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WO2013176067A1 - Matériau actif d'électrode positive pour batteries secondaires non aqueuses - Google Patents

Matériau actif d'électrode positive pour batteries secondaires non aqueuses Download PDF

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Publication number
WO2013176067A1
WO2013176067A1 PCT/JP2013/063883 JP2013063883W WO2013176067A1 WO 2013176067 A1 WO2013176067 A1 WO 2013176067A1 JP 2013063883 W JP2013063883 W JP 2013063883W WO 2013176067 A1 WO2013176067 A1 WO 2013176067A1
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Prior art keywords
positive electrode
active material
electrode active
carbon
secondary battery
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English (en)
Japanese (ja)
Inventor
崇 中林
心 ▲高▲橋
寛 北川
将成 織田
豊隆 湯浅
秀一 高野
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Hitachi Ltd
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Hitachi Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode active material for a non-aqueous secondary battery, a manufacturing method thereof, and a positive electrode for a non-aqueous secondary battery and a non-aqueous secondary battery using the positive electrode active material.
  • Lithium ion secondary batteries have a higher energy density than nickel metal hydride batteries and the like, and are used, for example, as power sources for portable electronic devices.
  • application to medium and large-sized applications such as hybrid vehicles, electric vehicles, stationary uninterruptible power supplies, and power leveling has been promoted.
  • the lithium ion secondary battery has a heat generation and ignition accident, and it is necessary to improve safety.
  • a layered oxide positive electrode active material such as LiCoO 2 is used as the positive electrode active material.
  • Li lithium
  • the layered oxide-based positive electrode active material lithium (Li) atoms themselves support the crystal structure, and the structure becomes unstable when Li atoms are desorbed by charging.
  • Li atoms supporting the Li layer are excessively desorbed due to overcharge, the structure collapses and oxygen is released, which may lead to heat generation and ignition.
  • an olivine-based positive electrode active material represented by LiMPO 4 (M is a metal) having an olivine structure that is excellent in safety. Since the olivine-based positive electrode active material has an olivine structure, the structure is stable even when Li atoms are desorbed by charging, and since oxygen and phosphorus are covalently bonded, oxygen is hardly released and safety is high.
  • olivine-based positive electrode active materials include olivine iron-based positive electrode active materials having iron as a constituent element, olivine manganese-based positive electrode active materials having manganese as a constituent element, and the like.
  • the reaction potential is as low as 3.4 V (vs. Li / Li + ), so the energy density is low, and the conductivity and Li ion diffusibility are low.
  • the olivine manganese-based positive electrode active material has attracted attention because of its high reaction potential of 4.1 V (vs. Li / Li + ) and high energy density.
  • the olivine manganese-based positive electrode active material has lower conductivity and Li ion diffusibility than the olivine iron-based positive electrode active material, and therefore has a low capacity.
  • Patent Document 1 a method for increasing the specific surface area and increasing the capacity of the olivine manganese-based positive electrode active material has been proposed in (Patent Document 1) and the like in order to improve the reactivity with the electrolytic solution.
  • Patent Document 2 and the like have proposed a method of increasing the capacity by coating the surface of the olivine-based positive electrode active material with a carbon material, increasing the crystallinity of the carbon layer, and improving the conductivity.
  • Non-patent document 1 when the positive electrode active material is stored at a high temperature (55 ° C.), manganese (Mn) is eluted, and as a result, capacity reduction occurs when charging / discharging at a high temperature (55 ° C.). Has been reported. And (Non-Patent Document 1) reports that by increasing the amount of acetylene black which is a carbon coating source, the elution amount of Mn is suppressed and the decrease in capacity due to charging and discharging during high temperature is suppressed.
  • Patent Document 3 when the olivine iron-based positive electrode active material absorbs water, the metal is easily eluted into the electrolytic solution, and Fe, Mn, etc. eluted into the electrolytic solution are deposited on the negative electrode, and the output resistance is reduced. There is a problem that the life performance is deteriorated due to a significant increase or a decrease in discharge capacity.
  • the zeolite is accommodated in the battery case to remove moisture, and the specific surface area of the positive electrode active material is increased to 5%.
  • a method has been proposed in which the amount of moisture brought in is reduced and the elution of Fe, Mn, and the like is suppressed by setting it to ⁇ 13 m 2 / g.
  • Non-patent Document 1 has a problem that the amount of acetylene black used for carbon coating is excessively 30% by weight and the electrode capacity is lowered. Further, (Non-Patent Document 1) has no description regarding the specific surface area. Furthermore, (Patent Document 3) is an invention related to an olivine iron-based positive electrode active material having higher conductivity and Li ion diffusibility than the olivine manganese-based positive electrode active material, and the properties required for specific surface area and the like are different. Further, since zeolite is stored in the battery case, the space for storing the positive electrode is narrowed, and the battery capacity is reduced. Furthermore, there is no description regarding the crystallinity of the carbon coating layer.
  • the present invention has been made in view of the above points, and is fired at a low temperature in order to obtain a small particle size, and even when the crystallinity of the carbon coating is low, there is little Mn elution during high-temperature storage and high-temperature storage characteristics.
  • An object of the present invention is to provide a positive electrode active material for a non-aqueous secondary battery.
  • the positive electrode active material for a non-aqueous secondary battery according to the present invention has a chemical formula Li A Mn X M 1-X (PO 4 ) B (where 0.8 ⁇ A ⁇ 1.2, 0 8 ⁇ B ⁇ 1.2, 0.3 ⁇ X ⁇ 1, and M is one or more metal atoms selected from Li, Fe, Ni, Co, Ti, Cu, Zn, Mg, and Zr)
  • the lithium composite oxide having a olivine type structure is covered, and a part or the whole of the surface of the lithium composite oxide is coated with a carbon material, and the area ratio of the carbon D band and the carbon G band by Raman measurement ( SD / S G ) is 3.5 or more, the specific surface area S is 13 m 2 / g ⁇ S ⁇ 40 m 2 / g, and the crystallite diameter D is determined from the particle diameter d and the half width obtained by X-ray diffraction.
  • the ratio (d / D) is 1 or more and 1.
  • the positive electrode active material for a non-aqueous secondary battery of the present invention even if the area ratio of the carbon D band and the carbon G band by Raman measurement is 3.5 or more and low crystallinity, Side reactions with certain lithium composite oxides can be suppressed, the amount of Mn elution is small, and high temperature storage characteristics are good. Problems, configurations, and effects other than those described above will be clarified by the following description of the embodiments.
  • FIG. 2 is a scanning electron micrograph of a positive electrode active material in Example 2.
  • FIG. It is a figure which shows the Raman measurement result of the positive electrode active material in Example 2.
  • 2 is a scanning electron micrograph of a positive electrode active material in Comparative Example 1.
  • 4 is a scanning electron micrograph of a positive electrode active material in Comparative Example 2. It is a fragmentary sectional view of one embodiment of the non-aqueous secondary battery of the present invention.
  • the positive electrode active material for a non-aqueous secondary battery of the present invention has a chemical formula Li A Mn X M 1-X (PO 4 ) B (where 0.8 ⁇ A ⁇ 1.2, 0.8 ⁇ B ⁇ 1. 2, 0.3 ⁇ X ⁇ 1, wherein M is one or more metal atoms selected from Li, Fe, Ni, Co, Ti, Cu, Zn, Mg, and Zr) Includes complex oxides.
  • M is one or more metal atoms selected from Li, Fe, Ni, Co, Ti, Cu, Zn, Mg, and Zr
  • M is one or more metal atoms selected from Li, Fe, Ni, Co, Ti, Cu, Zn, Mg, and Zr
  • M is one or more metal atoms selected from Li, Fe, Ni, Co, Ti, Cu, Zn, Mg, and Zr
  • M is one or more metal atoms selected from Li, Fe, Ni, Co, Ti, Cu, Zn, Mg, and Zr
  • M is one or more metal
  • Li and P are 80 mol% or more and 120 mol% or less with respect to Mn and other metal atoms. If Li is in the above range, the lithium composite oxide can have an olivine structure. In particular, Li and P are preferably 100 mol% or more and 120 mol% or less with respect to Mn and other metal atoms. When Li and P are within the above ranges, generation of metal as a by-product can be prevented. Therefore, precipitation of the metal foreign material in a negative electrode can be prevented, a short circuit can be prevented and safety can be improved.
  • the positive electrode active material has a ratio (d / D) of a particle diameter (denoted as d) to a crystallite diameter (denoted as D) obtained from a half width obtained by X-ray diffraction is 1 or more and 1.35 or less. is there.
  • d / D is 1.35 or less
  • the crystallinity of the core material Li A Mn X M 1-X PO 4 is good, and since there are few defects, the diffusibility of Li ions increases, resulting in high capacity. It is done.
  • the crystallite diameter D does not become larger than the particle diameter d and coincides with the particle diameter d when the crystallite diameter D is maximum, so the minimum value of d / D is 1. Therefore, the closer d / D is to 1, the better the crystallinity.
  • the particle diameter d is the result of observing a randomly extracted positive electrode active material using a scanning electron microscope (SEM) or a transmission electron microscope (TEM) and observing three or more randomly selected fields.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the average particle diameter is an average value obtained from all the particle diameters extracted from the order of 40 particle diameters in each visual field extracted from the order in which the particle diameters are close to the median value.
  • the crystallite diameter D is a physical property value obtained from the half width in the X-ray diffraction (XRD) measurement result.
  • the XRD measurement is performed by the concentration method, the X-ray is CuK ⁇ ray, and the output is 40 kV and 40 mA. Measurement was performed under the condition that the step width was 0.03 °, and the measurement time per step was 15 seconds. The measurement data was smoothed by the Savitzky-Goley method, and then the background and K ⁇ 2 line were removed. ) Find the full width at half maximum ⁇ exp of the peak (space group is Pmna). Further, a standard Si sample (NIST standard sample 640d) was measured under the same apparatus and under the same conditions, and a half width ⁇ i of the peak was obtained.
  • ⁇ is the wavelength of the X-ray source
  • ⁇ is the reflection angle
  • K is a Scherrer constant
  • K 0.9.
  • the positive electrode active material of the present invention a part or the whole of the surface of the lithium composite oxide is coated with a carbon material, and the area of the carbon D band (S D ) and the area of the carbon G band (S G ) by Raman measurement.
  • the area ratio (S D / S G ) is 3.5 or more.
  • the carbon material becomes low crystalline, and the area ratio (S D / S G ) is 3.5 or more.
  • the coating with the carbon material does not necessarily have to be a carbon material, and a part thereof may be a material other than the carbon material.
  • the carbon content of the positive electrode active material is preferably 0.5% by weight or more and less than 30% by weight.
  • the carbon content is more preferably 1% by weight or more.
  • conductivity is improved and rate characteristics are improved.
  • the carbon content is more than 30% by weight, the battery capacity decreases.
  • the carbon content is more preferably 5% by weight or less. When the carbon content is 5% by weight or less, the decrease in electrode capacity can be more effectively suppressed.
  • the specific surface area S of the positive electrode active material is 13 m 2 / g ⁇ S ⁇ 40 m 2 / g.
  • the specific surface area S is larger than 13 m 2 / g, the reaction field between the positive electrode active material and the electrolyte is widened, the resistance is lowered, and the capacity is increased.
  • the specific surface area S is 40 m 2 / g or less, side reaction between hydrogen fluoride in the electrolyte and Li A Mn X M 1-X (PO 4 ) B as a core material can be suppressed, and Mn and Elution of metal and generation of a resistance layer can be suppressed, and high-temperature storage characteristics are improved.
  • the particle size of the positive electrode active material is preferably 10 nm or more and 500 nm or less.
  • the particle diameter d is less than 10 nm, the bulk density is high and the capacity per volume is reduced.
  • the particle diameter d exceeds 500 nm, the Li ion diffusion path becomes longer, resulting in higher resistance and lower capacity.
  • the particle diameter d is more preferably 30 nm or more and 50 nm or less.
  • a capacity of 30 nm or more and 50 nm or less results in a high capacity and good high-temperature storage characteristics.
  • the positive electrode active material may be made into secondary particles by granulation or the like.
  • the positive electrode active material for a non-aqueous secondary battery as described above includes a step of mixing raw materials of a lithium composite oxide, a step of pre-baking the mixed raw materials, and a carbon source mixed with a pre-fired body obtained by pre-baking And a method including a step of subjecting the mixed calcined body and the carbon source to main firing.
  • the firing temperature in the main firing step is preferably not less than the crystallization temperature of the lithium composite oxide and not more than a temperature obtained by adding 400 ° C. to the crystallization temperature.
  • the carbon source to be mixed with the calcined product can be appropriately selected from sucrose, lactose, maltose, trehalose, turanose, cellobiose, glucose, glycogen, starch, cellulose, dextrin and other sugars, pitch-based carbon materials, and the like.
  • the amount to be mixed can be determined in consideration of the above-described carbon content.
  • a positive electrode for a non-aqueous secondary battery having a high capacity and good high-temperature storage characteristics can be produced.
  • the positive electrode can be produced by a conventionally known method. Specifically, for example, the above positive electrode active material, a conductive material and a binder are kneaded, and a dispersion solvent such as N-methylpyrrolidone is added. A positive electrode mixture slurry is prepared by appropriately diluting. The positive electrode mixture slurry is applied to the surface of an aluminum foil or the like used as a positive electrode current collector, and then dried and pressed with a pressure roller to form a positive electrode mixture layer on the current collector to form a positive electrode. Make it.
  • the binder is not particularly limited, but polyvinylidene fluoride, polyacrylonitrile, styrene-butadiene rubber and the like are applicable.
  • the conductive material for example, carbon materials such as graphite, acetylene black, carbon black, carbon fiber, and metal carbide can be applied, and each can be used alone or in admixture of two or more.
  • Non-aqueous secondary battery By using the positive electrode, a non-aqueous secondary battery having a high capacity and good high-temperature storage characteristics can be obtained.
  • a configuration of the non-aqueous secondary battery a conventionally known general configuration can be adopted.
  • FIG. 5 shows a partial cross-sectional view of an embodiment of a non-aqueous secondary battery according to the present invention.
  • a separator 7 is disposed between the positive electrode 5 and the negative electrode 6.
  • the positive electrode 5, the negative electrode 6 and the separator 7 are wound and sealed together with a non-aqueous electrolyte (not shown) in a battery can 10 made of stainless steel or aluminum.
  • the positive electrode 5 is provided with a positive electrode lead 8, and the negative electrode 6 is provided with a negative electrode lead 9, each configured to extract current.
  • Insulating plates 12 are respectively provided between the positive electrode 5 and the negative electrode lead 9 and between the negative electrode 6 and the positive electrode lead 8. Further, between the battery can 10 in contact with the negative electrode lead 9 and the sealing lid portion 13 in contact with the positive electrode lead 8, a packing for separating the positive electrode and the negative electrode as well as preventing leakage of the electrolyte. 11 is provided.
  • LiPF 6 is contained in the electrolytic solution.
  • the positive electrode active material for a non-aqueous secondary battery of the present invention high temperature storage characteristics are improved even when LiPF 6 is contained in the electrolytic solution, and good output characteristics resulting from LiPF 6 can be obtained. That is, it is possible to obtain a secondary battery having a high capacity, good high-temperature storage characteristics, and good output characteristics.
  • its content is preferably 0.01 to 5 mol% in the electrolytic solution.
  • Example 1 Iron citrate (FeC 6 H 5 O 7 .nH 2 O) and citric acid monohydrate (C 6 H 8 O 7 .H 2 O) were dissolved in pure water. To the obtained solution, a solution in which manganese acetate tetrahydrate (Mn (CH 3 COO) 2 .4H 2 O) was dissolved in pure water was added. Further, lithium dihydrogen phosphate and an aqueous lithium acetate solution were added to the pure water. The dissolved solution was added. The obtained solution was dried using a spray dryer to obtain a raw material powder. This raw material powder was temporarily fired at 440 ° C. for 10 hours to obtain a temporarily fired body.
  • Mn (CH 3 COO) 2 .4H 2 O manganese acetate tetrahydrate
  • lithium dihydrogen phosphate and an aqueous lithium acetate solution were added to the pure water. The dissolved solution was added.
  • the obtained solution was dried using a spray dryer to obtain a raw material powder. This
  • the obtained positive electrode active material was measured by X-ray diffraction.
  • the core material was a lithium composite oxide having an olivine structure represented by the chemical formula LiMnFePO 4. When the Raman measurement was performed, the surface was coated with a carbon material. It was.
  • the carbon content of the positive electrode active material was 2.0% by weight.
  • the specific surface area of the positive electrode active material was 15.0 m 2 / g as measured using a catalyst analyzer BEL-CAT (manufactured by Nippon Bell Co., Ltd.).
  • the carbon coating amount per surface area was 1.3 mg / m 2 .
  • the area ratio (S D / S G ) of the carbon D band and the carbon G band by Raman measurement was 4.4.
  • the particle diameter d of the positive electrode active material is 45 nm
  • the crystallite diameter D is 38 nm
  • the ratio of the particle diameter d to the crystallite diameter D (d / G) was 1.2.
  • Example 2 A positive electrode active material was prepared in the same manner as in Example 1 except that 7 parts by weight of sucrose was used.
  • FIG. 1 shows an SEM image of the positive electrode active material 1.
  • the obtained positive electrode active material was subjected to elemental analysis by high frequency inductively coupled plasma optical emission spectrometry (ICP-AES). As a result, the Mn content was 27% by weight and the Fe content was 6.5% by weight.
  • the carbon content was 2.0% by weight.
  • the particle diameter d was 39 nm
  • the crystallite diameter D was 32 nm
  • d / D was 1.2.
  • the specific surface area was 23.1 m 2 / g as measured using a catalyst analyzer BEL-CAT (manufactured by Nippon Bell Co., Ltd.).
  • the carbon coating amount per surface area was 0.9 mg / m 2 .
  • the Raman measurement result of a positive electrode active material is shown.
  • the area ratio (S D / S G ) of the carbon D band 3 and the carbon G band 2 by Raman measurement was 4.4.
  • Example 3 A positive electrode active material was produced in the same manner as in Example 1 except that 10 parts by weight of sucrose was used. The carbon content was 2.0% by weight. The specific surface area of the positive electrode active material was 36.1 m 2 / g. The carbon coating amount per surface area was 0.9 mg / m 2 . Further, the area ratio (S D / S G ) of the carbon D band and the carbon G band by Raman measurement was 4.4. Furthermore, the particle diameter d of the positive electrode active material was 35 nm, the crystallite diameter D determined from the half width obtained by X-ray diffraction was 30 nm, and d / D was 1.2.
  • FIG. 3 shows an SEM image of the positive electrode active material 1.
  • the carbon content was 1.9% by weight.
  • the specific surface area was 6.2 m 2 / g.
  • the carbon coating amount per surface area was 3.0 mg / m 2 .
  • the area ratio (S D / S G ) of the carbon D band and the carbon G band by Raman measurement was 4.4.
  • FIG. 4 shows an SEM image of the positive electrode active material 1.
  • the carbon content was 3.8% by weight.
  • the specific surface area was 41.9 m 2 / g.
  • the carbon coating amount per surface area was 0.9 mg / m 2 .
  • the area ratio (S D / S G ) of the carbon D band and the carbon G band by Raman measurement was 4.4.
  • Example 3 A positive electrode active material was produced in the same manner as in Example 1 except that the atmosphere during the pre-baking was argon and sucrose was not added after the pre-baking.
  • the obtained positive electrode active material had a particle diameter d of 35 nm, a crystallite diameter D of 22 nm, and d / D of 1.6.
  • the carbon content was 6.3% by weight.
  • Example 4 A positive electrode active material was produced in the same manner as in Example 2 except that the main firing temperature was 900 ° C.
  • the particle diameter d of the obtained positive electrode active material was 150 nm.
  • the area ratio (S D / S G ) of the carbon D band and the carbon G band by Raman measurement was 3.1.
  • a positive electrode fabrication method 82.5 parts by weight of the positive electrode active material prepared in Examples 1 to 3 and Comparative Examples 1 to 4, 10 parts by weight of acetylene black (Denka Black (registered trademark) manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive material, and binder A mixture of 7.5 parts by weight of modified polyacrylonitrile dissolved in N-methylpyrrolidone was kneaded to prepare a positive electrode mixture slurry. The obtained positive electrode mixture slurry was uniformly coated on an aluminum foil using a coating machine. After drying at 80 ° C. in the air, a positive electrode was obtained by punching and pressing to ⁇ 15 mm.
  • acetylene black Denki Kagaku Kogyo Co., Ltd.
  • Electrode characteristics were evaluated for each positive electrode produced as described above.
  • the electrolytic solution vinylene carbonate was added to a mixed solvent of ethylene carbonate and ethyl methyl carbonate, and 1M LiPF 6 was added thereto. Moreover, lithium metal was used for the negative electrode.
  • Mn elution evaluation and maintenance rate evaluation With respect to the positive electrodes using the positive electrode active materials of Examples 1 to 3, Comparative Example 1 and Comparative Example 2, the Mn elution amount was evaluated. First, charge / discharge is performed for 3 cycles under the same conditions as in the charge / discharge test. Next, after washing the positive electrode with dimethyl carbonate, it is immersed in 5 ml of an electrolytic solution. And it preserve
  • the area ratio (S D / S G ) of the carbon D band and the carbon G band by Raman measurement of the positive electrode active material is 4.4, and the specific surface area of the positive electrode active material is larger than 13 m 2 / g as shown in Table 1.
  • the initial discharge capacity is as high as 131 Ah / kg or more
  • the Mn elution amount after high-temperature storage is as small as 2.2% or less
  • the discharge capacity maintenance rate is also 97 Since it is as high as% or more, high capacity and high temperature storage characteristics are good.
  • Comparative Example 1 in which the positive electrode active material has a specific surface area of 13 m 2 / g or less has an initial discharge capacity as low as 110 Ah / kg. Further, in Comparative Example 2 having a specific surface area larger than 40 m 2 / g, the elution amount of Mn is as high as 4.9%, the discharge capacity retention rate after high-temperature storage is as low as 89%, and high-temperature storage characteristics are poor. I understood. Further, since d / D is 1.6, Comparative Example 3 in which the core material has low crystallinity has an initial discharge capacity as low as 110 Ah / kg. Further, in Comparative Example 4 in which the area ratio (S D / S G ) of the carbon D band and the carbon G band by Raman measurement is 3.1, the particle diameter is enlarged and the initial discharge capacity is as low as 121 Ah / kg.
  • the positive electrode active material of the present invention has a high capacity and good high-temperature storage characteristics.
  • the positive electrode for a non-aqueous secondary battery of the present invention is expected to be applied to a mobile body and a stationary power storage power source that require a large-capacity large-sized lithium ion secondary battery.

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PCT/JP2013/063883 2012-05-24 2013-05-20 Matériau actif d'électrode positive pour batteries secondaires non aqueuses Ceased WO2013176067A1 (fr)

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JP2012118767A JP2013246936A (ja) 2012-05-24 2012-05-24 非水系二次電池用正極活物質
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Cited By (8)

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CN105406045A (zh) * 2015-12-21 2016-03-16 李梦思 一种复合锂离子电池正极材料及其制备方法
WO2016182044A1 (fr) * 2015-05-14 2016-11-17 株式会社村田製作所 Cellule secondaire à électrolyte non aqueux
WO2017203223A1 (fr) * 2016-05-23 2017-11-30 Johnson Matthey Public Limited Company Matériaux de cathode pour pile
EP3614466A1 (fr) * 2018-08-21 2020-02-26 Sumitomo Osaka Cement Co., Ltd. Matériau de cathode pour batterie secondaire lithium-ion, électrode et batterie secondaire lithium-ion le comprenant
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WO2017203223A1 (fr) * 2016-05-23 2017-11-30 Johnson Matthey Public Limited Company Matériaux de cathode pour pile
CN112189268B (zh) * 2018-06-27 2024-04-26 三星电子株式会社 锂离子电池及其阴极活性材料
CN112189268A (zh) * 2018-06-27 2021-01-05 三星电子株式会社 锂离子电池及其阴极活性材料
EP3614466A1 (fr) * 2018-08-21 2020-02-26 Sumitomo Osaka Cement Co., Ltd. Matériau de cathode pour batterie secondaire lithium-ion, électrode et batterie secondaire lithium-ion le comprenant
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JP2024527744A (ja) * 2022-06-17 2024-07-26 寧徳時代新能源科技股▲分▼有限公司 正極活物質及びその製造方法、正極極板、二次電池、電池モジュール、電池パックと電力消費装置
JP7661605B2 (ja) 2022-06-17 2025-04-14 香港時代新能源科技有限公司 正極活物質及びその製造方法、正極極板、二次電池、電池モジュール、電池パックと電力消費装置
JP7668417B2 (ja) 2022-06-17 2025-04-24 香港時代新能源科技有限公司 正極活物質及び製造方法、正極極板、二次電池、電池モジュール、電池パック及び電力消費装置

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