmosphere were obtained. Obtained.
  • Comparative Example 1 Using the precursor of the composite compound synthesized in Example 1 above, the precursor and lithium carbonate were mixed for 1 hour in a mortar so that the Li / (Ni + Co + Mn) molar ratio was 1.16. A mixture was obtained. 50 g of the obtained mixture was put in an alumina crucible and held at 1010 ° C. in an air atmosphere for 5 hours to obtain positive electrode active material particles that became Li 1.16 (Ni 0.33 Co 0.33 Mn 0.33 ) O 2. Obtained.
  • Comparative Example 2 Using the precursor of the composite compound synthesized in Example 1 above, the precursor and lithium carbonate were mixed for 1 hour in a mortar so that the Li / (Ni + Co + Mn) molar ratio was 1.16. A mixture was obtained. 50 g of the obtained mixture was put in an alumina crucible and kept at 970 ° C. in an air atmosphere for 5 hours to obtain positive electrode active material particles that became Li 1.16 (Ni 0.33 Co 0.33 Mn 0.33 ) O 2. Obtained.
  • Comparative Example 3 Using the precursor of the composite compound synthesized in Example 1 above, the precursor and lithium carbonate were mixed for 1 hour in a mortar so that the Li / (Ni + Co + Mn) molar ratio was 1.18. A mixture was obtained. 50 g of the obtained mixture was put in an alumina crucible, and positive electrode active material particles that became Li 1.18 (Ni 0.33 Co 0.33 Mn 0.33 ) O 2 by holding at 980 ° C. in an air atmosphere for 5 hours were obtained. Obtained.
  • Comparative Example 4 Using the precursor of the composite compound synthesized in Example 1 above, the precursor and lithium carbonate were mixed for 1 hour in a mortar so that the Li / (Ni + Co + Mn) molar ratio was 1.12. A mixture was obtained. 50 g of the obtained mixture was put in an alumina crucible, and positive electrode active material particles that became Li 1.12 (Ni 0.33 Co 0.33 Mn 0.33 ) O 2 by holding in an air atmosphere at 930 ° C. for 5 hours were obtained. Obtained.
  • the crystallite size, average secondary particle diameter (D50) and (D90-D10) / D50 were measured according to the above-described methods. Further, a coin cell was prepared using the positive electrode active material particles of each Example and Comparative Example according to the above method, a dQ / dV curve was created in the same manner as described above, and a peak value in the range of 4.3 V to 4.5 V was obtained. Were determined. The results are shown in Table 1 below, and the dQ / dV curves of Example 1, Comparative Example 1 and Comparative Example 3 are shown in FIG. Further, FIG. 2 shows the result of identifying the phase of the precursor compound by performing XRD diffraction on the precursor of the positive electrode active material particles of Example 1.
  • the coin-type battery using the positive electrode active material particles of Example 1 has a peak of 100 mAh / g / V or more and 200 mAh / g in the range of 4.3 V to 4.5 V in the dQ / dV curve described above. It was in the range below / V and showed a low value. On the other hand, in Comparative Example 1 and Comparative Example 3, it can be seen that the peak exceeds 200 mAh / g / V in the range of 4.3 V to 4.5 V in the dQ / dV curve.
  • the molar ratio of Li / (Ni + Co + Mn) is 1.09 or more and 1.15 or less, and the firing temperature is 950 ° C. to 1050 ° C.
  • the peak height in the range of 4.3 V to 4.5 V is 100 mAh / g / V to 200 mAh / g / V in the dQ / dV curve. That is, a battery with high safety can be obtained by using the positive electrode active material particles of Examples 1 to 8.
  • the positive electrode active material particles for a non-aqueous electrolyte secondary battery according to the present invention can be made highly safe when used as a battery, they are suitable as a positive electrode active material for a non-aqueous electrolyte secondary battery.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Les particules de matière active d'électrode positive de l'invention possèdent une structure de sel de roche stratifiée, et comprennent au moins un oxyde complexe de lithium contenant Li, Ni, Co et Mn en tant que composants principaux, le rapport molaire Li/(Ni + Co + Mn) étant situé entre 1,09 et 1,15 inclus. Lorsque les particules de matière active d'électrode positive sont utilisées dans une électrode positive et que Li est utilisé en tant qu'électrode négative pour assembler une batterie rechargeable à électrolyte non aqueux, une charge initiale à 4,6 V est effectuée dans un environnement à 60 °C, et un graphique (courbe dQ/dV) est construit, représentant la tension sur l'axe horizontal et représentant dQ/dV sur l'axe vertical, qui est la valeur de la dérivée, par rapport à la tension, de la capacité de charge initiale, la hauteur d'un pic dans une plage de tensions comprise entre 4,3 V et 4,5 V inclus est située entre 100 mAh/g/V et 200 mAh/g/V.
PCT/JP2017/005446 2016-02-22 2017-02-15 Particules de matière active d'électrode positive pour batterie rechargeable à électrolyte non aqueux, son procédé de production, et batterie rechargeable à électrolyte non aqueux WO2017145888A1 (fr)

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KR102659679B1 (ko) * 2019-04-22 2024-04-19 주식회사 엘지에너지솔루션 배터리의 미분 전압 커브를 결정하기 위한 장치 및 방법과, 상기 장치를 포함하는 배터리 팩
KR20210150863A (ko) * 2020-06-04 2021-12-13 에스케이이노베이션 주식회사 리튬 이차 전지
CN113461058B (zh) * 2021-07-15 2022-09-09 宜宾职业技术学院 无序岩盐结构的正极材料Li1.3Mo0.3V0.4O2的合成方法

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