WO2015079546A1 - Electrode positive de batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion - Google Patents

Electrode positive de batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion Download PDF

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WO2015079546A1
WO2015079546A1 PCT/JP2013/082119 JP2013082119W WO2015079546A1 WO 2015079546 A1 WO2015079546 A1 WO 2015079546A1 JP 2013082119 W JP2013082119 W JP 2013082119W WO 2015079546 A1 WO2015079546 A1 WO 2015079546A1
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positive electrode
active material
electrode active
lithium ion
ion secondary
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PCT/JP2013/082119
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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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Priority to PCT/JP2013/082119 priority Critical patent/WO2015079546A1/fr
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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
    • H01M4/362—Composites
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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 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.
  • the molar ratio Li / Me (a / (x + y + z)) of Li to the total transition metal element Me is 1.25 to 1.40, and the molar ratio Co / Me (x / (x + y + z)) is 0.020 to 0
  • a positive electrode active material is described which is characterized by having a molar ratio of Mn / Me (z / (x + y + z)) of 0.625 to 0.719.
  • Patent Document 2 describes a composition formula Li a Mn b M c O z (M is more than Ni, Co, Al and F) in order to provide a battery having high capacity, high temperature storage performance, and excellent cycle performance.
  • Lithium manganese-containing oxide represented by one or more elements selected from the group consisting of 0 ⁇ a ⁇ 2.5, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, 2 ⁇ z ⁇ 3), and an olivine structure
  • a positive electrode containing an Fe-containing phosphorus compound is a composition formula Li a Mn b M c O z (M is more than Ni, Co, Al and F) in order to provide a battery having high capacity, high temperature storage performance, and excellent cycle performance.
  • Lithium manganese-containing oxide represented by one or more elements selected from the group consisting of 0 ⁇ a ⁇ 2.5, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, 2 ⁇ z ⁇ 3
  • JP 2012-151084 A JP, 2012-033507, A
  • the positive electrode active material of the composition shown by patent document 1 can obtain high energy density, since resistance is high, the subject that a high output is not obtained occurs. In particular, at low SOC (State of Charge) where the potential is low and the resistance increases, further improvement of the output is desired.
  • An object of the present invention is to provide a lithium ion secondary battery having a high energy density and a high output.
  • the positive electrode for a lithium ion secondary battery according to the present invention is a positive electrode including a positive electrode mixture layer containing a positive electrode material and a current collector having a positive electrode mixture layer formed on the surface, and the positive electrode material is Li And a lithium transition metal oxide containing a metal element, containing at least Ni and Mn as the metal element, and the atomic ratio of Li to the metal element is 1.15 ⁇ Li / metal element ⁇ 1.5
  • a first positive electrode active material having an atomic ratio of Ni to Mn of 0.334 ⁇ Ni / Mn ⁇ 1.0, and a composition formula LiFe 1-y M ′ y PO 4 (0 ⁇ y ⁇ 0.2, M 'Includes a second positive electrode active material represented by at least one element of Mn, Co, Ni, V, Mg, Mo, W, Al, Nb, Ti, and Cu), and is in contact with the current collector In the region of the positive electrode mixture layer, the ratio of the second positive electrode active material is higher than that of the first
  • ⁇ Positive material> When using a lithium ion secondary battery for an electric vehicle, it is expected that the traveling distance per charge is long. In order to increase the travel distance per charge, the battery is required to have a high energy density and to be able to use the battery in a wider range of SOC.
  • a layered solid solution represented by Li 2 MO 3 -LiM′O 2 is expected as a high energy density positive electrode active material.
  • the layered solid solution can be expected to increase the energy density of the positive electrode because a high capacity can be obtained.
  • the layered solid solution can also be represented by the composition formula Li 1 + x M 1-x O 2 .
  • the layered solid solution is a lithium transition metal oxide having a rock salt type layered structure, and is a material containing an excess of Li relative to the transition metal and having a composition ratio of 50% or more of Mn in the transition metal. Indicates
  • a lithium ion secondary battery using a layered solid solution as a positive electrode active material can be expected to have a high energy density but has high resistance at the end of discharge. There is a problem that a sufficient output can not be obtained because the potential is also low at the end of discharge.
  • Figure 1 shows the relationship between SOC and output of layered solid solution. In FIG. 1, the vertical axis is the power density, and the horizontal axis is the SOC. It can be seen that the output is low in the low SOC region. In a car-mounted lithium ion secondary battery requiring high output, a low output region can not be used, so the range of usable SOC is narrowed, and as a result, the battery capacity is reduced. Therefore, in order to improve the output, it is necessary to reduce the resistance at the end of discharge and to improve the potential.
  • reaction in which a transition metal participates in redox occurs in the early stage of charging, and a redox reaction in which oxygen participates in the late stage of charging.
  • a reaction involving the transition metal occurs at the beginning of the discharge, and at the end of the discharge, a redox reaction involving the oxygen occurs.
  • Reactions involving transition metals are at high potential while reactions involving oxygen are at low potential and high resistance.
  • FIG. 2 shows discharge curves of LiNi 0.35 Mn 0.45 O 2 + ⁇ and Li 1.2 Ni 0.2 Mn 0.6 O 2 + ⁇ .
  • the discharge curve of LiNi 0.35 Mn 0.45 O 2 + ⁇ is indicated by a solid line
  • the discharge curve of Li 1.2 Ni 0.2 Mn 0.6 O 2 + ⁇ is indicated by a dotted line.
  • both capacities are equal, but Li 1 Ni 0.35 Mn 0.45 O 2 + ⁇ has a higher potential than Li 1.2 Ni 0.2 Mn 0.6 O 2 + ⁇
  • the capacity becomes high at a high potential.
  • the resistance can be reduced by mixing an active material that reacts at 2.5 to 3.5 V, which is the potential at the end of discharge of LiNi 0.35 Mn 0.45 O 2 + ⁇ .
  • the Fe-containing phosphorus compound having an olivine structure represented by LiFePO 4 has a reaction potential of about 3.5 V, and has good electron conductivity by coating carbon. Therefore, the resistance at the end of the discharge can be reduced by mixing the layered solid solution having a small atomic ratio of Li to the transition metal element and the Fe-containing phosphorus compound having an olivine structure. As a result, the output can be improved and the range of usable SOC can be expanded.
  • the positive electrode material for a lithium ion secondary battery according to the present invention includes a first positive electrode active material and a second positive electrode active material.
  • the first positive electrode active material is made of a lithium transition metal oxide containing Li and a metal element, the metal element contains at least Ni and Mn, and the atomic ratio of Li, Ni, and Mn is It is characterized in that 1.15 ⁇ Li / metal element ⁇ 1.5 and 0.334 ⁇ Ni / Mn ⁇ 1 are satisfied.
  • the second positive electrode active material has a composition formula LiFe 1-y M ′ y PO 4 (0 ⁇ y ⁇ 0.2, where M ′ is Mn, Co, Ni, V, Mg, Mo, W, Al, Nb, And at least one element of Ti and Cu).
  • the first positive electrode active material when Li / (Ni + Mn) is less than 1.15, the amount of Li contributing to the reaction is reduced, and a high capacity can not be obtained. On the other hand, when it is larger than 1.5, the crystal lattice becomes unstable and the discharge capacity is reduced. When 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. When Ni / Mn is larger than 1, almost no charge / discharge reaction involving oxygen occurs, and the capacity decreases.
  • 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 second positive electrode active material is preferably coated with a carbon material.
  • the content of the second positive electrode active material in the positive electrode material is preferably 2% by mass or more and 15% by mass or less. If the content of the second positive electrode active material exceeds 15% by mass, the proportion of the first positive electrode active material having a high energy density is reduced, and a high energy density can not be obtained.
  • the content of the second positive electrode active material is preferably 10% by mass or less.
  • 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 is prepared by mixing compounds containing Li, Fe, and P in appropriate proportions, and then mixing with a carbon source such as polyvinyl alcohol to ensure conductivity, and firing. can do.
  • Examples of the compound containing Li include lithium acetate, lithium nitrate, lithium carbonate, lithium hydroxide, lithium oxide and the like.
  • Examples of the compound containing Fe include iron oxalate, iron nitrate, iron sulfide and iron chloride.
  • Examples of the compound containing P include ammonium dihydrogen phosphate, phosphoric acid and the like.
  • 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 positive electrode for a lithium ion secondary battery according to the present invention comprises a positive electrode mixture layer containing the above-described positive electrode material and a current collector, and a positive electrode mixture layer is formed on the surface of the current collector.
  • the ratio of the second positive electrode active material in the positive electrode mixture layer in the region in contact with the current collector is higher than that of the first positive electrode active material, and the surface of the positive electrode mixture layer opposite to the surface in contact with the current collector is And a ratio of the first positive electrode active material is higher than that of the second positive electrode active material.
  • the output can react for about a few seconds. Therefore, it is preferable to dispose a second positive electrode active material having high electron conductivity in the vicinity of the current collector.
  • the second positive electrode active material By arranging the second positive electrode active material closer to the current collector than the first positive electrode active material, the second positive electrode active material can be brought into contact with the current collector, and the second positive electrode active material has high electron conductivity. Can contribute to the flow of electrons.
  • the first positive electrode active material is disposed closer to the current collector than the second positive electrode active material, the second positive electrode active material can not be in direct contact with the current collector, and the first positive electrode has high resistance. Since the contact is made via the active material, the performance of the second positive electrode active material can not be sufficiently exhibited.
  • FIG. 3 is a view schematically showing the arrangement of the current collector, the first positive electrode active material, and the second positive electrode active material in the positive electrode.
  • 1 is a current collector
  • 2 is a mixture layer containing a second positive electrode active material
  • 3 is a mixture layer containing a first positive electrode active material.
  • the second positive electrode active material is collected by applying a slurry containing the second positive electrode active material to the current collector and applying a slurry containing the first positive electrode active material thereon. A large amount of the first positive electrode active material can be distributed on the side opposite to the current collector.
  • the proportion of the second positive electrode active material is higher in the vicinity of the current collector than the first positive electrode active material, The proportion of the first positive electrode active material may be higher on the side than the second positive electrode active material.
  • a lithium ion secondary battery according to the present invention includes the above-described positive electrode. By using the above positive electrode, it is possible to provide a lithium ion secondary battery having a high energy density and a high output. Furthermore, since the resistance at the end of discharge can be reduced, the range of usable SOC is expanded. Therefore, 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 oxide represented by Li 0.8 M 0.8 O 1.6 has a composition ratio of Li in a full discharge state (2.5 V) when used in a potential range of 2.5 to 4.3 V Is known to be about 0.75.
  • the amount of Li after charge and discharge of the layered solid solution is also estimated to be reduced by about 15 to 30% in the fully discharged state as compared to that before the charge and discharge.
  • 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 4 includes an electrode group including a positive electrode 5 having a positive electrode material coated on both sides of a current collector, a negative electrode 6 having a negative electrode material coated on both sides of the current collector, and a separator 7.
  • the positive electrode 5 and the negative electrode 6 are wound via the separator 7 to form a wound electrode group.
  • the wound body is inserted into the battery can 8.
  • the negative electrode 6 is electrically connected to the battery can 8 via the negative electrode lead piece 10.
  • a sealing lid 11 is attached to the battery can 8 via a packing 12.
  • the positive electrode 5 is electrically connected to the sealing lid 11 through the positive electrode lead piece 9.
  • the wound body is insulated by the insulating plate 13.
  • the electrode group may not be a wound body shown in FIG. 4, and may be a laminate in which the positive electrode 5 and the negative electrode 6 are stacked via the separator 7.
  • 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 and classified with a 45 ⁇ m sieve to obtain a first positive electrode active material represented by the composition formula Li x Ni a Mn b O 2 + ⁇ .
  • the second positive electrode active material was produced by the following method. Lithium carbonate, iron oxalate, and ammonium dihydrogen phosphate were mixed in a ball mill to obtain a precursor. The obtained precursor was calcined at 300 ° C. for 8 hours in argon. Then, after mixing the material after temporary baking with a polyvinyl alcohol by a ball mill, the main baking was performed at 700 ° C. for 8 hours in argon. By this firing, a material in which the positive electrode active material represented by the composition formula LiFePO 4 was covered with the carbon material was obtained. This was used as a second positive electrode active material.
  • Example 1 to 10 and Comparative Examples 2 to 4 and 6 first, the second positive electrode active material, the conductive agent, and the binder were uniformly mixed to prepare a slurry containing the second positive electrode active material.
  • the slurry containing the second positive electrode active material was applied onto a 20 ⁇ m thick aluminum current collector foil and dried at 120 ° C.
  • the first positive electrode active material, the conductive agent, and the binder were uniformly mixed to prepare a slurry containing the first positive electrode active material.
  • the slurry containing the first positive electrode active material was applied over the second positive electrode active material and dried at 120 ° C. After drying, compression molding was performed with a press so that the electrode density was 2.2 g / cm 3 , 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 first positive electrode active material, the conductive agent, and the binder were uniformly mixed to prepare a positive electrode slurry containing the first positive electrode active material.
  • the positive electrode slurry was applied onto a 20 ⁇ m thick aluminum current collector foil and dried at 120 ° C. After drying, compression molding was performed with a press so that the electrode density was 2.2 g / cm 3 , 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 first positive electrode active material, the conductive agent, and the binder were uniformly mixed to prepare a slurry containing the first positive electrode active material.
  • the slurry containing the first positive electrode active material was applied onto a 20 ⁇ m thick aluminum current collector foil and dried at 120 ° C.
  • the second positive electrode active material, the conductive agent, and the binder were uniformly mixed to prepare a slurry containing the second positive electrode active material.
  • the slurry containing the second positive electrode active material was applied over the first positive electrode active material and dried at 120 ° C. After drying, compression molding was performed with a press so that the electrode density was 2.2 g / cm 3 , 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.
  • composition of the first positive electrode active material and the content of the second positive electrode active material used in the positive electrode of each of Examples 1 to 10 and Comparative Examples 1 to 7 are shown in Table 1.
  • 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.
  • FIG. 5 shows discharge curves of Example 5 and Comparative Example 1 at 4.6 to 3.3V.
  • the discharge curve of Example 5 is indicated by a solid line
  • the discharge curve of Comparative Example 1 is indicated by a dotted line.
  • Example 5 has a higher capacity than Comparative Example 1.
  • Example 5 has a higher potential than the Comparative Example 1 when the discharge capacity is the same.
  • Examples 1 to 4 and 6 to 10 the same discharge curves as in Example 5 were obtained. Accordingly, it was found that in Examples 1 to 10, high discharge capacity was obtained in the region where the potential was high.
  • Comparative Example 1 has a smaller discharge capacity and higher DC resistance than the example.
  • the composition of the first positive electrode active material does not satisfy the relationship of 1.15 ⁇ Li / (Ni + Mn) ⁇ 1.5 and 0.334 ⁇ Ni / Mn ⁇ 1, 3.3 V
  • the above discharge capacity is small, and the DC resistance is high because the second positive electrode active material is not included.
  • Comparative Examples 2 to 6 it was not possible to simultaneously achieve high capacity and low resistance.
  • the positive electrode containing the first positive electrode active material and the Fe-containing phosphorus compound having an olivine structure is mixed.
  • the first positive electrode active material already has a high resistance at the end of discharge.
  • the reaction of the Fe-containing phosphorus compound having an olivine structure, which is the second positive electrode active material is completed. Therefore, since the first positive electrode active material having high resistance reacts at the end of discharge, the resistance at the end of discharge can not be improved. Therefore, in Comparative Example 2, the resistance of the second positive electrode active material was not completed before reaching the SOC of 20% in the discharge process, so that the resistance could not be reduced.
  • the first positive electrode in which the atomic weight ratio of Li, Ni, and Mn satisfies the relationships 1.15 ⁇ Li / (Ni + Mn) ⁇ 1.5 and 0.334 ⁇ Ni / Mn ⁇ 1 is satisfied.
  • M ′ is at least any of Mn, Co, Ni, V, Mg, Mo, W, Al, Nb, Ti, and Cu
  • Higher discharge capacity because the second positive electrode active material is contained in the vicinity of the current collector and the second positive electrode active material is disposed in a larger amount than the first positive electrode active material. The resistance at the end of discharge is small. As a result, a lithium ion secondary battery with high energy density and high output can be provided.
  • the discharge capacity is particularly high. This is because the composition of the first positive electrode active material satisfies 0.334 ⁇ Ni / Mn ⁇ 0.8 and the content of the second positive electrode active material is 10% by mass or less.

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une électrode positive de batterie secondaire au lithium-ion et une batterie secondaire au lithium-ion la contenant, et traite du problème consistant à concevoir une batterie secondaire au lithium-ion à haute densité d'énergie et à sortie élevée. La solution au problème mentionné ci-dessus selon l'invention porte sur une électrode positive de batterie secondaire au lithium-ion dotée d'une couche liante d'électrode positive contenant un matériau d'électrode positive et un collecteur de courant comportant la couche liante d'électrode positive formée sur sa surface par adoption d'une configuration selon laquelle le matériau d'électrode positive contient un premier matériau actif d'électrode positive constitué d'une solution solide lamellaire spécifique et un second matériau actif d'électrode positive spécifique qui réagit au potentiel à la période de fin d'une décharge électrique de la solution solide de couche, la couche liante d'électrode positive d'une région en contact avec le collecteur de courant comportant une proportion du second matériau actif d'électrode positive plus élevée que le premier matériau actif d'électrode positive, et la surface de la couche liante d'électrode positive en regard de la surface en contact avec le collecteur de courant comportant une proportion du premier matériau actif d'électrode positive plus élevée que le second matériau actif d'électrode positive.
PCT/JP2013/082119 2013-11-29 2013-11-29 Electrode positive de batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion WO2015079546A1 (fr)

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CN115020635A (zh) * 2022-06-14 2022-09-06 蔚来汽车科技(安徽)有限公司 正极片、锂离子电池和车辆

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JP2007250499A (ja) * 2006-03-20 2007-09-27 Nec Tokin Corp リチウムイオン二次電池
WO2008081839A1 (fr) * 2006-12-27 2008-07-10 Sanyo Electric Co., Ltd. Batterie secondaire électrolytique non aqueuse et son procédé de fabrication
JP2009525568A (ja) * 2006-02-01 2009-07-09 イドロ−ケベック 多層材料、それを製造するための方法、および電極としての使用
JP2009252497A (ja) * 2008-04-04 2009-10-29 Nissan Motor Co Ltd 電池用電極および電池
JP2009252498A (ja) * 2008-04-04 2009-10-29 Nissan Motor Co Ltd 電池用電極
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JP2009525568A (ja) * 2006-02-01 2009-07-09 イドロ−ケベック 多層材料、それを製造するための方法、および電極としての使用
JP2007250499A (ja) * 2006-03-20 2007-09-27 Nec Tokin Corp リチウムイオン二次電池
WO2008081839A1 (fr) * 2006-12-27 2008-07-10 Sanyo Electric Co., Ltd. Batterie secondaire électrolytique non aqueuse et son procédé de fabrication
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115020635A (zh) * 2022-06-14 2022-09-06 蔚来汽车科技(安徽)有限公司 正极片、锂离子电池和车辆
CN115020635B (zh) * 2022-06-14 2024-05-31 蔚来汽车科技(安徽)有限公司 正极片、锂离子电池和车辆

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