WO2015132844A1 - Matériau d'électrode positive pour piles rechargeables au lithium ion et pile rechargeable au lithium ion - Google Patents

Matériau d'électrode positive pour piles rechargeables au lithium ion et pile rechargeable au lithium ion Download PDF

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WO2015132844A1
WO2015132844A1 PCT/JP2014/055216 JP2014055216W WO2015132844A1 WO 2015132844 A1 WO2015132844 A1 WO 2015132844A1 JP 2014055216 W JP2014055216 W JP 2014055216W WO 2015132844 A1 WO2015132844 A1 WO 2015132844A1
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positive electrode
ion secondary
lithium ion
active material
secondary battery
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PCT/JP2014/055216
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English (en)
Japanese (ja)
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小西　宏明
小林　満
豊隆 湯浅
所　久人
秀一 高野
崇 中林
章 軍司
達哉 遠山
孝亮 馮
翔 古月
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株式会社日立製作所
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 material for a lithium ion secondary battery, and a lithium ion secondary battery including the same.
  • the problem with electric vehicles is that the energy density of the driving battery is low and the travel distance for one charge is short. Therefore, there is a demand for an inexpensive secondary battery with high energy density.
  • Lithium ion secondary batteries have a higher energy density per weight than secondary batteries such as nickel hydrogen batteries and lead batteries. Therefore, the application to an electric vehicle and a power storage system is expected. However, in order to meet the demand for electric vehicles, it is necessary to further increase the energy density. In order to realize high energy density, it is necessary to increase the energy density of the positive electrode and the negative electrode.
  • a layered solid solution represented by Li 2 MO 3 -LiM′O 2 attracts attention.
  • the layered solid solution can also be represented by the composition formula Li 1 + x M 1-x O 2 as a lithium-enriched cathode active material of the layered oxide.
  • the molar ratio Co / Me (x / (x + y + z)) is 0.020 to 0.230
  • the molar ratio Mn / Me (z / (x + y + z)) is 0.625 to 0.
  • the positive electrode active material characterized in that it is .719 is described.
  • Patent Document 2 discloses a lithium manganese oxide having a layered structure and a lithium manganese having a spinel structure in order to provide a lithium ion secondary battery having a high capacity without a sharp decrease in output over a wide SOC (State of Charge) section.
  • the oxide is mixed.
  • JP 2012-151084 A Japanese Patent Publication No. 2013-520782
  • the layered solid solution has high resistance as compared with the layered oxide LiMO 2 , the reduction of the resistance is desired. Moreover, since the positive electrode active material currently disclosed by patent document 1 has low electrode density, improvement of volume energy density is desired.
  • the positive electrode material disclosed in Patent Document 2 has a high electrode density, and high volume energy density can be expected. However, high volumetric energy density can be obtained when the lower limit potential is lowered to 2.0 V.
  • an object of the present invention is to provide a lithium ion secondary battery with high output and high volumetric energy density.
  • the positive electrode material for a lithium ion secondary battery according to the present invention is made of a lithium transition metal oxide containing Li and a metal element, contains at least Ni and Mn as the metal element, and an atom of Li to the metal element
  • a first positive electrode active material having a ratio of 1.15 ⁇ Li / metal element ⁇ 1.5 and an atomic ratio of Ni to Mn of 0.334 ⁇ Ni / Mn ⁇ 1, and a composition formula LiMn 2 ⁇ y M ′ y O 4 (0 ⁇ y ⁇ 0.2, M ′ is represented by at least one element of Mn, Co, Ni, V, Mg, Mo, W, Al, Nb, Ti and Cu)
  • a second positive electrode active material is included, and the content of the second positive electrode active material is 5% by mass or more and less than 30% by mass with respect to the positive electrode material.
  • ⁇ Positive material> When using a lithium ion secondary battery for an electric vehicle, it is desirable that the travel distance per charge be long. In order to increase the travel distance per charge, it is necessary to improve the energy density per unit volume.
  • a lithium ion secondary battery using a layered solid solution as a positive electrode active material is expected to have a high capacity and a high weight energy density.
  • the electrode density is low, there is a problem in volume energy density. Since layered solid solutions have high resistance, they need to be micronized to obtain high capacity. However, when the particles are made finer, the electrode density decreases due to interparticle friction and the like. As a result, the volumetric energy density is reduced. Therefore, in order to obtain high volumetric energy density, it is necessary to improve the electrode density.
  • a positive electrode active material having a spinel structure capable of obtaining a large capacity even with a large particle size can be mixed to achieve high density.
  • layered solid solutions generally do not have high capacity unless the lower limit potential is lowered to 2.0 V.
  • a lithium manganese oxide having a spinel structure represented by LiMn 2 O 4 is accompanied by a change in the abundance of Mn 3+ and a change in crystal structure at 3.2 V or less, so the lower limit potential is up to 2.0 V If it is lowered, LiMn 2 O 4 may be degraded and the cycle characteristics may be degraded.
  • FIG. 1 is a discharge curve of Li 1.05 Ni 0.35 Mn 0.45 O 2 and 2 is a discharge curve of Li 1.2 Ni 0.2 Mn 0.6 O 2 .
  • 1 is a discharge curve of Li 1.05 Ni 0.35 Mn 0.45 O 2
  • 2 is a discharge curve of Li 1.2 Ni 0.2 Mn 0.6 O 2 .
  • lithium manganese oxide having a spinel structure represented by LiMn 2 O 4 has high output. Accordingly, the reaction area of the LiMn 2 O 4 (3.9 ⁇ 4.1V ), because LiMn 2 O 4 also react, thus improving the cell output.
  • the first positive electrode active material is made of a lithium transition metal oxide containing Li and a metal element, contains at least Ni and Mn as the metal element, and the atomic ratio of Li to the metal element is 1 It is characterized in that 15 ⁇ Li / metal element ⁇ 1.5, and the atomic ratio of Ni to Mn is 0.334 ⁇ Ni / Mn ⁇ 1.
  • the ratio of lithium element to metal element Li / metal element
  • the amount of Li contributing to the reaction is reduced and high capacity can not be obtained.
  • Li / metal element is larger than 1.5, the crystal lattice becomes unstable and the discharge capacity is reduced.
  • Ni / Mn is lower than 0.334, the discharge potential decreases, and a large difference occurs between the reaction end potential and the reaction potential of the second positive electrode active material, and the second positive electrode active material improves the resistance at the discharge end Can not.
  • Ni / Mn is larger than 1, almost no charge / discharge reaction involving oxygen occurs, and the capacity decreases.
  • the amount of oxygen contained in the first positive electrode active material is maintained while maintaining the layered solid solution structure by the valence of the metal and the amount of Li on the basis that the total molar number of the metal element and lithium is equivalent. Since it is considered that the amount of oxygen to be supplied is appropriately increased or decreased, -1.ltoreq..delta..ltoreq.1.
  • the metal element may further contain an additive element M.
  • the atomic ratio of Ni and Mn to the metal element is preferably 0.975 ⁇ (Ni + Mn) / metal element ⁇ 1.0.
  • the additive element M is an additive or an impurity added within a range not affecting the present invention, and at least one element selected from Co, V, Mo, W, Zr, Nb, Ti, Cu, Al, Fe It is.
  • y represents the content ratio (the mass ratio of substance) of M ′.
  • M ′ is an element to be added appropriately, and the addition amount thereof needs to be suppressed to the range of 0 ⁇ y ⁇ 0.2 so that the effect of the present invention is not suppressed.
  • the content of the second positive electrode active material is preferably 5% by mass or more and less than 30% by mass with respect to the positive electrode material.
  • the content of the second positive electrode active material is less than 5% by mass, the effect of improving the electrode density is small, and a high volume energy density can not be obtained.
  • the content of the second positive electrode active material is 30% by mass or more, the proportion of the first positive electrode active material from which high capacity can be obtained decreases, so that high energy density can not be obtained.
  • the content of the second positive electrode active material is preferably 5% by mass or more and 20% by mass or less.
  • the particle diameter of the first positive electrode active material is preferably 100 to 400 nm.
  • the resistance can be reduced by reducing the particle size.
  • the particle diameter of the second positive electrode active material is preferably 5 to 15 ⁇ m.
  • the second positive electrode active material represented by LiMn 2 O 4 can obtain high capacity even if the particle size is large.
  • the positive electrode material according to the present invention can be produced by a method generally used in the technical field to which the present invention belongs.
  • the first positive electrode active material can be produced, for example, by mixing and firing compounds containing Li, Ni, and Mn in appropriate proportions.
  • the composition of the positive electrode material can be appropriately adjusted by changing the ratio of the compounds to be mixed.
  • the compound containing Li include lithium acetate, lithium nitrate, lithium carbonate, lithium hydroxide, lithium oxide and the like.
  • the compound containing Ni include nickel acetate, nickel nitrate, nickel carbonate, nickel sulfate, nickel hydroxide and the like.
  • Mn manganese acetate, manganese nitrate, manganese carbonate, manganese sulfate, manganese oxide etc. can be mentioned, for example.
  • the second positive electrode active material can be produced by mixing and calcining compounds containing Li and Mn respectively in appropriate proportions.
  • the compound containing Li include lithium acetate, lithium nitrate, lithium carbonate, lithium hydroxide, lithium oxide and the like.
  • Mn manganese acetate, manganese nitrate, manganese carbonate, manganese sulfate, manganese oxide etc. can be mentioned, for example.
  • composition of the positive electrode material can be determined, for example, by elemental analysis using inductively coupled plasma (ICP) or the like.
  • ICP inductively coupled plasma
  • the lithium ion secondary battery according to the present invention is characterized by containing the above-mentioned positive electrode material.
  • positive electrode material for the positive electrode, high volume energy density and high output can be achieved.
  • the cycle characteristics may be degraded. Therefore, in use, by setting the lower limit potential to 3.3 V or more based on Li metal, deterioration of the second positive electrode active material can be suppressed, and high cycle characteristics can be maintained.
  • the lithium ion secondary battery according to the present invention can be preferably used for an electric vehicle.
  • the positive electrode active material occludes and releases lithium ions by charge and discharge. Since not all lithium ions released from the positive electrode active material return to the positive electrode, the composition of the positive electrode active material after charge and discharge is expected to be different from that before charge and discharge.
  • the positive electrode active material of a layered compound represented by LiMO 2 has a composition ratio of Li in a full discharge state (2.0 V) when used in a potential range of 2.0 to 4.3 V based on Li metal. It is known to be about 0.75.
  • the substance mass of Li after charging and discharging of the layered solid solution is also reduced by about 20% in the fully discharged state compared to before charging and discharging. Therefore, when a lithium secondary battery is manufactured using the positive electrode material according to the present invention and charged and discharged, the first positive electrode active material is represented by the composition formula Li x Ni a Mn b M c O 2 + in a full discharge state.
  • the atomic ratio of Li to metal elements other than Li in the first positive electrode active material satisfies the relationship 0.90 ⁇ Li / metal element ⁇ 1.5.
  • the lithium ion secondary battery is composed of a positive electrode containing a positive electrode material, a negative electrode containing a negative electrode material, a separator, an electrolytic solution, an electrolyte and the like.
  • the negative electrode material is not particularly limited as long as it is a substance capable of inserting and extracting lithium ions.
  • Materials generally used in lithium ion secondary batteries can be used as the negative electrode material.
  • graphite, lithium alloy and the like can be exemplified.
  • a separator those generally used in lithium ion secondary batteries can be used.
  • a microporous film or non-woven fabric made of polyolefin such as polypropylene, polyethylene, and a copolymer of propylene and ethylene can be exemplified.
  • the electrolytic solution and the electrolyte those generally used in lithium ion secondary batteries can be used.
  • the electrolytic solution diethyl carbonate, dimethyl carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, methyl acetate, ethyl methyl carbonate, methyl propyl carbonate, dimethoxyethane and the like can be exemplified.
  • the electrolyte LiClO 4, LiPF 6, LiBF 4, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiC 4 F 9 SO 3, LiCF 3 CO 2, Li 2 C 2 F 4 (SO 3) 2, LiN (CF 3 SO 2) 2, LiC (CF 3 SO 2) can be exemplified 3 or the like.
  • the lithium ion secondary battery 12 includes an electrode group including a positive electrode 3 having a positive electrode material coated on both sides of a current collector, a negative electrode 4 having a negative electrode material coated on both sides of the current collector, and a separator 5.
  • the positive electrode 3 and the negative electrode 4 are wound via the separator 5 to form a wound electrode group.
  • the wound body is inserted into the battery can 6.
  • the negative electrode 4 is electrically connected to the battery can 6 via the negative electrode lead piece 8.
  • a sealing lid 9 is attached to the battery can 6 via a packing 10.
  • the positive electrode 3 is electrically connected to the sealing lid 9 through the positive electrode lead piece 7.
  • the wound body is insulated by the insulating plate 11.
  • the electrode group may not be a wound body shown in FIG. 2, and may be a laminate in which the positive electrode 3 and the negative electrode 4 are stacked via the separator 5.
  • the first positive electrode active material was produced by the following method. Lithium carbonate, nickel carbonate and manganese carbonate were mixed in a ball mill to obtain a precursor. The obtained precursor was calcined at 500 ° C. for 12 hours in the air to obtain a lithium transition metal oxide. The obtained lithium transition metal oxide was pelletized and then fired at 850 to 1050 ° C. for 12 hours in the air. The fired pellet was ground in an agate mortar to obtain a first positive electrode active material represented by the composition formula Li x Ni a Mn b M c O 2 + ⁇ .
  • the second positive electrode active material was produced by the following method. Lithium hydroxide and manganese oxide were mixed in a ball mill to obtain a precursor. The obtained precursor was calcined at 500 ° C. for 12 hours in the air to obtain a lithium transition metal oxide. The obtained lithium transition metal oxide was pelletized and then fired at 800 ° C. for 12 hours in the air. The fired pellet was crushed in an agate mortar to obtain LiMn 2 O 4 . This was used as a second positive electrode active material.
  • the first positive electrode active material and the second positive electrode active material were mixed to obtain a positive electrode material.
  • the composition of the first positive electrode active material and the content of the second positive electrode active material in the manufactured positive electrode material are shown in Table 1.
  • a positive electrode was produced using the above-mentioned positive electrode material, and trial batteries of Examples 1 to 12 and Comparative Examples 1 to 6 were produced.
  • a positive electrode slurry was prepared by uniformly mixing the positive electrode material of the battery used in the trial battery, the conductive agent, and the binder. The positive electrode slurry was applied onto a 20 ⁇ m thick aluminum current collector foil and dried at 120 ° C. After drying, it was pressed at a pressure of 40 MPa to obtain an electrode plate. Thereafter, the electrode plate was punched into a disk shape having a diameter of 15 mm to produce a positive electrode.
  • the negative electrode was produced using metallic lithium.
  • a non-aqueous electrolytic solution one in which LiPF 6 was dissolved at a concentration of 1.0 mol / L in a mixed solvent of ethylene carbonate and dimethyl carbonate at a volume ratio of 1: 2 was used.
  • the experimental battery of Example 12 measured the discharge capacity in the same manner as in Example 1 except that the upper limit voltage for charge and discharge was 4.6 V and the lower limit voltage was 2.0 V.
  • the measured discharge capacities are shown in Table 1.
  • the upper limit voltage is 4.6 V at a current of 0.05 C equivalent and the lower limit voltage is 3.3 V at a current of 0.05 C equivalent for discharging.
  • a charge and discharge test was conducted, and the discharge capacity at the second cycle was taken as the rated capacity.
  • the prototype battery after two cycles was charged to 4.6 V and then discharged to a capacity of 50% of the rated capacity. Thereafter, a current of 1.2 mA was applied for 10 seconds to measure the direct current resistance. The value obtained by dividing the potential difference before and after applying the current for 10 seconds by the applied current value (1.2 mA) was defined as the DC resistance value.
  • the experimental battery of Example 12 measured DC resistance in the same manner as in Example 1 except that the upper limit voltage for charging and discharging was set to 4.6 V and the lower limit voltage was set to 2.0 V.
  • the measured DC resistance values are shown in Table 1. ⁇ Measurement of capacity retention rate> The capacity retention rate after 100 cycles was determined for the trial batteries of each example and comparative example.
  • the upper limit voltage is 4.6 V at a current of 0.05 C equivalent and the lower limit voltage is 3.3 V at a current of 0.05 C equivalent for discharging.
  • a charge and discharge test was conducted, and the discharge capacity at the second cycle was taken as the rated capacity. Thereafter, after 99 cycles of charge 1 C and discharge 1 C, charge and discharge were carried out at 0.05 C, and the capacity after 100 cycles was measured. A value obtained by dividing the discharge capacity after 100 cycles by the rated capacity was defined as a capacity retention rate.
  • the capacity retention ratio of the prototype battery manufactured using the positive electrode material of Example 12 was measured in the same manner as in Example 1 except that the upper limit voltage for charging and discharging was set to 4.6 V and the lower limit voltage was set to 2.0 V.
  • Example 1 has a higher capacity than Comparative Example 1 in the potential range of 3.3 V or more.
  • Example 1 has a higher potential than Comparative Example 1. Therefore, Example 1 can obtain higher energy density than Comparative Example 1.
  • the same results as in Example 1 were obtained for the discharge curves of Examples 2 to 12. Therefore, Examples 1 to 12 can obtain higher energy density as compared to the Comparative Example.
  • the discharge capacity per unit volume is higher than in Comparative Examples 1 to 6. Furthermore, in Examples 1 to 12, the direct current resistance is equal to or less than Comparative Example 2 in which the second positive electrode active material is not contained.
  • Comparative Examples 2 to 6 it was not possible to simultaneously achieve high capacity and low resistance.
  • Comparative Example 1 since Li / (Ni + Mn) of the first positive electrode active material is as high as 1.5 and Ni / Mn is as small as 0.33, discharge per unit volume in the region of 4.6 to 3.3 V Capacity is low.
  • Comparative Example 2 since only the first positive electrode active material with low electrode density is formed, the discharge capacity per unit volume is low.
  • the discharge capacity per unit volume is low because only the second positive electrode active material with low capacity is used.
  • Comparative Example 4 since the content of the second positive electrode active material having a low capacity is as large as 30%, the discharge capacity per unit volume is low.
  • Comparative Example 5 since Li / (Ni + Mn) of the first positive electrode active material is as low as 1.125, the discharge capacity is low and the discharge capacity per unit volume is low. In Comparative Example 6, since Li / (Ni + Mn) of the first positive electrode active material is as high as 1.50, the discharge capacity is low and the discharge capacity per unit volume is low.
  • the first positive electrode active material satisfying the relationship of atomic weight ratios of Li, Ni, and Mn of 1.15 ⁇ Li / (Ni + Mn) ⁇ 1.5 and 0.334 ⁇ Ni / Mn ⁇ 1, and the composition formula LiMn 2 -y M ' y O 4 (0 y y 0.2 0.2, M' is represented by Fe, Co, Ni, V, Mg, Mo, W, Al, Nb, Ti, Cu, or any other element)
  • Per unit volume of a lithium ion secondary battery by using a positive electrode material containing a second positive electrode active material and having a content of the second positive electrode active material to the positive electrode material of 5% by mass or more and less than 30% by mass. Discharge capacity is improved and resistance is reduced. As a result, it is possible to provide a lithium ion secondary battery having a high volumetric energy density and a high output.
  • Example 1 has a higher capacity retention rate than Example 12. This is because the lower limit potentials of charge and discharge are different. In Example 12, since the lower limit potential of charge and discharge was as low as 2.0 V, when the cycle was repeated, the second positive electrode active material was deteriorated, and the capacity retention rate was lowered. On the other hand, in Example 1, by setting the lower limit potential of charge and discharge to 3.3 V, deterioration of the second positive electrode active material was suppressed, and a high capacity retention rate could be achieved.
  • Li / (Ni + Mn) and Ni / Mn of the lithium transition metal oxide having a metal element containing at least Ni and at least Ni and Mn are optimized, and the composition formula LiMn 1 ⁇ y M ′ y O 4 (0 ⁇ y ⁇ 0.2, M ′ is represented by at least one element of Mn, Co, Ni, V, Mg, Mo, W, Al, Nb, Ti and Cu)

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'objectif de la présente invention est de fournir une pile rechargeable au lithium-ion qui présente une haute densité énergétique et une grande puissance de sortie. Cet objectif peut être atteint grâce à un matériau d'électrode positive qui est caractérisé en ce qu'il contient un premier matériau actif d'électrode positive qui est composé d'un oxyde métallique de transition au lithium contenant du Li et des éléments métalliques comprenant au moins du Ni et du Mn, le rapport atomique entre le Li et les éléments métalliques étant le suivant: 1,15 < Li/(éléments métalliques) < 1,5 et le rapport atomique entre le Ni et le Mn étant le suivant: 0,334 < Ni/Mn ≤ 1, et un second matériau actif d'électrode positive qui est représenté par la formule de composition suivante: LiMn2-yM'yO4 (dans laquelle 0 ≤ y ≤ 0,2 et M' représente au moins un élément choisi parmi du Mn, Co, Ni, V, Mg, Mo, W, Al, Nb, Ti et Cu), et qui est également caractérisé en ce que la teneur en second matériau actif d'électrode positive est égale ou supérieure à 5% en masse mais inférieure à 30% en masse par rapport au matériau d'électrode positive.
PCT/JP2014/055216 2014-03-03 2014-03-03 Matériau d'électrode positive pour piles rechargeables au lithium ion et pile rechargeable au lithium ion WO2015132844A1 (fr)

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WO2017138382A1 (fr) * 2016-02-12 2017-08-17 Ｎｅｃエナジーデバイス株式会社 Électrode positive pour batterie secondaire au lithium-ion ainsi que procédé de fabrication de celle-ci, batterie secondaire au lithium-ion, et procédé d'évaluation
JP2018113130A (ja) * 2017-01-10 2018-07-19 日揮触媒化成株式会社 マンガン酸リチウム、該マンガン酸リチウムを含む正極、及び該正極を備える非水電解質二次電池

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WO2017138382A1 (fr) * 2016-02-12 2017-08-17 Ｎｅｃエナジーデバイス株式会社 Électrode positive pour batterie secondaire au lithium-ion ainsi que procédé de fabrication de celle-ci, batterie secondaire au lithium-ion, et procédé d'évaluation
JPWO2017138382A1 (ja) * 2016-02-12 2018-12-06 Ｎｅｃエナジーデバイス株式会社 リチウムイオン二次電池用正極及びリチウムイオン二次電池、並びにリチウムイオン二次電池用正極の製造方法および評価方法
JP2018113130A (ja) * 2017-01-10 2018-07-19 日揮触媒化成株式会社 マンガン酸リチウム、該マンガン酸リチウムを含む正極、及び該正極を備える非水電解質二次電池

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