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WO2015019482A1 - Matériau d'électrode positive pour piles rechargeables lithium-ion - Google Patents

Matériau d'électrode positive pour piles rechargeables lithium-ion Download PDF

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Publication number
WO2015019482A1
WO2015019482A1 PCT/JP2013/071589 JP2013071589W WO2015019482A1 WO 2015019482 A1 WO2015019482 A1 WO 2015019482A1 JP 2013071589 W JP2013071589 W JP 2013071589W WO 2015019482 A1 WO2015019482 A1 WO 2015019482A1
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WIPO (PCT)
Prior art keywords
positive electrode
lithium ion
ion secondary
secondary battery
active material
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Ceased
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PCT/JP2013/071589
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English (en)
Japanese (ja)
Inventor
小西　宏明
章 軍司
孝亮 馮
翔 古月
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Hitachi Ltd
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Hitachi Ltd
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Priority to PCT/JP2013/071589 priority Critical patent/WO2015019482A1/fr
Priority to PCT/JP2014/066764 priority patent/WO2015019729A1/fr
Publication of WO2015019482A1 publication Critical patent/WO2015019482A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • 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
    • H01M4/48—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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, a positive electrode for a lithium ion secondary battery including the positive electrode material, and a lithium ion secondary battery.
  • 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, a secondary battery having a high energy density is demanded.
  • 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 a high energy density of the battery, 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 lithium-containing transition metal oxide Li a having a hexagonal layered rock salt type crystal structure belonging to the space group R-3m in order to provide a lithium battery having low electric resistance and high output.
  • Ni x Mn y O 2 (1 ⁇ a ⁇ 1.5,0.5 ⁇ x + y ⁇ 1,0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1) lithium manganese oxide having a spinel structure Li 1 + b Mn 2 -b O 4 is used (0 ⁇ b ⁇ 0.33) and the combined cathode material.
  • the state of charge (SOC: State of Charge) is detected from the battery voltage.
  • SOC State of Charge
  • the layered solid solution positive electrode 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 in the charging process is different from the OCV in the discharging process, and there are two OCVs in the same SOC. Therefore, it is difficult to detect the SOC of the battery from the OCV. If the SOC cannot be accurately grasped, it is necessary to see a margin in the state of charge, and the battery capacity that can be used decreases.
  • an object of the present invention is to provide a lithium ion secondary battery that can obtain a high energy density and can improve the accuracy of SOC detection.
  • the present invention it is possible to provide a lithium ion secondary battery having high energy density and capable of detecting SOC with high 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 from the battery voltage with high accuracy. In order to increase the travel distance per charge, a high energy density is required. 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 the OCV has hysteresis.
  • the SOC is detected from the battery voltage.
  • the hysteresis in the OCV 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. When the difference between two SOCs at the same potential is large, an error in detecting the SOC from the OCV becomes large. Therefore, if the OCV has hysteresis, it is difficult to detect the SOC from the battery voltage. Therefore, in order to improve the accuracy in detecting the SOC from the battery voltage, it is necessary to suppress the hysteresis of the OCV.
  • the 5V class spinel compound represented by LiNi 0.5 Mn 1.5 O 4 has a high reaction potential and is constant. Therefore, by mixing a 5V class spinel compound with the layered solid solution, it is possible to avoid the use of the layered solid solution and use the 5V class spinel compound in a region where the SOC is high (at the end of charging). As a result, it is possible to suppress hysteresis between the OCV during the charging process and the OCV during the discharging process.
  • x represents the ratio of Li in Li x Ni a Mn b M1 c O 2 .
  • x represents the ratio of Li in Li x Ni a Mn b M1 c O 2 .
  • x represents the amount of Li contributing to the reaction is reduced, and a high capacity cannot be obtained.
  • x is larger than 1.2, the crystal lattice becomes unstable, and the discharge capacity decreases.
  • a represents the content ratio (substance ratio) of Ni in the first positive electrode active material.
  • a is 0.2 or less, the contribution of oxygen to the charge / discharge capacity increases, and the OCV hysteresis during the charge process and the OCV during the discharge process increase.
  • M1 is an additive or impurity contained at a composition ratio of 0.02 or less, and does not significantly affect the capacity and OCV of the first positive electrode active material. M1 may contain two or more elements.
  • y represents the Ni content ratio (substance ratio) of LiNi 0.5 + y Mn 1.5-y M2 z O 4 . Since the Ni content is related to the reacting capacity in the vicinity of 4.7 V, it is necessary to keep it in a range of ⁇ 0.2 ⁇ z ⁇ 0.2 so that the effect of the present invention is not suppressed.
  • M2 is an additive or an impurity contained in a composition ratio of 0.02 or less, and does not significantly affect the capacity and OCV of the second positive electrode active material.
  • M2 is Co, Al, Mg, or the like, and may contain two or more elements.
  • the positive electrode material does not contain Co. 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 content of the first positive electrode active material is preferably 80% by mass or more with respect to the positive electrode material, and the content of the second positive electrode active material is preferably 20% by mass or less with respect to the positive electrode material.
  • content of a 2nd positive electrode active material it is more preferable that it is 10 mass% or less with respect to positive electrode material.
  • 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.
  • the second positive electrode active material In order to reduce the difference between the OCV in the charging process and the OCV in the discharging process, the second positive electrode active material only needs to be contained in an amount of 5% or more with respect to the positive electrode active 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. For example, it can be prepared 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.
  • Examples of the compound containing Li include lithium acetate, lithium nitrate, lithium carbonate, lithium hydroxide, and lithium oxide.
  • Examples of the Ni-containing compound include nickel acetate, nickel nitrate, nickel carbonate, nickel sulfate, and nickel hydroxide.
  • Examples of the compound containing Mn include manganese acetate, manganese nitrate, manganese carbonate, manganese sulfate, manganese oxide, and the like.
  • composition of the positive electrode material can be determined by elemental analysis such as by inductively coupled plasma (ICP).
  • ICP inductively coupled plasma
  • the positive electrode material according to the present invention does not depend on the mixed state and particle form of two types of positive electrode active materials, and it is sufficient that two types of materials are included.
  • the positive electrode material may further contain an Fe-containing phosphorus compound having an olivine structure such as LiFePO 4 as the third positive electrode active material.
  • an Fe-containing phosphorus compound having an olivine structure such as LiFePO 4 as the third positive electrode active material.
  • the Fe-containing phosphorus compound having an olivine structure When the Fe-containing phosphorus compound having an olivine structure is mixed with the positive electrode material, the Fe-containing phosphorus compound having an olivine structure reacts preferentially in a region where the SOC is low, thereby causing OCV hysteresis of the layered solid solution. Reactions involving oxygen can be suppressed. As a result, OCV hysteresis can be reduced, particularly at the end of discharge, and the accuracy of detection of the remaining battery level can be improved.
  • Fe-containing phosphorus compound having an olivine structure has the composition formula LiFe 1-d M3 d PO 4 (0 ⁇ d ⁇ 0.2, M3 is Mn, Co, Ni, V, Mg, Mo, W, Al, Nb, Ti And at least any element of Cu).
  • d shows the content ratio (substance ratio) of M3.
  • M ′ is an element that is added as appropriate, and the amount added must be kept within the range of 0 ⁇ d ⁇ 0.2 so that the effects of the present invention are not suppressed.
  • the content of the third positive electrode active material with respect to the whole positive electrode material is preferably 20% by mass or less.
  • the content of the third positive electrode active material is more preferably 10% by mass or less. If the content of the third positive electrode active material is too large, the content of the layered solid solution is reduced, so that a high energy density cannot be obtained.
  • the third positive electrode active material is preferably contained at 5% or more with respect to the positive electrode material.
  • 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 it is possible to provide a lithium ion secondary battery that has high energy density and suppresses hysteresis between OCV during charging and OCV during discharging. Therefore, the SOC can be detected with high accuracy from the OCV.
  • the lithium ion secondary battery using the positive electrode material according to the present invention can be used in a potential range of 3.4 V to 4.8 V.
  • the lithium ion secondary battery according to the present invention can be preferably used for, for example, 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 includes a negative electrode active material capable of occluding and releasing lithium ions.
  • a material generally used in a lithium ion secondary battery can be used as the negative electrode active 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.
  • a 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 circuit that controls charging and discharging based on the charging state . According to 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 charging / discharging 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, so the accuracy of the SOC estimated from the battery voltage is low, and the estimated SOC is It is difficult to control charging and discharging.
  • the battery system of the present invention since a lithium ion secondary battery with high SOC detection accuracy is used, charge / discharge control based on the SOC becomes possible. As a result, control stability and reliability are improved.
  • the battery system according to the present invention uses a lithium ion secondary battery with high accuracy particularly in a high SOC region, overcharge due to an estimated SOC error can be prevented.
  • 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, nickel carbonate, and manganese carbonate were mixed with a ball mill to obtain a precursor. The obtained precursor was calcined in the atmosphere at 900 ° C. for 12 hours to obtain a lithium transition metal oxide. The obtained lithium transition metal oxide was pelletized and then calcined at 700 ° C. for 12 hours in oxygen. The fired pellets were pulverized in an agate mortar and classified with a 45 ⁇ m sieve to obtain a second positive electrode active 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.
  • ⁇ Charge / discharge test> a charge / discharge test was performed on 19 types of prototype batteries produced as described above.
  • the charging was constant current constant voltage charging (CC-CV mode), and the upper limit voltage was 4.8V.
  • 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 is obtained by dividing the energy density in the region of 4.8 to 3.4 V where high output is obtained by the energy density in the region of 4.8 to 3.4 V in comparative example 1. Ratio. Table 2 shows the results of the charge / discharge test.
  • a charge / discharge test was performed on the prototype battery. Charging was in CC-CV mode, and the upper limit voltage was 4.8V. 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. Then, 10% of the rated capacity was charged with a current corresponding to 0.05 C, and the test of 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 rated capacity reached 0%. At this time, the voltage after 5 hours was defined as OCV.
  • the upper limit potential of charging was 4.8 V, and when this potential was reached, charging was terminated at that point.
  • the voltage after charging to 50% of the rated capacity from the fully discharged state and waiting for 5 hours is the OCV during the charging process
  • the voltage after discharging to 50% of the rated capacity from the fully charged state and waiting for 5 hours was defined as the OCV of the discharge process.
  • a value obtained by dividing the difference between the OCV in the charging process and the OCV in the discharging process by the difference between the OCV in the charging process and the OCV in the discharging process in Comparative Example 1 was defined as the OCV ratio (SOC 50%).
  • the voltage after charging to 90% of the rated capacity from the fully discharged state and waiting for 5 hours is the OCV in the charging process
  • the voltage after discharging to 10% of the rated capacity from the fully charged state and waiting for 5 hours was obtained by dividing the difference between the OCV in the discharging process and the OCV (SOC 90%) in the charging process and the OCV (SOC 90%) in the discharging process of Comparative Example 1. The results are shown in Table 1.
  • FIG. 2 shows the OCV curve of Example 6, and FIG. 3 shows the OCV curve of Comparative Example 1.
  • 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.
  • the difference between the OCV in the charging process and the OCV in the discharging process when the SOC is 50% is less than 0.5V
  • FIG. 3 the difference between the OCV in the charging process and the OCV in the discharging process when the SOC is 50%.
  • the difference in SOC at the same potential is 15% or less.
  • the difference in SOC at the same potential exceeds 15%.
  • the OCV hysteresis can be reduced as compared with the material of the layered solid solution having a low Ni content.
  • the reaction involving oxygen causing the OCV difference of the layered solid solution is suppressed.
  • the same element type as in the charging process contributes to the reaction, and OCV hysteresis is reduced.
  • Examples 1 to 13 have a higher energy density ratio and a lower OCV ratio. This is because the positive electrode materials of Examples 1 to 13 include the first positive electrode active material and the second positive electrode active material, and the composition of the first positive electrode active material is 1 ⁇ x ⁇ 1.15, 0.2 ⁇ . It is because it was in the range of a ⁇ 0.4. On the other hand, in Comparative Example 2, the composition of the first positive electrode active material is included in the range of 1 ⁇ x ⁇ 1.15 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 4 and 5. This is because the composition of the first positive electrode active material 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 composition of the first positive electrode active material is 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 5 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.
  • Examples 1 to 3, 5 to 7 have high energy density ratios. This is because the first positive electrode active material satisfies a ⁇ b. Moreover, it turns out that OCV ratio becomes small as Ni content becomes high.
  • FIG. 4 shows the relationship between the Ni content of the example and the OCV ratio. Therefore, in order to suppress a high energy density ratio and OCV hysteresis, the first positive electrode active material preferably satisfies 0.2 ⁇ a ⁇ 0.4.
  • the energy density ratio is particularly high and the OCV ratio is small. This is because the composition of the first positive electrode active material is in the range of 1 ⁇ x ⁇ 1.15 and 0.2 ⁇ a ⁇ 0.4, and the second positive electrode active material is 10% or less of the whole positive electrode. This is because.
  • a high energy density can be obtained even in a high potential region of 3.4 V or more, and the OCV difference between the charging process and the discharging process can be reduced. it can.

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Abstract

L'objectif de la présente invention est de pourvoir à une pile rechargeable lithium-ion qui possède une haute densité d'énergie et soit apte à détecter l'état de charge (SOC) avec une haute précision. L'objectif peut être atteint par un matériau d'électrode positive pour piles rechargeables 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 LixNiaMnbM1cO2 (dans laquelle 1 < x ≤ 1,2, 0,2 < a ≤ 0,4, 0,4 ≤ b < 0,6, 0 ≤ c < 0,02, a + b + c = 0,8 et M1 représente un élément tel que V, Mo, W, Zr, Nb, Ti, Al, Fe, Cu ou Co) et un second matériau actif d'électrode positive qui est représenté par la formule de composition LiNi0,5+yMn1,5-yM2zO4 (dans laquelle -0,2 ≤ y ≤ 0,2, 0 ≤ z ≤ 0,02 et M2 représente un élément tel que Co, Al ou Mg), et qui est également caractérisé en ce que la proportion du second matériau actif d'électrode positive va de 5% en poids à 20% en poids (inclus) par rapport au matériau d'électrode positive.
PCT/JP2013/071589 2013-08-09 2013-08-09 Matériau d'électrode positive pour piles rechargeables lithium-ion Ceased WO2015019482A1 (fr)

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PCT/JP2014/066764 WO2015019729A1 (fr) 2013-08-09 2014-06-25 Matériau d'électrode positive pour des batteries secondaires au lithium-ion

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JP2023105454A (ja) * 2022-01-19 2023-07-31 トヨタ自動車株式会社 Ｓｏｃ推定方法

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CN106226705B (zh) * 2016-08-29 2019-09-20 超威电源有限公司 一种铅酸蓄电池电极电位检测方法

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