WO2013065513A1 - Matériau actif d'électrode positive d'accumulateur à électrolyte non aqueux, et accumulateur à électrolyte non aqueux - Google Patents

Matériau actif d'électrode positive d'accumulateur à électrolyte non aqueux, et accumulateur à électrolyte non aqueux Download PDF

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WO2013065513A1
WO2013065513A1 PCT/JP2012/077231 JP2012077231W WO2013065513A1 WO 2013065513 A1 WO2013065513 A1 WO 2013065513A1 JP 2012077231 W JP2012077231 W JP 2012077231W WO 2013065513 A1 WO2013065513 A1 WO 2013065513A1
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oxide
positive electrode
electrolyte secondary
active material
secondary battery
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PCT/JP2012/077231
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English (en)
Japanese (ja)
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デニス ヤウワイ ユ
柳田　勝功
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三洋電機株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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 positive electrode active material for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery.
  • non-aqueous electrolyte secondary batteries have been widely used as power sources for electronic devices and the like.
  • a carbon material such as graphite is used as the negative electrode active material of the non-aqueous electrolyte secondary battery.
  • graphite is used as the negative electrode active material of the non-aqueous electrolyte secondary battery.
  • a negative electrode active material that can replace the graphite and that can further increase the battery capacity has been conducted.
  • negative electrode active materials Materials that can be alloyed with lithium such as silicon have been studied as negative electrode active materials that can replace graphite.
  • the negative electrode active material made of a material alloyed with lithium generally has a large irreversible capacity, and the charge / discharge cycle is likely to decrease.
  • Patent Document 1 as a positive electrode active material, a first Li-containing transition metal composite oxide as a main component and a second Li-containing transition metal composite as a subcomponent are used. And using Li (Li x Mn 2x Co 1-3x ) O 2 (where 0 ⁇ x ⁇ 1/3) as the second Li-containing transition metal composite oxide.
  • Li (Li x Mn 2x Co 1-3x ) O 2 where 0 ⁇ x ⁇ 1/3) as the second Li-containing transition metal composite oxide.
  • Patent Document 1 when an irreversible capacity is given to the negative electrode active material, it is necessary to increase the initial charge end voltage of the battery. However, when the initial charge end voltage of the battery is increased, the nonaqueous electrolyte may be decomposed, and the charge / discharge cycle characteristics of the battery may be deteriorated.
  • the present invention does not require a high initial charge end voltage of a non-aqueous electrolyte secondary battery, and can impart excellent charge / discharge cycle characteristics to the non-aqueous electrolyte secondary battery.
  • the main purpose is to provide active materials.
  • the positive electrode active material of the nonaqueous electrolyte secondary battery of the present invention includes a first oxide and a second oxide.
  • the first oxide has a general formula: LiCo z M 1-z O 2 [wherein z is 0.3 ⁇ z ⁇ 1 and M is at least one of Ni and Mn. ] It consists of a compound represented by this.
  • the second oxide is a non-aqueous electrolyte secondary battery using a positive electrode using the second oxide as a positive electrode active material and a negative electrode made of lithium metal, and the positive electrode potential is 3.0 V (vs. Li / Li + ) To 4.3 V (vs.
  • the initial charge capacity of the nonaqueous electrolyte secondary battery is that the first oxide is used as the positive electrode active material instead of the second oxide.
  • the initial charge capacity of the non-aqueous electrolyte secondary battery is larger than the initial charge capacity of the non-aqueous electrolyte secondary battery using the positive electrode, and the first oxide is used as the positive electrode active material instead of the second oxide.
  • the lithium-containing metal oxide is lower than the initial charge / discharge efficiency of the nonaqueous electrolyte secondary battery using the positive electrode.
  • the nonaqueous electrolyte secondary battery of the present invention includes a positive electrode including the positive electrode active material, a negative electrode, a nonaqueous electrolyte, and a separator.
  • the nonaqueous electrolyte secondary battery can provide excellent charge / discharge cycle characteristics to the nonaqueous electrolyte secondary battery.
  • the positive electrode active material can be provided.
  • FIG. 1 is a schematic cross-sectional view of a nonaqueous electrolyte secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram of a three-electrode test cell using the positive electrodes prepared in Examples, Comparative Examples and Reference Examples as working electrodes.
  • the nonaqueous electrolyte secondary battery 1 includes a battery container 17.
  • the battery case 17 is a cylindrical shape.
  • the shape of the battery container is not limited to a cylindrical shape.
  • the shape of the battery container may be, for example, a flat shape.
  • an electrode body 10 impregnated with a nonaqueous electrolyte is accommodated.
  • non-aqueous electrolyte for example, a known non-aqueous electrolyte can be used.
  • the non-aqueous electrolyte includes a solute, a non-aqueous solvent, and the like.
  • LiXF y As the solute of the nonaqueous electrolyte, for example, LiXF y (wherein X is P, As, Sb, B, Bi, Al, Ga or In, and y is 6 when X is P, As or Sb)
  • X is B, Bi, the y when Al, Ga or in, a 4
  • LiPF 6 LiBF 4 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 and the like are preferable.
  • the nonaqueous electrolyte may contain one type of solute or may contain a plurality of types of solutes.
  • non-aqueous solvent for the non-aqueous electrolyte examples include cyclic carbonate, chain carbonate, or a mixed solvent of cyclic carbonate and chain carbonate.
  • cyclic carbonate examples include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, and the like.
  • chain carbonate examples include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and the like.
  • a mixed solvent of a cyclic carbonate and a chain carbonate is preferably used as a non-aqueous solvent having a low viscosity, a low melting point, and a high lithium ion conductivity.
  • the mixing ratio of cyclic carbonate and chain carbonate should be in the range of 1: 9 to 5: 5 by volume ratio. Is preferred.
  • the non-aqueous solvent may be a mixed solvent of a cyclic carbonate and an ether solvent such as 1,2-dimetaxethane and 1,2-diethoxyethane.
  • an ionic liquid can be used as a nonaqueous solvent for the nonaqueous electrolyte.
  • the cation species and anion species of the ionic liquid are not particularly limited. From the viewpoint of low viscosity, electrochemical stability, and hydrophobicity, for example, a pyridinium cation, an imidazolium cation, or a quaternary ammonium cation is preferably used as the cation.
  • an ionic liquid containing a fluorine-containing imide anion is preferably used as the anion.
  • the non-aqueous electrolyte may be a gel polymer electrolyte obtained by impregnating a polymer electrolyte such as polyethylene oxide or polyacrylonitrile with an electrolytic solution, or an inorganic solid electrolyte such as LiI or Li 3 N.
  • the electrode body 10 is formed by winding a negative electrode 11, a positive electrode 12, and a separator 16 disposed between the negative electrode 11 and the positive electrode 12.
  • the separator 16 is not particularly limited as long as it can suppress a short circuit due to contact between the negative electrode 11 and the positive electrode 12 and can impregnate a nonaqueous electrolyte to obtain lithium ion conductivity.
  • the separator 16 can be formed of a resin porous film.
  • the resin porous film include a polypropylene or polyethylene porous film, a laminate of a polypropylene porous film and a polyethylene porous film, and the like.
  • the negative electrode 11 has a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector.
  • the negative electrode current collector can be composed of, for example, a foil made of a metal such as Cu or an alloy containing a metal such as Cu.
  • the negative electrode active material layer contains a negative electrode active material.
  • the negative electrode active material is not particularly limited as long as it can reversibly store and release lithium.
  • Examples of the negative electrode active material include a carbon material, a material alloyed with lithium, and a metal oxide such as tin oxide.
  • Specific examples of the carbon material include natural graphite, artificial graphite, mesophase pitch-based carbon fiber (MCF), mesocarbon microbeads (MCMB), coke, hard carbon, fullerene, and carbon nanotube.
  • Examples of the material to be alloyed with lithium include one or more metals selected from the group consisting of silicon, germanium, tin and aluminum, or one or more types selected from the group consisting of silicon, germanium, tin and aluminum. The thing which consists of an alloy containing a metal is mentioned.
  • the negative electrode active material layer may contain a known carbon conductive agent such as graphite and a known binder such as sodium carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR).
  • a known carbon conductive agent such as graphite
  • a known binder such as sodium carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR).
  • the positive electrode 12 has a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector.
  • the positive electrode current collector can be made of, for example, a metal such as Al or an alloy containing a metal such as Al.
  • the positive electrode active material layer includes a positive electrode active material.
  • the positive electrode active material layer may contain appropriate materials such as a binder and a conductive agent in addition to the positive electrode active material.
  • a binder preferably used include, for example, polyvinylidene fluoride.
  • a conductive agent preferably used include carbon materials such as graphite and acetylene black.
  • the positive electrode active material includes a first oxide and a second oxide.
  • the first oxide has a general formula: LiCo z M 1-z O 2 [wherein z is 0.3 ⁇ z ⁇ 1 and M is at least one of Ni and Mn. ] It consists of a compound represented by this.
  • the first oxide preferably has a crystal structure belonging to the space group R-3m.
  • the first oxide is preferably lithium cobalt oxide (LiCoO 2 ).
  • the lithium cobalt oxide preferably has a layered structure.
  • the first oxide is preferably contained in the positive electrode active material by about 60% by mass to 95% by mass, and more preferably by about 70% by mass to 90% by mass.
  • the second oxide is a non-aqueous electrolyte secondary battery using a positive electrode using the second oxide as a positive electrode active material and a negative electrode made of lithium metal, and the positive electrode potential is 3.0 V (vs. Li / Li + ) To 4.3 V (vs. Li / Li + ), the initial charge capacity of the nonaqueous electrolyte secondary battery is that the first oxide is used as the positive electrode active material instead of the second oxide.
  • the initial charge capacity of the non-aqueous electrolyte secondary battery is larger than the initial charge capacity of the non-aqueous electrolyte secondary battery using the positive electrode, and the first oxide is used as the positive electrode active material instead of the second oxide.
  • the second oxide is a non-aqueous electrolyte secondary battery using a positive electrode using the second oxide as a positive electrode active material and a negative electrode made of lithium metal, and the potential of the positive electrode is 3.0 V (vs.
  • the initial state of the non-aqueous electrolyte secondary battery is The charge / discharge efficiency is positive when the first oxide is used as the positive electrode active material instead of the second oxide. Aqueous lower than the initial charge-discharge efficiency of electrolyte secondary battery using a lithium-containing metal oxide.
  • the second oxide is a non-aqueous electrolyte secondary battery using a positive electrode using the second oxide as a positive electrode active material and a negative electrode made of lithium metal, and the positive electrode potential is 3.0 V (vs. Li / Li + ) To 4.3 V (vs. Li / Li + ), the initial charge capacity of the nonaqueous electrolyte secondary battery exceeds 170 mAh / g, and the initial charge of the nonaqueous electrolyte secondary battery is A lithium-containing metal oxide that has a discharge efficiency of less than 70% is preferable.
  • the initial charge capacity is more preferably over 180 mAh / g.
  • the initial charge / discharge efficiency is more preferably less than 60%.
  • the surface area of the second oxide is preferably greater than 3 m 2 / g and more preferably greater than 7 m 2 / g in terms of BET specific surface area.
  • the surface area of the second oxide is a BET specific surface area and usually does not exceed 50 m 2 / g.
  • the second oxide is preferably contained in the positive electrode active material by about 5% by mass to 40% by mass, and more preferably by about 10% by mass to 30% by mass.
  • the second oxide is preferably a lithium-containing manganese oxide, and more preferably lithium manganate (LiMnO 2 ).
  • LiMnO 2 preferably has a crystal structure belonging to the space group c2 / m or a crystal structure belonging to the space group Pmnm.
  • the negative electrode active material made of a material that is alloyed with lithium such as silicon generally has a problem that the irreversible capacity is large and the charge / discharge cycle tends to decrease.
  • Patent Document 1 it is necessary to increase the initial charge end voltage of the battery when providing the irreversible capacity to the negative electrode active material. If the initial charge end voltage of the battery is increased, the nonaqueous electrolyte may be decomposed, and the charge / discharge cycle characteristics of the battery may deteriorate.
  • the positive electrode active material according to the present embodiment includes the first oxide and the second oxide. According to the positive electrode active material according to the present embodiment, it is not necessary to set the initial charge end voltage of the nonaqueous electrolyte secondary battery 1 high, and excellent charge / discharge cycle characteristics are imparted to the nonaqueous electrolyte secondary battery 1. obtain.
  • the reason for this can be considered as follows. That is, the second oxide of the positive electrode active material according to the present embodiment is a non-aqueous electrolyte secondary battery using a positive electrode using the second oxide as a positive electrode active material and a negative electrode made of lithium metal, and the potential of the positive electrode. Is charged from 3.0 V (vs. Li / Li + ) to 4.3 V (vs.
  • the initial charge / discharge efficiency of the nonaqueous electrolyte secondary battery is Instead, it comprises a lithium-containing metal oxide that is lower than the initial charge / discharge efficiency of the nonaqueous electrolyte secondary battery using the positive electrode using the first oxide as the positive electrode active material. For this reason, in the initial charge / discharge process of the nonaqueous electrolyte secondary battery 1, a sufficient amount of irreversible capacity can be given from the positive electrode active material to the negative electrode active material, and the negative electrode active material is prevented from being overdischarged. be able to.
  • the lithium-containing metal oxide constituting the second oxide is a non-aqueous electrolyte secondary battery using a positive electrode using the second oxide as a positive electrode active material and a negative electrode made of lithium metal.
  • the initial charge capacity of the non-aqueous electrolyte secondary battery is replaced with the second oxide.
  • the initial charge capacity of the nonaqueous electrolyte secondary battery using the positive electrode using the first oxide as the positive electrode active material is larger. For this reason, it is possible to give a sufficient amount of irreversible capacity to the negative electrode active material in the initial charge / discharge process while suppressing a decrease in the initial charge capacity of the nonaqueous electrolyte secondary battery 1.
  • a nonaqueous electrolyte using a positive electrode using the second oxide as a positive electrode active material and a negative electrode made of lithium metal in addition to the first oxide, a nonaqueous electrolyte using a positive electrode using the second oxide as a positive electrode active material and a negative electrode made of lithium metal.
  • the initial charge / discharge of the nonaqueous electrolyte secondary battery A second oxide composed of a lithium-containing metal oxide whose efficiency is lower than the initial charge / discharge efficiency of a nonaqueous electrolyte secondary battery using a positive electrode in which the first oxide is used as the positive electrode active material instead of the second oxide.
  • the negative electrode active material By including the negative electrode active material, a sufficient amount of irreversible capacity can be imparted to the negative electrode active material even when the end-of-charge voltage is set low when the nonaqueous electrolyte secondary battery 1 is initially charged. Can be made difficult.
  • the negative electrode active material is a material that is alloyed with lithium, the charge / discharge cycle is likely to be reduced. Without setting it high, the non-aqueous electrolyte secondary battery 1 can be provided with excellent charge / discharge cycle characteristics.
  • the non-aqueous electrolyte secondary battery in which the second oxide is a positive electrode using the second oxide as a positive electrode active material and a negative electrode made of lithium metal has a positive electrode potential of 3.0 V (vs. Li / Li + ) To 4.3 V (vs. Li / Li + ), the initial charge capacity of the nonaqueous electrolyte secondary battery exceeds 170 mAh / g, and the initial charge of the nonaqueous electrolyte secondary battery is When the discharge efficiency is a lithium-containing metal oxide that is less than 70%, a sufficient amount from the positive electrode active material to the negative electrode active material even if the initial charge end voltage of the nonaqueous electrolyte secondary battery 1 is set lower. Of irreversible capacity.
  • the surface area of the second oxide exceeds 3 m 2 / g in terms of the BET specific surface area, a sufficient amount of irreversible capacity can be imparted to the negative electrode active material even if the amount of the second oxide in the positive electrode active material is reduced.
  • the charge / discharge cycle of the non-aqueous electrolyte secondary battery 1 can be improved.
  • the positive electrode active material in the nonaqueous electrolyte secondary battery 1, by using the positive electrode active material according to the present embodiment, a sufficient amount for the negative electrode active material even when the charge end potential of the positive electrode is 4.3 V (vs. Li / Li + ) or less. Of irreversible capacity.
  • Example 1 [Positive electrode active material] ⁇ First oxide> A predetermined amount of Li 2 CO 3 and Co 3 O 4 were mixed and held in air at 900 ° C. for 10 hours to obtain LiCoO 2 as the first oxide. When the obtained LiCoO 2 was analyzed by an X-ray diffraction method, the LiCoO 2 had a layered structure. LiCoO 2 had a crystal structure belonging to the space group R-3m.
  • LiMnO 2 As a second oxide.
  • the obtained LiMnO 2 had a BET specific surface area of 13 m 2 / g and an average particle size of 13 ⁇ m in d50.
  • LiMnO 2 was analyzed by X-ray diffraction, LiMnO 2 had a crystal structure belonging to the space group Pmnm.
  • the ratio (Ia / Ib) between the peak intensity Ia at 24.6 ° and the peak intensity Ib at 15.3 ° of LiMnO 2 was 0.37.
  • the ratio (Ic / Ib) of the peak intensity Ic at 45.0 ° to the peak intensity Ib at 15.3 ° of LiMnO 2 was 0.99.
  • the obtained positive electrode active material, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder were mixed at a mass ratio of 90: 5: 5.
  • N-methyl-2-pyrrolidone was added to this mixture to prepare a positive electrode mixture slurry.
  • the obtained positive electrode mixture slurry was applied to a positive electrode current collector made of an aluminum foil and vacuum-dried at 110 ° C. to produce a positive electrode.
  • a three-electrode test cell 20 as shown in FIG. 2 was produced.
  • the above positive electrode was used as the working electrode 21 in an argon atmosphere.
  • Lithium metal was used as the counter electrode 22 and the reference electrode 23.
  • a polyethylene separator was used as the separator.
  • the non-aqueous electrolyte 24 a solution obtained by dissolving LiPF 6 to a concentration of 1.0 mol / l in a non-aqueous solvent in which ethylene carbonate and diethyl carbonate are mixed so as to have a volume ratio of 3: 7 is used. It was.
  • a current collecting tab was attached to each of the working electrode 21, the counter electrode 22, and the reference electrode 23.
  • An electrode-type test cell 20 was produced, and the initial charge capacity, initial discharge capacity, initial charge / discharge efficiency, and capacity maintenance ratio at the 35th cycle were measured. These measurement results are shown in Table 1.
  • Example 1 A three-electrode test cell 20 was prepared in the same manner as in Example 1 except that the positive electrode active material was prepared using only the first oxide, and the initial charge capacity, initial discharge capacity, initial charge / discharge efficiency, and 35 The capacity retention rate at the cycle was measured. These measurement results are shown in Table 1.
  • Comparative Example 2 A three-electrode test cell 20 was prepared in the same manner as in Example 1 except that the positive electrode active material was prepared using only the second oxide, and the initial charge capacity, initial discharge capacity, initial charge / discharge efficiency, and 35 The capacity retention rate at the cycle was measured. These measurement results are shown in Table 1. In Comparative Example 2, since the initial discharge capacity was low, charging / discharging after the first cycle was not performed.
  • the second oxidation has a high initial charge capacity when charged from the positive electrode potential of 3.0 V (vs. Li / Li + ) to 4.3 V (vs. Li / Li + ).
  • the charge / discharge cycle characteristics were improved as compared with Comparative Example 1. This is presumably because the positive electrode active material having a high initial charge capacity suppressed the negative electrode active material from being overdischarged by giving the negative electrode active material an irreversible capacity at a low potential.
  • Example 1 A three-electrode test cell 20 was produced in the same manner as in Example 1 except that only LiMnO 2 having a BET specific surface area shown in Table 2 was used as the positive electrode active material.
  • Reference Example 2 A three-electrode test cell 20 was prepared in the same manner as in Reference Example 1 except that LiMnO 2 having the BET specific surface area shown in Table 2 was used as the second oxide, and the initial charge capacity, initial discharge capacity, and The initial charge / discharge efficiency was measured. These results are shown in Table 2.
  • Reference Example 3 A three-electrode test cell 20 was prepared in the same manner as in Reference Example 1 except that LiMnO 2 having the BET specific surface area shown in Table 2 was used as the second oxide, and the initial charge capacity, initial discharge capacity, and The initial charge / discharge efficiency was measured. These results are shown in Table 2.
  • Reference Example 5 A three-electrode test cell 20 was prepared in the same manner as in Reference Example 4 except that LiOH, MnO 2 and carbon were mixed at a molar ratio of 1.10: 1.00: 0.375. The capacity, initial discharge capacity, and initial charge / discharge efficiency were measured. These results are shown in Table 3. Also in Reference Example 5, LiMnO 2 having a crystal structure belonging to the space group c2 / m was included in the second oxide.
  • Reference Example 6 A three-electrode test cell 20 was prepared in the same manner as in Reference Example 4 except that LiOH, MnO 2 and carbon were mixed at a molar ratio of 1.20: 1.00: 0.375. The capacity, initial discharge capacity, and initial charge / discharge efficiency were measured. These results are shown in Table 3. Also in Reference Example 6, LiMnO 2 having a crystal structure belonging to the space group c2 / m was included in the second oxide.
  • Reference Example 7 A three-electrode test cell 20 was prepared in the same manner as in Reference Example 4 except that LiOH, MnO 2 and carbon were mixed at a mass molar ratio of 1.30: 1.00: 0.375. The charge capacity, initial discharge capacity, and initial charge / discharge efficiency were measured. These results are shown in Table 3. Also in Reference Example 7, LiMnO 2 having a crystal structure belonging to the space group c2 / m was included in the second oxide.
  • LiMnO 2 having a crystal structure belonging to the space group c2 / m of Reference Examples 4 to 7 is LiMnO having a crystal structure belonging to the space group Pmnm of Example 1 and Example 2.
  • FIG. 2 it can be seen that a large initial charge capacity can be imparted to the three-electrode test cell 20.

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Abstract

L'invention concerne un matériau actif d'électrode positive d'un accumulateur à électrolyte non aqueux qui ne requiert pas de définir une haute tension la première fois que la charge est terminée pour l'accumulateur à électrolyte non aqueux, et peut conférer d'excellentes caractéristiques du cycle de charge-décharge à l'accumulateur à électrolyte non aqueux. Le présent matériau actif d'électrode positive d'un accumulateur à électrolyte non aqueux (1) comporte un premier oxyde et un second oxyde.
PCT/JP2012/077231 2011-10-31 2012-10-22 Matériau actif d'électrode positive d'accumulateur à électrolyte non aqueux, et accumulateur à électrolyte non aqueux WO2013065513A1 (fr)

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JP2011-238686 2011-10-31

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JPH10208730A (ja) * 1997-01-24 1998-08-07 Japan Storage Battery Co Ltd 非水電解質二次電池
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JP2006298750A (ja) * 2005-03-22 2006-11-02 Nippon Chem Ind Co Ltd マンガン酸リチウム、その製造方法、リチウム二次電池正極副活物質、リチウム二次電池正極活物質及びリチウム二次電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06349493A (ja) * 1993-06-12 1994-12-22 Haibaru:Kk 二次電池
JPH07230802A (ja) * 1993-12-24 1995-08-29 Sharp Corp 非水系二次電池およびその正極活物質の製造方法
JPH10208730A (ja) * 1997-01-24 1998-08-07 Japan Storage Battery Co Ltd 非水電解質二次電池
JP2000348722A (ja) * 1999-06-04 2000-12-15 Sony Corp 非水電解質電池
JP2006222072A (ja) * 2005-01-14 2006-08-24 Matsushita Electric Ind Co Ltd 非水電解質二次電池
JP2006298750A (ja) * 2005-03-22 2006-11-02 Nippon Chem Ind Co Ltd マンガン酸リチウム、その製造方法、リチウム二次電池正極副活物質、リチウム二次電池正極活物質及びリチウム二次電池

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