WO2014050115A1 - Batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux Download PDF

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WO2014050115A1
WO2014050115A1 PCT/JP2013/005720 JP2013005720W WO2014050115A1 WO 2014050115 A1 WO2014050115 A1 WO 2014050115A1 JP 2013005720 W JP2013005720 W JP 2013005720W WO 2014050115 A1 WO2014050115 A1 WO 2014050115A1
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secondary battery
borate
electrolyte secondary
rare earth
aqueous electrolyte
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PCT/JP2013/005720
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English (en)
Japanese (ja)
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山本　諭
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三洋電機株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 non-aqueous electrolyte secondary battery, and more particularly to improvement of battery performance of the non-aqueous electrolyte secondary battery.
  • Non-aqueous electrolyte secondary batteries represented by lithium ion secondary batteries have high energy density and high voltage, so they are used as driving power sources for mobile information terminals such as mobile phones and laptop computers, and electric vehicles. It has been.
  • Patent Document 1 discloses a technique in which a positive electrode contains at least one compound that is a hydroxide salt, a borate salt, or a silicate salt and whose aqueous solution is alkaline. Proposed. According to the technique of Patent Document 1, the storage performance and cycle performance of the nonaqueous electrolyte battery can be improved.
  • non-aqueous electrolyte secondary batteries used as drive power sources are also required to have higher capacities.
  • raising the end-of-charge voltage has been studied.
  • Patent Document 2 proposes a technique in which a positive electrode active material that contains fluoroethylene carbonate as a solvent in a nonaqueous electrolytic solution and adheres to the surface in a state where fine particles of a rare earth element compound are dispersed is included in the positive electrode. Yes.
  • a positive electrode active material that contains fluoroethylene carbonate as a solvent in a nonaqueous electrolytic solution and adheres to the surface in a state where fine particles of a rare earth element compound are dispersed is included in the positive electrode.
  • Cathode active material particles adhered to the surface in a state where fine particles of rare earth element compound are dispersed usually have a rare earth element hydroxide adhered to the surface of the cathode active material particles, and the cathode active material particles are dried and heat-treated. It is produced by.
  • a coprecipitation method, a wet powder method (spray coating), or the like is generally used. Through such a process, alkaline components such as LiOH and Li 2 CO 3 present on the surface of the positive electrode active material particles are washed.
  • the decomposition of the non-aqueous electrolyte is accelerated starting from this, causing a significant decrease in battery performance.
  • the alkali component is too small, there is no substance that neutralizes HF produced by thermal decomposition of a fluorinated nonaqueous solvent or oxidative decomposition of a Li salt, and the pH of the nonaqueous electrolyte tends to be low. Under such a low pH environment, the fluorinated non-aqueous solvent becomes unstable due to impaired oxidation resistance, and oxidative decomposition at the positive electrode is accelerated. Furthermore, the transition metal is eluted from the positive electrode active material and the polarization resistance of the positive electrode is increased, and the battery characteristics are deteriorated. In addition, such a decrease in battery characteristics becomes significant under a high temperature environment.
  • an object of the present invention is to provide a high-capacity nonaqueous electrolyte secondary battery excellent in high-temperature battery characteristics such as high-temperature storage characteristics and high-temperature cycle characteristics.
  • the present invention relates to a non-aqueous electrolyte secondary battery comprising a positive electrode having lithium transition metal composite oxide particles as a positive electrode active material, a negative electrode, and a non-aqueous electrolyte.
  • the rare earth compound is at least one selected from the group consisting of rare earth hydroxides and rare earth oxyhydroxides, and the positive electrode contains a borate and is a nonaqueous electrolyte. Includes a fluorinated non-aqueous solvent.
  • oxidative decomposition of the nonaqueous electrolyte can be suppressed even in a high temperature environment.
  • decomposition of the fluorinated non-aqueous solvent or the fluorinated lithium salt having high oxidation resistance is suppressed even under a high temperature environment. Even if these two effects act synergistically to increase the end-of-charge voltage and increase the capacity, it is considered that the high-temperature battery characteristics such as high-temperature storage characteristics and high-temperature cycle characteristics can be significantly improved.
  • the average particle diameter of the lithium transition metal composite oxide particles as the positive electrode active material is larger than the average particle diameter of the rare earth compound particles.
  • the average particle size of the lithium transition metal composite oxide particles can be 3 to 30 ⁇ m.
  • the average particle diameter of the rare earth compound particles is preferably 100 nm or less.
  • the average particle diameter of the lithium transition metal composite oxide particles and the average particle diameter of the rare earth compound particles can be determined using, for example, a scanning electron microscope.
  • the borate includes lithium borate, sodium borate, potassium borate, calcium borate, barium borate, manganese tetraborate, cobalt borate, nickel borate, And at least one selected from the group consisting of aluminum borate.
  • the borate is selected from the group consisting of LiBO 2 , Li 2 B 4 O 7 , LiB 3 O 5 , and Li 2 B 8 O 13 because the effect of suppressing decomposition of a fluorinated non-aqueous solvent is high.
  • at least one lithium borate is used.
  • the borate as described above is chemically stable and can be obtained relatively easily.
  • the ratio of the borate mass to the total mass of the lithium transition metal composite oxide and borate may be 0.1 to 5.0 mass%. it can. Thereby, decomposition
  • the number of moles of the rare earth element of the rare earth compound may be 0.01 to 0.3 mol% with respect to the number of moles of the lithium transition metal composite oxide.
  • the rare earth compound can include at least one rare earth element selected from Nd, Sm, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
  • the fluorinated non-aqueous solvent includes a fluorinated cyclic carbonate such as fluoroethylene carbonate and trifluoropropylene carbonate, and a fluorinated chain carbonate such as ethyl fluoromethyl carbonate and fluoroethyl ethyl carbonate. It can be set as the structure which is at least 1 sort (s) of fluorinated carbonate selected from the group which consists of. These fluorinated carbonates have high oxidation resistance and are easily available. The type and amount of the fluorinated carbonate are appropriately selected in consideration of desired oxidation resistance and the viscosity of the nonaqueous electrolyte.
  • the non-aqueous electrolyte includes a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the nonaqueous solvent may be composed of only a fluorinated nonaqueous solvent, or may be composed of a fluorinated nonaqueous solvent and a solvent other than the fluorinated nonaqueous solvent.
  • the concentration of the fluorinated non-aqueous solvent in the non-aqueous electrolyte is 0.5% by mass or more and 20% by mass or less. Is preferable, and it is more preferable to set it as 5 mass% or less.
  • the present invention it is possible to provide a high-capacity nonaqueous electrolyte secondary battery excellent in high-temperature battery characteristics such as high-temperature storage characteristics and high-temperature cycle characteristics.
  • FIG. 1 is a graph showing a change in capacity retention rate when the charge / discharge cycle of the battery according to Example 1 and the battery according to Comparative Example 1 is repeated.
  • Example 1 [Preparation of positive electrode active material]
  • nickel, cobalt, lithium manganate, and lithium cobaltate were used as the positive electrode active material.
  • Nickel, cobalt and lithium manganate were synthesized as follows. Lithium hydroxide hydrate (LiOH.H 2 O) was used as the lithium source.
  • a nickel-cobalt-manganese composite hydroxide containing nickel, cobalt, and manganese in predetermined amounts was obtained by a coprecipitation method.
  • the obtained composite hydroxide and lithium hydroxide were mixed so that the molar ratio of lithium to the total of nickel, cobalt, and manganese was 1.03: 1.
  • This mixture was calcined at 400 ° C. for 12 hours in an oxygen atmosphere, the obtained calcined product was pulverized in a mortar, and this pulverized product was calcined at 850 ° C. for 24 hours in an oxygen atmosphere.
  • Lithium acid LiNi 0.5 Co 0.2 Mn 0.3 O 2
  • the obtained nickel / cobalt / lithium manganate was ground in an mortar until the average particle size became 15 ⁇ m.
  • the chemical composition of nickel, cobalt, and lithium manganate was measured with an ICP (Inductively Coupled Plasma) emission analyzer.
  • the solid content was suction filtered from the above suspension, washed with water, and the obtained powder was dried at 120 ° C.
  • nickel, cobalt, and lithium manganate particles having erbium hydroxide uniformly adhered to the surface were obtained.
  • Nickel / cobalt / lithium manganate particles with erbium hydroxide adhered were heat-treated in air at 300 ° C. for 5 hours, and at least part of the erbium hydroxide was changed to erbium oxyhydroxide, thereby erbium hydroxide.
  • nickel / cobalt / lithium manganate particles having erbium oxyhydroxide particles adhering to the surface thereof were obtained, and these particles were designated as positive electrode active material particles a-1.
  • erbium compound particles having an average particle diameter of 100 nm or less were found to be uniformly dispersed on the surfaces of the nickel, cobalt, and lithium manganate particles. It was confirmed that it was adhered.
  • the adhesion amount of the erbium compound particles was 0.10 mol% with respect to nickel, cobalt, and lithium manganate in terms of erbium element.
  • the adhesion amount of erbium compound particles was measured with an ICP emission spectrometer.
  • Lithium cobaltate was synthesized as follows. Lithium carbonate (Li 2 CO 3 ) was used as the lithium source. As the cobalt source, tricobalt tetroxide (Co 3 O 4 ) obtained by calcining cobalt carbonate at 550 ° C. and thermal decomposition reaction was used.
  • Lithium carbonate Li 2 CO 3
  • cobalt source tricobalt tetroxide (Co 3 O 4 ) obtained by calcining cobalt carbonate at 550 ° C. and thermal decomposition reaction was used.
  • Lithium carbonate and tricobalt tetroxide were weighed so that the molar ratio of lithium to cobalt was 1: 1. Thereafter, these were mixed in a mortar, and the obtained mixture was fired at 850 ° C. for 20 hours in an air atmosphere to obtain lithium cobaltate (LiCoO 2 ). The obtained lithium cobaltate was ground to an average particle size of 15 ⁇ m in a mortar.
  • lithium cobaltate particles having erbium compound particles composed of at least one selected from the group consisting of erbium hydroxide and erbium oxyhydroxide attached to the surface This was designated as positive electrode active material particles a-2.
  • the adhesion amount of erbium compound particles was 0.10 mol% with respect to lithium cobaltate in terms of erbium element.
  • the positive electrode active material particles a-1 and the positive electrode active material particles a-2 were mixed at a mass ratio of 70:30.
  • the obtained mixed active material and Li 2 B 4 O 7 were mixed at a mass ratio of 99: 1.
  • 96 parts by mass of the obtained mixture, 2 parts by mass of carbon powder as a conductive agent, 2 parts by mass of polyvinylidene fluoride powder as a binder, and N-methylpyrrolidone were mixed to prepare a positive electrode slurry.
  • This positive electrode slurry was applied to both surfaces of an aluminum positive electrode current collector having a thickness of 15 ⁇ m by a doctor blade method so that the coating mass was 21.2 mg / cm 2 on one side and 42.4 mg / cm 2 on both sides.
  • the length of the coated portion along the positive electrode current collector length direction on one surface of the positive electrode current collector is 277 mm
  • the length of the uncoated portion is 57 mm
  • the length of the positive electrode current collector on the other surface is The length of the coated part along the direction was 208 mm
  • the length of the uncoated part was 126 mm.
  • the length of the coated portion along the length direction of the negative electrode current collector on one surface of the negative electrode current collector is 284 mm
  • the length of the uncoated portion is 18 mm
  • the length of the negative electrode current collector on the other surface The length of the coated part along the direction was 226 mm, and the length of the uncoated part was 73 mm.
  • the negative electrode current collector coated with the negative electrode slurry was passed through a dryer and dried to obtain an electrode plate. This electrode plate was compressed using a compression roller so that the thickness of the coated part on both sides was 155 ⁇ m.
  • a negative electrode having a negative electrode active material layer formed on both sides of the negative electrode current collector was obtained.
  • the potential of graphite at the time of charging is about 0.1 V with respect to Li.
  • the positive electrode and negative electrode active material filling amount is obtained by setting the charge capacity ratio (negative electrode charge capacity / positive electrode charge capacity) of the positive electrode and the negative electrode to 1. It adjusted so that it might be set to 1.
  • LiPF 6 was dissolved in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 30:70 (25 ° C., 1 atm) to a concentration of 1 mol / L.
  • vinylene carbonate (VC) was added to a concentration of 1% by mass
  • fluoroethylene carbonate (FEC) was added to a concentration of 2.0% by mass. In this way, a non-aqueous electrolyte was prepared.
  • Electrode body An aluminum lead wire is welded to the positive electrode, a nickel lead wire is welded to the negative electrode, and the positive electrode and the negative electrode are wound in a flat shape through a separator made of a polyethylene microporous film to form a spiral electrode body. Produced.
  • Example 2 to 9 instead of erbium hydroxide and / or erbium oxyhydroxide, the types of rare earth elements contained in the rare earth hydroxide and / or rare earth oxyhydroxide present on the surfaces of the positive electrode active materials a-1 and a-2 are listed.
  • the batteries of Examples 2 to 9 were produced in the same manner as in Example 1 except that the changes were made as shown in FIG.
  • Examples 10 to 17 Batteries of Examples 10 to 14 were fabricated in the same manner as in Example 1, except that the type and amount of borate were changed as shown in Table 2. Further, Examples 10 to 12 except that lutetium hydroxide and / or lutetium oxyhydroxide was used as the rare earth hydroxide and / or rare earth oxyhydroxide present on the surfaces of the positive electrode active materials a-1 and a-2. Similar Examples 15 to 17 were produced.
  • Example 18 was produced in the same manner as Example 9 except that the positive electrode active material particles a-1 and the positive electrode active material particles a-2 were mixed at a mass ratio of 30:70.
  • Example 19 was produced in the same manner as Example 9 except that the positive electrode active material was not a mixed active material and only LiNi 0.33 Co 0.34 Mn 0.33 O 2 was used.
  • Example 19 was produced in the same manner as Example 9 except that the positive electrode active material was not a mixed active material and only LiCoO 2 was used.
  • Comparative Example 7 Comparative Example 7 similar to Example 19 except that borate was not used when producing the positive electrode, FEC was not added to the nonaqueous electrolyte, and the rare earth compound was not attached to the surface of the positive electrode active material particles. was made.
  • Comparative Example 8 Comparative Example 8 similar to Example 20 except that borate was not used when producing the positive electrode, FEC was not added to the nonaqueous electrolyte, and the rare earth compound was not attached to the surface of the positive electrode active material particles. Was made.
  • Comparative Example 9 Comparative Example 9 similar to Example 21 except that borate was not used when producing the positive electrode, FEC was not added to the nonaqueous electrolyte, and the rare earth compound was not attached to the surface of the positive electrode active material particles. Was made.
  • Cycle test conditions Charging condition: Charging at a constant current of 1.0 It until the voltage reaches 4.40 V, then charging at a constant voltage of 4.40 V until the current value becomes 1/20 It Pause 10 minutes Discharging condition: 1.0 It Discharge 10 minutes until battery voltage reaches 3.0V
  • the battery of Example 1 in which a rare earth compound is adhered to the surface of the positive electrode active material particles, the positive electrode active material layer contains lithium borate, and the non-aqueous electrolyte contains FEC has high temperature cycle characteristics and high temperature storage. It can be seen that the characteristic values are 80% and 75%, respectively.
  • the battery of Comparative Example 1 that does not contain borate the battery of Comparative Example 2 that does not contain FEC, the battery of Comparative Example 5 that does not have the rare earth compound attached thereto, and the rare earth compound attached to the surface of the positive electrode active material particles.
  • the high temperature cycle characteristic value and the high temperature storage characteristic value of the battery of Comparative Example 6 that does not contain borate and FEC are 35 to 55% and 35 to 50%, respectively, which are lower than the battery of Example 1. It can be seen that the value is shown.
  • Example 9 This tendency is the same as Example 9, Comparative Examples 3 and 4 in which the rare earth compound was changed from erbium to lutetium on the surface of the positive electrode active material particles, and Comparative Examples 5 and 6 in which the rare earth compound was not attached to the surface of the positive electrode active material particles. It was the same in the comparison.
  • the rare earth compound particles were adhered to the surface of the positive electrode active material particles, and the nonaqueous electrolyte contained FEC, but the positive electrode contained no borate (Comparative Example). 1, 3) Even when the rare earth compound particles were adhered to the surface of the positive electrode active material particles and the borate was included in the positive electrode, but the nonaqueous electrolyte did not include FEC (Comparative Examples 2 and 4), the high temperature cycle The effect which improves a characteristic and a high temperature storage characteristic was hardly acquired.
  • FIG. 1 shows a change in capacity retention rate of the batteries of Example 1 and Comparative Example 1 when the charge / discharge cycle is repeated in the high-temperature cycle test. As shown in FIG. 1, the capacity of the battery of Comparative Example 1 suddenly decreases around 50 to 100 cycles.
  • Li metal begins to deposit on the negative electrode. Such deposition of Li metal on the negative electrode is caused by the oxidative decomposition of the non-aqueous electrolyte on the positive electrode and the lithium intercalation reaction on the negative electrode side as the charge compensation reaction, or the transition dissolved from the positive electrode active material. It is considered that metal ions and non-aqueous electrolyte decomposition products (cations) are deposited on the negative electrode, and the deposits clog the active surface of the negative electrode.
  • the battery of Example 1 has the effect of suppressing side reactions as described above, particularly the oxidative decomposition of the nonaqueous electrolyte, so that Li metal does not deposit on the negative electrode (that is, a rapid capacity reduction occurs). It shows good high-temperature cycle characteristics. It is considered that the high temperature storage characteristics are also improved by the same effect.
  • Example 2 using Sm (samarium) as the rare earth element of the rare earth compound
  • the battery of Example 3 using Yb (ytterbium)
  • the battery of Example 4 using Nd (neodymium), Tb (terbium)
  • the battery of Example 5 using Dy
  • the battery of Example 6 using Dy (dysprosium)
  • the battery of Example 7 using Ho (holmium)
  • the battery of Example 8 using Tm (thulium)
  • Lu The same effect as in Example 1 was confirmed for the battery of Example 9 using lutetium. Therefore, other rare earth elements are considered to have the same effect.
  • Example 13 in which the addition amount of borate was changed from 1.0% by mass to 3.0% by mass and Example 14 in which the amount of borate was changed from 0.5% by mass were the same as in the battery of Example 1. The effect was confirmed.
  • Example 1 the batteries of Example 1 were used for Examples 15 to 17 in which the rare earth compound was changed from erbium to lutetium on the surface of the positive electrode active material particles and LiB 3 O 5 , Na 2 B 4 O 7 or MgB 2 O 4 was used. Similar effects were confirmed.
  • Example 9 using lutetium as the rare earth compound on the surface of the positive electrode active material particles was changed to use only LiNi 0.33 Co 0.34 Mn 0.33 O 2
  • Example 19 In Example 20, which was changed to use only LiNi 0.5 Co 0.2 Mn 0.3 O 2 and Example 21 was changed to use only LiCoO 2 , a rare earth compound was added to the surface of the positive electrode active material particles.
  • the properties were superior to those of Comparative Examples 7 to 9 which were not adhered and did not contain borate and FEC, and the same effects as in Example 9 were confirmed.
  • Example 18 the same effect as in Example 9 was confirmed for Example 18 in which the ratio of the positive electrode active material particles a-1 and the positive electrode active material particles a-2 in Example 9 was changed.
  • Li a (M 1-b M ′ b ) O 2 (where M is at least one of Co, Ni, and Mn, and M ′ is B, Al, Mg, Ti, It is at least one of Zr, Fe, Mn, Cr, Zn, 0.9 ⁇ a ⁇ 1.2, 0 ⁇ b ⁇ 0.1), Li a Mn 2 ⁇ x M3 x O 4 (0. 9 ⁇ a ⁇ 1.2, M3 is at least one of Al, B, Ni, Fe, Ti, Cr, V), and Li a FePO 4 (0.9 ⁇ a ⁇ 1.2)
  • a lithium transition metal composite oxide that is at least one selected from the group consisting of:
  • a lithium transition metal composite oxide to which an element such as Al, Mg, B, Zr, or Ti is added as the element M ′ or the element M3 in the above composition formula may be used.
  • the borate is uniformly mixed with the positive electrode active material and the binder in the positive electrode active material layer.
  • the effect of the present invention can be obtained. .
  • the negative electrode active material is not particularly limited.
  • the negative electrode active material Li, Si, SiO x , Sn, SnO x , Li [Li 1/3 Ti 5/3 ] O 4, etc. can be used in addition to the graphite used in the above examples. .
  • the non-aqueous solvent contained in the non-aqueous electrolyte may be composed of a fluorinated non-aqueous solvent and a solvent other than the fluorinated non-aqueous solvent.
  • Non-aqueous solvents other than fluorinated non-aqueous solvents include high dielectric constant solvents having high lithium salt solubility such as ethylene carbonate, propylene carbonate, butylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, diethyl carbonate, dimethyl carbonate, Low viscosity solvents such as chain carbonates such as ethyl methyl carbonate, tetrahydrofuran, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, 1,3-dioxolane, 2-methoxytetrahydrofuran, diethyl ether, ethyl acetate, propyl acetate, ethyl propionate , May be included.
  • Examples of the electrolyte salt dissolved in the non-aqueous solvent include LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2) (C 4 F 9 SO 2), LiC (C 2 F 5 SO 2) 3, LiAsF 6, LiClO 4, Li 2 B 10 Cl 10, Li 2 B 12 Cl 12, LiB (C 2 O 4) F 2 , LiP (C 2 O 4 ) 2 F 2 or other lithium salts can be used.
  • the total concentration of the electrolyte salt in the non-aqueous electrolyte is preferably 0.5 to 2.0 mol / liter.
  • additives such as vinylene carbonate, cyclohexylbenzene, tert-amylbenzene and the like can be added to the nonaqueous electrolyte.
  • a microporous film made of olefin resin such as polyethylene, polypropylene, a mixture or laminate thereof can be used.
  • a high-capacity nonaqueous electrolyte secondary battery excellent in high-temperature battery characteristics such as high-temperature storage characteristics and high-temperature cycle characteristics can be provided. Therefore, industrial applicability is great.

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une batterie secondaire à électrolyte non aqueux qui possède une capacité élevée et des caractéristiques de batterie à haute température supérieures telles que des caractéristiques de stockage à haute température et des caractéristiques de cyclage à haute température à l'aide d'une batterie secondaire à électrolyte non aqueux comprenant un électrolyte non aqueux, une anode, et une cathode contenant des particules d'un oxyde complexe de métal de transition et de lithium en tant que matériau actif de cathode, un composé des terres rares étant collé sur la surface des particules d'un oxyde complexe de métal de transition et de lithium, le composé des terres rares étant au moins un composé choisi parmi le groupe comprenant un hydroxyde de terre rare et un oxyhydroxyde de terre rare, un borate étant contenu dans la cathode, et l'électrolyte non aqueux contenant un solvant non aqueux au fluorure.
PCT/JP2013/005720 2012-09-28 2013-09-26 Batterie secondaire à électrolyte non aqueux WO2014050115A1 (fr)

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JP2012217419A JP2015232923A (ja) 2012-09-28 2012-09-28 非水電解質二次電池

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WO2014156094A1 (fr) * 2013-03-29 2014-10-02 三洋電機株式会社 Batterie secondaire à électrolyte non aqueux
WO2015079664A1 (fr) * 2013-11-29 2015-06-04 三洋電機株式会社 Électrode positive pour batterie rechargeable à électrolyte non aqueux
WO2016017074A1 (fr) * 2014-07-30 2016-02-04 三洋電機株式会社 Électrode positive pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux la comprenant
US10553878B2 (en) 2015-09-30 2020-02-04 Panasonic Intellectual Property Management Co., Ltd. Positive electrode active material for non-aqueous electrolyte secondary batteries
CN111033865A (zh) * 2017-08-24 2020-04-17 三井化学株式会社 锂二次电池及非水电解液
CN114665095A (zh) * 2022-03-29 2022-06-24 珠海冠宇电池股份有限公司 一种电池

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JP6809313B2 (ja) * 2017-03-14 2021-01-06 株式会社村田製作所 正極、電池、電池パック、電子機器、電動車両、蓄電装置および電力システム
US11652237B2 (en) 2017-08-24 2023-05-16 Mitsui Chemicals, Inc. Nonaqueous electrolyte solution including boron compound additive having higher reductive decomposition potential than additional additive and lithium secondary battery including the same
WO2019180945A1 (fr) 2018-03-23 2019-09-26 富山薬品工業株式会社 Électrolyte pour dispositifs de stockage d'énergie et solution électrolytique non aqueuse
WO2024038571A1 (fr) * 2022-08-19 2024-02-22 国立大学法人東北大学 Électrolyte de batterie secondaire au lithium métallique et batterie secondaire au lithium métallique

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WO2014156165A1 (fr) * 2013-03-29 2014-10-02 三洋電機株式会社 Matiere active d'electrode positive pour batteries secondaires a electrolyte non aqueux, son procede de production, electrode positive pour batteries secondaires a electrolyte non aqueux utilisant ladite matiere active d'electrode positive et batterie secondaire a electrolyte non aqueux utilisant ladite electrode positive
WO2014156094A1 (fr) * 2013-03-29 2014-10-02 三洋電機株式会社 Batterie secondaire à électrolyte non aqueux
JPWO2014156094A1 (ja) * 2013-03-29 2017-02-16 三洋電機株式会社 非水電解質二次電池
US9960422B2 (en) 2013-03-29 2018-05-01 Sanyo Electric Co., Ltd. Positive electrode active material for nonaqueous electrolyte secondary batteries, method for producing the same, positive electrode for nonaqueous electrolyte secondary batteries incorporating the positive electrode active material, and nonaqueous electrolyte secondary battery incorporating the positive electrode
WO2015079664A1 (fr) * 2013-11-29 2015-06-04 三洋電機株式会社 Électrode positive pour batterie rechargeable à électrolyte non aqueux
WO2016017074A1 (fr) * 2014-07-30 2016-02-04 三洋電機株式会社 Électrode positive pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux la comprenant
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US10283768B2 (en) 2014-07-30 2019-05-07 Sanyo Electric Co., Ltd. Positive electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same
US10553878B2 (en) 2015-09-30 2020-02-04 Panasonic Intellectual Property Management Co., Ltd. Positive electrode active material for non-aqueous electrolyte secondary batteries
CN111033865A (zh) * 2017-08-24 2020-04-17 三井化学株式会社 锂二次电池及非水电解液
CN114665095A (zh) * 2022-03-29 2022-06-24 珠海冠宇电池股份有限公司 一种电池

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