WO2015019481A1 - Matériau d'électrode positive pour batteries secondaires au lithium-ion et batterie secondaire au lithium-ion - Google Patents

Matériau d'électrode positive pour batteries secondaires au lithium-ion et batterie secondaire au lithium-ion Download PDF

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WO2015019481A1
WO2015019481A1 PCT/JP2013/071588 JP2013071588W WO2015019481A1 WO 2015019481 A1 WO2015019481 A1 WO 2015019481A1 JP 2013071588 W JP2013071588 W JP 2013071588W WO 2015019481 A1 WO2015019481 A1 WO 2015019481A1
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positive electrode
lithium ion
ion secondary
secondary battery
active material
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PCT/JP2013/071588
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English (en)
Japanese (ja)
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小西　宏明
章 軍司
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/JP2013/071588 priority Critical patent/WO2015019481A1/fr
Priority to PCT/JP2014/065834 priority patent/WO2015019709A1/fr
Publication of WO2015019481A1 publication Critical patent/WO2015019481A1/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
    • H01M4/48—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/58—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 material for a lithium ion secondary battery, and a positive electrode for a lithium ion secondary battery, a lithium ion secondary battery, and a lithium ion secondary battery system including the same.
  • the problem with electric vehicles is that the energy density of the drive battery is low and the distance traveled by one charge is short. Therefore, there is a need for a secondary battery that is inexpensive and has a high energy density.
  • Lithium ion secondary batteries have a higher energy density per weight than secondary batteries such as nickel metal hydride batteries and lead batteries. Therefore, application to electric vehicles and power storage systems is expected. However, in order to meet the demands of 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 is expected.
  • the layered solid solution uses a highly active property while solidly dissolving electrochemically inactive Li 2 MO 3 and electrochemically active LiM′O 2 to extract a high capacity.
  • the layered solid solution can also be represented by the composition formula Li 1 + x M 1-x ′ O 2 .
  • Patent Document 1 discloses a composition formula Li a Mn b M c O z (M represents Ni, Co, Al, and F) in order to provide a battery having a high capacity, excellent storage performance at high temperature, and excellent cycle performance.
  • One or more elements selected from the group consisting of: a lithium manganese-containing oxide represented by 0 ⁇ a ⁇ 2.5, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, 2 ⁇ z ⁇ 3), and an olivine structure
  • a negative electrode containing a titanium-containing metal oxide represented by 0 ⁇ a ⁇ 2.5, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, 2 ⁇ z ⁇ 3
  • the layered solid solution positive electrode active material having the composition shown in Patent Document 1 has a high energy density, but has hysteresis in the open circuit voltage (OCV). That is, the OCV differs depending on the charging process and the discharging process, and there are two OCVs in the same SOC. Therefore, there is a problem that it is difficult to detect the state of charge (SOC) of the battery from the voltage. In particular, when the state of charge cannot be accurately grasped in a region where the SOC is low, it is necessary to allow a surplus in the remaining capacity of the battery, and the capacity of the battery that can be used decreases.
  • SOC state of charge
  • an object of the present invention is to provide a lithium ion secondary battery that can obtain a high energy density and improve the SOC detection accuracy from voltage.
  • First positive electrode active material and composition formula LiFe 1-y M ′ y PO 4 (0 ⁇ y ⁇ 0.2, M ′ is Mn, Co, Ni, V, Mg, Mo, W, Al, Nb , At least one element of Ti and Cu), and the content of the second positive electrode active material is 5% by mass or more and 20% by mass or less with respect to the positive electrode material. It is characterized by.
  • the present invention it is possible to provide a lithium ion secondary battery capable of obtaining high energy density and improving the SOC detection accuracy from voltage.
  • ⁇ Positive electrode material> When a lithium ion secondary battery is employed in an electric vehicle, it is expected that the mileage per charge is long and that the SOC can be detected with high accuracy from the battery voltage. In order to increase the travel distance per charge, the battery is required to have a high energy density. 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 there is a problem that it is difficult to detect the SOC of the battery from the battery voltage. This is because there is hysteresis in the OCV during the charging process and the OCV during the discharging process.
  • the SOC is detected from the battery voltage.
  • the hysteresis in the OCV in the charging process and the OCV in the discharging process means that the OCV in the charging process is different from the OCV in the discharging process in the same SOC. That is, there are two SOCs corresponding to the same potential.
  • the difference between the two SOCs at the same potential is large, a large error occurs when the SOC is detected from the OCV, so that it is difficult to detect the SOC from the battery voltage. Therefore, in order to detect the SOC with high accuracy, it is necessary to suppress the hysteresis of the OCV.
  • the Fe-containing phosphorus compound having an olivine structure typified by LiFePO 4 has a low reaction potential and is constant. Therefore, by mixing the Fe-containing phosphorus compound having an olivine structure with the layered solid solution, the Fe-containing phosphorus compound having the olivine structure is preferentially reacted over the reaction of the layered solid solution in a region where the SOC is low. Reactions involving oxygen that cause hysteresis in the OCV during the charging process and the OCV during the discharging process are suppressed. As a result, the hysteresis of OCV can be suppressed.
  • the detection accuracy be high, particularly in a region where the SOC is low. This is because in a region where the SOC is low, if the SOC error is large, there is a possibility that the battery will run out and the device will not be able to operate.
  • the Fe-containing phosphorus compound having an olivine structure preferentially reacts in a low SOC region, particularly the hysteresis of OCV at the end of discharge is reduced, and the SOC detection error at the end of discharge is reduced. Can be reduced.
  • a high energy density can be obtained even in a high potential region of 3.4 V or higher.
  • x represents the proportion of Li in Li x Ni a Mn b M c O 2 .
  • x represents the proportion of Li in Li x Ni a Mn b M c O 2 .
  • x represents the proportion of Li in Li x Ni a Mn b M c O 2 .
  • x represents the proportion of Li in Li x Ni a Mn b M c O 2 .
  • x represents the proportion of Li in Li x Ni a Mn b M c O 2 .
  • x represents the proportion of Li in Li x Ni a Mn b M c O 2 .
  • M is an additive or impurity such as V, Mo, W, Zr, Nb, Ti, Al, Fe, Mg, Cu, etc., and does not significantly affect the capacity and OCV of the first positive electrode active material. is there.
  • y represents the content ratio (substance ratio) of M ′.
  • M ′ is an element that is added as appropriate, and the amount added must be kept within the range of 0 ⁇ y ⁇ 0.2 so that the effects of the present invention are not suppressed.
  • the layered solid solution below the reaction potential of the Fe-containing phosphorus compound having an olivine structure cannot be used, when the layered solid solution not included in the above composition range and the Fe-containing phosphorus compound having the olivine structure are mixed, when discharged
  • the wasted capacity will increase.
  • the capacity that is wasted can be reduced by using the layered solid solution having the above composition range, the performance of the layered solid solution can be fully utilized, and a high capacity can be obtained.
  • the content of the second positive electrode active material in the positive electrode material is preferably 5% by mass or more and 20% by mass or less. When the content of the second positive electrode active material exceeds 20% by mass, the ratio of the first positive electrode active material is reduced, so that a high energy density cannot be obtained. As for content of the 2nd positive electrode active material with respect to positive electrode material, it is more preferable that it is 10 mass% or less. From the viewpoint of energy density, the content of the first positive electrode active material is preferably 80% by mass or more.
  • the positive electrode material does not contain Co as a transition metal. Since Co is expensive, the positive electrode material according to the present embodiment has an advantage of low cost in addition to high energy density.
  • the present invention does not depend on the mixed state and particle form of the two types of positive electrode active materials, and it is sufficient that the two types of positive electrode active materials are included in the positive electrode material.
  • 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 compounds containing Li, Ni, and Mn at an appropriate ratio and firing.
  • the composition of the positive electrode material can be appropriately adjusted by changing the ratio of the compound to be mixed.
  • the compound containing Li include lithium acetate, lithium nitrate, lithium carbonate, lithium hydroxide, and lithium oxide.
  • the Ni-containing compound include nickel acetate, nickel nitrate, nickel carbonate, nickel sulfate, and nickel hydroxide.
  • the compound containing Mn include manganese acetate, manganese nitrate, manganese carbonate, manganese sulfate, manganese oxide, and the like.
  • the second positive electrode active material is prepared by mixing a compound containing Li, Fe, and P at an appropriate ratio, and then mixing and baking with a carbon source such as polyvinyl alcohol in order to ensure conductivity. can do.
  • Examples of the compound containing Li include lithium acetate, lithium nitrate, lithium carbonate, lithium hydroxide, and lithium oxide.
  • 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 and phosphoric acid.
  • composition of the positive electrode material can be determined by elemental analysis such as by inductively coupled plasma (ICP).
  • ICP inductively coupled plasma
  • a lithium ion secondary battery according to the present invention includes the above positive electrode material.
  • the above positive electrode material for the positive electrode high energy density can be obtained and hysteresis of OCV can be suppressed.
  • the state of charge of the battery can be detected with high accuracy from the battery voltage.
  • the lithium ion secondary battery according to the present invention can be preferably used for an electric vehicle.
  • a lithium ion secondary battery includes a positive electrode including a positive electrode material, a negative electrode including 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 that can occlude and release lithium ions.
  • Substances generally used in lithium ion secondary batteries can be used as the negative electrode material.
  • graphite, a lithium alloy, etc. can be illustrated.
  • separator those generally used in lithium ion secondary batteries can be used.
  • examples thereof include polyolefin microporous films and nonwoven fabrics such as polypropylene, polyethylene, and a copolymer of propylene and ethylene.
  • electrolytic solution and the electrolyte those generally used in lithium ion secondary batteries can be used.
  • 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 as the electrolytic solution.
  • the lithium ion secondary battery 10 includes an electrode group having a positive electrode 1 in which a positive electrode material is applied on both sides of a current collector, a negative electrode 2 in which a negative electrode material is applied on both sides of the current collector, and a separator 3.
  • the positive electrode 1 and the negative electrode 2 are wound through a separator 3 to form a wound electrode group. This wound body is inserted into the battery can 4.
  • the negative electrode 2 is electrically connected to the battery can 4 via the negative electrode lead piece 6.
  • a sealing lid 7 is attached to the battery can 4 via a packing 8.
  • the positive electrode 1 is electrically connected to the sealing lid 7 through the positive electrode lead piece 5.
  • the wound body is insulated by the insulating plate 9.
  • the electrode group may not be the wound body shown in FIG. 1, but may be a laminated body in which the positive electrode 1 and the negative electrode 2 are laminated via the separator 3.
  • a battery system includes the above lithium ion secondary battery.
  • the lithium ion secondary battery system includes a lithium ion secondary battery, a voltage information acquisition unit that detects a battery voltage, a calculation unit that determines a charging state from the voltage, and a battery control unit that controls charging and discharging based on the charging state. .
  • the battery system it is possible to determine the state of charge from the voltage detected by the voltage information acquisition unit, and to control charge / discharge based on the state of charge.
  • a battery system including a lithium ion battery using a layered solid solution as a positive electrode active material has hysteresis in the OCV during the charging process and the OCV during the discharging process of the lithium ion secondary battery, so the accuracy of the SOC estimated from the battery voltage is low. It is difficult to control charge / discharge based on the estimated SOC.
  • the battery system of the present invention since a lithium ion secondary battery with high SOC detection accuracy is used, control based on voltage is possible. As a result, control stability and reliability are improved. In particular, since a secondary battery with high SOC detection accuracy is used in a region where the SOC is low, the SOC is not overestimated and the reliability of management of the remaining capacity of the battery is improved.
  • the 1st positive electrode active material was produced with the following method. Lithium carbonate, nickel carbonate, and manganese carbonate were mixed with a ball mill to obtain a precursor. The obtained precursor was calcined in the atmosphere at 500 ° C. for 12 hours 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 pellets were pulverized in an agate mortar and classified with a 45 ⁇ m sieve to obtain a first positive electrode active material.
  • a second positive electrode active material was produced by the following method. Lithium carbonate, iron oxalate, and ammonium dihydrogen phosphate were mixed with a ball mill to obtain a precursor. The obtained precursor was temporarily calcined at 300 ° C. for 8 hours in argon. Thereafter, the material after provisional baking was mixed with polyvinyl alcohol by a ball mill, and then main baking was performed at 700 ° C. for 8 hours in argon. The fired material was used as the second positive electrode active material.
  • the prepared first and second positive electrode active materials were mixed at an appropriate weight ratio to obtain a positive electrode material.
  • Table 1 shows the composition of the positive electrode material used in each example and comparative example.
  • a positive electrode slurry, a conductive agent, and a binder were mixed uniformly to prepare a positive electrode slurry.
  • the positive electrode slurry was applied onto an aluminum current collector foil having a thickness of 20 ⁇ m, dried at 120 ° C., and compression-molded 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 negative electrode was produced using metallic lithium.
  • a solution obtained by dissolving LiPF 6 at a concentration of 1.0 mol / L in a mixed solvent of ethylene carbonate and dimethyl carbonate having a volume ratio of 1: 2 was used.
  • a charge / discharge test was performed on the prototype battery.
  • the charging was constant current constant voltage charging (CC-CV mode), and the upper limit voltage was 4.6V.
  • the discharge was constant current discharge (CC mode), and the lower limit voltage was 2.5V.
  • the charge / discharge current was 0.05 C, and the charge cutoff current was 0.005 C.
  • the energy density obtained by dividing the energy density in the region of 4.6 to 3.4 V where high output is obtained by the energy density in the region of 4.6 to 3.4 V in Comparative Example 1 is used. Ratio. The results are shown in Table 2.
  • a charge / discharge test was performed on the prototype battery. Charging was in CC-CV mode and the upper limit voltage was 4.6V. The discharge was CC mode and the lower limit voltage was 2.5V. The charge / discharge current was 0.05 C, and the charge cutoff current was 0.005 C. The charge / discharge test was performed for two cycles, and the discharge capacity at the second cycle was defined as the rated capacity. Thereafter, the test of charging to 10% of the rated capacity with a current corresponding to 0.05 C and waiting for 5 hours was repeated until the rated capacity was reached. After charging to the rated capacity, the test of discharging 10% of the rated capacity and waiting for 5 hours was repeated until the battery was fully discharged. At this time, the voltage after 5 hours was defined as OCV.
  • the voltage after charging to 20% of the rated capacity (SOC 20%) from the fully discharged state and waiting for 5 hours is the OCV during the charging process, discharged from the fully charged state to 20% of the rated capacity and waiting for 5 hours.
  • the voltage after the discharge was defined as OCV (SOC 20%) in the discharge process.
  • the voltage after charging to 50% of the rated capacity from the fully discharged state and waiting for 5 hours is the OCV (SOC 50%) in the charging process, and after discharging to 50% of the rated capacity from the fully charged state and waiting for 5 hours was defined as OCV (SOC 50%) of the discharging process.
  • FIG. 2 shows the OCV curve of Example 6, and FIG. 3 shows the OCV curve of Comparative Example 1. 2 and 3, the vertical axis represents OCV (V) and the horizontal axis represents SOC (%).
  • the measurement result of the charging process is shown on the upper side, and the measurement result of the discharging process is shown on the lower side. From FIG. 2, in Example 6, the difference between the OCV in the charging process and the OCV in the discharging process at 10% SOC was less than 0.1V, and the difference between the OCV in the charging process and the OCV in the discharging process at 50% SOC was less than 0.3V. It was.
  • Example 6 can reduce the hysteresis of the OCV during the charging process and the OCV during the discharging process as compared with Comparative Example 1, and in particular, can reduce the hysteresis of the OCV of SOC 10% or less.
  • Example 6 the difference in SOC at the same OCV is 15% or less.
  • Comparative Example 1 it can be seen from FIG. 3 that the difference in SOC at the same OCV is about 30%. From the above, by using the positive electrode material of Example 6, a battery with high SOC detection accuracy can be provided.
  • the OCV ratio at SOC 50% and the OCV ratio at SOC 20% are lower.
  • the positive electrode materials of Examples 1 to 14 contain the second positive electrode active material LiFePO 4 . Therefore, it has been found that by mixing Li x Ni a Mn b O 2 and LiFePO 4 , it is possible to suppress the hysteresis of the OCV during the charging process and the OCV during the discharging process, particularly in a low SOC region.
  • the composition of the first positive electrode active material is included in the range of 1 ⁇ x ⁇ 1.2 and 0.2 ⁇ a ⁇ 0.4, but does not include the second positive electrode active material. Therefore, the OCV ratio is high.
  • Examples 1 to 4 have a higher energy density ratio than Comparative Examples 5 and 6. This is because the molar ratio of Li is in the range of 1 ⁇ x ⁇ 1.2. In Examples 1 and 2, the energy density ratio is particularly high. This is because the molar ratio of Li is included in the range of 1 ⁇ x ⁇ 1.15.
  • Comparative Example 4 since the amount of Li in the first positive electrode active material was too small, the amount of Li that can participate in the reaction was small and the energy density was lowered.
  • Comparative Example 6 since the amount of Li in the first positive electrode active material was too large, the crystal structure became unstable and the energy density decreased.
  • FIG. 4 shows the relationship between the Ni content and the OCV ratio in Examples 1, 5, and 8 and Examples 3, 7, and 10.
  • FIG. 4 shows that the OCV ratio decreases as the Ni content increases.
  • filled a ⁇ b it turned out that an energy density ratio becomes high. Therefore, it can be seen that when the Ni content is in the range of 0.2 ⁇ a ⁇ 0.4, the energy density ratio is high and the OCV ratio is small.
  • Examples 1, 11, and 12 have a higher energy density ratio and a lower OCV ratio than Comparative Example 7. This is because the contents of the second positive electrode active materials in Examples 1, 11, and 12 are 5% by mass or more and 20% by mass or less. On the other hand, since the comparative example 7 contained 30 mass% of the second positive electrode active material, the energy density ratio was low. In addition, Example 11 has a lower energy density than Examples 1 and 12. This is because the content of the first positive electrode active material capable of obtaining a high energy density was less than 90% by mass.
  • the energy density ratio is particularly high and the OCV ratio is low. This is because the composition of the first positive electrode active material is in the range of 1 ⁇ x ⁇ 1.15, 0.2 ⁇ y ⁇ 0.4, and the second positive electrode active material is 10% by mass or less of the positive electrode active material. Because it was.
  • a high energy density can be obtained even in a high potential region of 3.4 V or more, and the charging process It is possible to provide a lithium ion secondary battery that can suppress the hysteresis of the OCV and the OCV during the discharge process and can detect the SOC from the voltage with high accuracy. In particular, the detection accuracy in a low SOC region can be improved.

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Abstract

La présente invention a pour objet de réaliser une batterie secondaire au lithium-ion qui possède une densité d'énergie élevée et qui est capable d'offrir une précision de détection d'état de charge améliorée dans la phase finale de la décharge. Cet objet peut être réalisé par un matériau d'électrode positive pour batteries secondaires au lithium-ion qui est caractérisé en ce qu'il contient un premier matériau actif d'électrode positive qui est représenté par la formule de composition LixNiaMnbMcO2 (où 1 < x ≤ 1,2, 0,2 < a ≤ 0,4, 0,4 ≤ b < 0,6, 0 ≤ c ≤ 0,02, a + b + c = 0,8, et M représente au moins un élément sélectionné parmi V, Mo, W, Zr, Nb, Ti, Al, Fe, Mg et Cu) et un deuxième matériau actif d'électrode positive qui est représenté par la formule de composition LiFe1-yM'yPO4 (où 0 ≤ y ≤ 0,2 et M' représente au moins un élément sélectionné parmi Mn, Co, Ni, V, Mg, Mo, W, Al, Nb, Ti et Cu), et qui est également caractérisé en ce que la teneur en deuxième matériau actif d'électrode positive est de 5 % massiques à 20 % massiques (inclus).
PCT/JP2013/071588 2013-08-09 2013-08-09 Matériau d'électrode positive pour batteries secondaires au lithium-ion et batterie secondaire au lithium-ion WO2015019481A1 (fr)

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PCT/JP2014/065834 WO2015019709A1 (fr) 2013-08-09 2014-06-16 Matériau d'électrode positive pour accumulateur lithium-ion, et accumulateur lithium-ion

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN116525815A (zh) * 2023-06-30 2023-08-01 宜宾锂宝新材料有限公司 球形镍锰酸锂正极材料、其制备方法和复合正极材料

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000195558A (ja) * 1998-12-28 2000-07-14 Toyota Central Res & Dev Lab Inc 非水電解液二次電池の充放電制御装置
JP2005019385A (ja) * 2003-05-30 2005-01-20 Matsushita Electric Ind Co Ltd 非水電解質二次電池の充電方法および充電器
JP2007250299A (ja) * 2006-03-15 2007-09-27 Hitachi Vehicle Energy Ltd 非水電解液二次電池
JP2010033924A (ja) * 2008-07-30 2010-02-12 Nec Tokin Corp リチウムイオン二次電池用正極、およびそれを用いたリチウムイオン二次電池
JP2010225486A (ja) * 2009-03-25 2010-10-07 Toshiba Corp 非水電解質電池
JP2013520783A (ja) * 2010-02-24 2013-06-06 エルジー ケム． エルティーディ． 出力向上のための正極活物質およびこれを含むリチウム二次電池

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5853662B2 (ja) * 2011-12-15 2016-02-09 株式会社Ｇｓユアサ 非水電解質電池の使用方法、及び、非水電解質電池を搭載したプラグインハイブリッド自動車
KR101382797B1 (ko) * 2012-03-22 2014-04-08 삼성정밀화학 주식회사 리튬이온 이차전지용 양극활물질 및 그것을 포함하는 리튬이온 이차전지

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000195558A (ja) * 1998-12-28 2000-07-14 Toyota Central Res & Dev Lab Inc 非水電解液二次電池の充放電制御装置
JP2005019385A (ja) * 2003-05-30 2005-01-20 Matsushita Electric Ind Co Ltd 非水電解質二次電池の充電方法および充電器
JP2007250299A (ja) * 2006-03-15 2007-09-27 Hitachi Vehicle Energy Ltd 非水電解液二次電池
JP2010033924A (ja) * 2008-07-30 2010-02-12 Nec Tokin Corp リチウムイオン二次電池用正極、およびそれを用いたリチウムイオン二次電池
JP2010225486A (ja) * 2009-03-25 2010-10-07 Toshiba Corp 非水電解質電池
JP2013520783A (ja) * 2010-02-24 2013-06-06 エルジー ケム． エルティーディ． 出力向上のための正極活物質およびこれを含むリチウム二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116525815A (zh) * 2023-06-30 2023-08-01 宜宾锂宝新材料有限公司 球形镍锰酸锂正极材料、其制备方法和复合正极材料
CN116525815B (zh) * 2023-06-30 2023-11-17 宜宾锂宝新材料有限公司 球形镍锰酸锂正极材料、其制备方法和复合正极材料

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