WO2015019851A1 - Matériau actif d'électrode positive, électrode positive et batterie secondaire au lithium-ion - Google Patents

Matériau actif d'électrode positive, électrode positive et batterie secondaire au lithium-ion Download PDF

Info

Publication number
WO2015019851A1
WO2015019851A1 PCT/JP2014/069455 JP2014069455W WO2015019851A1 WO 2015019851 A1 WO2015019851 A1 WO 2015019851A1 JP 2014069455 W JP2014069455 W JP 2014069455W WO 2015019851 A1 WO2015019851 A1 WO 2015019851A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
active material
electrode active
capacity
battery
Prior art date
Application number
PCT/JP2014/069455
Other languages
English (en)
Japanese (ja)
Inventor
雄一 上村
西村　直人
智寿 吉江
貴洋 松山
正悟 江▲崎▼
俊平 西中
俊次 末木
Original Assignee
シャープ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by シャープ株式会社 filed Critical シャープ株式会社
Priority to JP2015530788A priority Critical patent/JPWO2015019851A1/ja
Publication of WO2015019851A1 publication Critical patent/WO2015019851A1/fr

Links

Images

Classifications

    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/58—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 active material, a positive electrode, and a lithium ion secondary battery. More specifically, the present invention relates to a positive electrode active material, a positive electrode, and a lithium ion secondary battery that can suppress a decrease in battery capacity (Ah) even after repeated charge and discharge.
  • Ah battery capacity
  • a lithium ion secondary battery is a battery that includes a positive electrode, a separator, and a negative electrode in this order, and uses insertion and desorption of lithium ions to and from an active material layer that constitutes the positive electrode and the negative electrode.
  • This battery has the subject that the battery capacity which can be utilized reduces by repeating charging / discharging. This problem becomes a big problem particularly in an electricity storage device that requires a guarantee of a battery capacity of 20 years or more, such as an electricity storage device for general households.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2012-234766
  • the positive electrode active material layer is an aggregate of primary particles in which D10 is larger than 1 nm and smaller than 65 nm, D50 is larger than 5 nm and smaller than 75 nm, D90 is larger than 50 nm and smaller than 100 nm,
  • the maximum peak pore size A in the pore size distribution between the pores is in the range of 10 to 75 nm, and the ratio A / B between the pore size A and the crystallite size B of the positive electrode active material layer is greater than 0.5 and less than 1 It is supposed to have.
  • Specific examples of the positive electrode active material include LiFePO 4 and LiFe 0.25 Mn 0.75 PO 4 .
  • the positive electrode active material has the above physical properties, so that the input / output characteristics of lithium ions can be improved, and as a result, a decrease in battery capacity can be suppressed.
  • the reason for this is that the movement resistance of lithium ions in the primary particles is extremely lowered because the diameter of the primary particles is extremely small and uniform.
  • the positive electrode active material described in the above publication it is difficult to suppress a sufficient decrease in battery capacity.
  • the positive electrode active material in which the Fe site is substituted with an element other than Mn and the positive electrode active material in which the P site is substituted with Si have insufficient suppression effects. Therefore, it is desired to provide a positive electrode active material that can further suppress a decrease in battery capacity.
  • the cause of the above problem is (1) a decrease in the amount of lithium ions that can be inserted and desorbed due to a change in the crystal structure of the positive electrode active material; Increase of inactive active material due to disconnection of lithium ion conductive path, (3) Decrease amount of lithium ion insertion / desorption due to formation of excessive film on negative electrode surface, (4) Positive electrode during charge / discharge cycle It is considered that dendrite is deposited on the surface of the negative electrode due to the collapse of the capacity balance between the negative electrode and the negative electrode. As a result of studying this problem, it has been found that a positive electrode active material having a specific particle size distribution can suppress a decrease in battery capacity, and has led to the present invention.
  • a mixture of particles defined by a particle size distribution D10 of 4 to 10 ⁇ m and a particle size distribution D50 of 11 to 30 ⁇ m is included, and the following general formula (1): Li x M y P a Si z O 4 (1) (However, M includes at least Fe or Mn, and 0 ⁇ x ⁇ 2, 0.8 ⁇ y ⁇ 1.2, 0 ⁇ z ⁇ 1, 0 ⁇ a ⁇ 1.1)
  • the positive electrode active material for lithium ion secondary batteries containing the lithium containing metal oxide represented by these is provided.
  • a current collector, and a positive electrode active material layer on the current collector Provided is a positive electrode for a lithium ion secondary battery in which the positive electrode active material layer includes the positive electrode active material and a binder. Furthermore, according to the present invention, the positive electrode, a separator, and a negative electrode having a negative electrode active material layer containing graphite are provided in this order, There is provided a lithium ion secondary battery in which the negative electrode has a capacity per unit area of 1.1 to 2.0 times the capacity per unit area of the positive electrode.
  • the lithium ion secondary battery by which the fall of the battery capacity by the repetition of charging / discharging was suppressed the positive electrode active material which can give this battery, and a positive electrode can be provided.
  • the positive electrode active material is a mixture of particles defined by a particle size distribution D90 of 40 to 60 ⁇ m
  • the battery capacity can be further prevented from decreasing.
  • the particle size distributions D10, D50, and D90 are 4.8 to 10 ⁇ m, 14 to 30 ⁇ m, and 40 to 58 ⁇ m, respectively, the battery capacity can be further prevented from decreasing.
  • M is only Fe, only Mn, a combination of Fe and Mn, Fe and A (where A is at least one element selected from the group consisting of Co, Ni, Zr, Sn, Al, and Y)
  • A is at least one element selected from the group consisting of Co, Ni, Zr, Sn, Al, and Y
  • the positive electrode includes a current collector and a positive electrode active material layer on the current collector, When a positive electrode active material layer contains the said positive electrode active material and a binder, the fall of battery capacity can be suppressed more.
  • a lithium ion secondary battery includes the above positive electrode, a separator, and a negative electrode having a negative electrode active material layer containing graphite in this order, When the negative electrode has a capacity per unit area that is 1.1 to 2.0 times the capacity per unit area of the positive electrode, the battery capacity can be further prevented from decreasing.
  • the positive electrode active material for the lithium ion secondary battery of the present invention has the following general formula (1): Li x M y P a Si z O 4 (1) (However, M includes at least Fe or Mn, and 0 ⁇ x ⁇ 2, 0.8 ⁇ y ⁇ 1.2, 0 ⁇ z ⁇ 1, 0 ⁇ a ⁇ 1.1) It is a lithium containing metal oxide represented by these.
  • the Li amount x, M amount y, Si amount z, and P amount a are values determined by ICP mass spectrometry (ICP-MS).
  • M is not particularly limited as long as it contains at least Fe or Mn and can be charged and discharged as a battery.
  • M is Fe only, Mn only, a combination of Fe and Mn, Fe and A (where A is at least one element selected from the group consisting of Co, Ni, Zr, Sn, Al, and Y) ), A combination of Mn and A, and a combination of Fe, Mn and A.
  • A is at least one element selected from the group consisting of Co, Ni, Zr, Sn, Al, and Y
  • Mn and A a combination of Fe, Mn and A.
  • Fe alone, a combination of Fe and Zr, a combination of Fe and Al, and the like are preferable.
  • the valence of M is not particularly limited.
  • Fe can take 2 to 4 and 6 valences
  • Zr can take 2 to 4 valences.
  • M may be a metal element having a single valence or a mixture of metal elements having a plurality of valences.
  • the valence of M means an average value.
  • Zr is preferably tetravalent from the viewpoint of little change in valence during the production of the lithium-containing metal oxide and during charge and discharge.
  • x may be 0 ⁇ x ⁇ 2
  • y may be 0.8 ⁇ y ⁇ 1.2
  • z may be 0 ⁇ z ⁇ 1
  • a may be 0 ⁇ a ⁇ 1.1.
  • x is 0.9 ⁇ x ⁇ 2
  • y is 0.9 ⁇ y ⁇ 1.2
  • z is 0 ⁇ z ⁇ 0.25
  • a is 0.7 ⁇ .
  • x is 0.95 ⁇ x ⁇ 2
  • y is 0.95 ⁇ y ⁇ 1.2
  • z is 0 ⁇ z ⁇ 0.1
  • a is 0.75 ⁇ .
  • a ⁇ 1.1 is a value that varies depending on the charge / discharge of the battery.
  • Most lithium-containing metal oxides having the composition of the general formula (1) have an olivine type structure, but may have a configuration not having an olivine type structure.
  • the positive electrode active material is a mixture of particles defined by a particle size distribution D10 of 4 to 10 ⁇ m and a particle size distribution D50 of 11 to 30 ⁇ m.
  • the inventors have presumed the reason why the decrease in battery capacity can be suppressed by the definition of the particle size distribution as follows.
  • the positive electrode active material is composed of lithium-containing metal oxide particles obtained by element substitution of LiFePO 4 .
  • a Li-rich phase different from the bulk composition exists on the surface of such element-substituted particles. A part of this Li-rich phase is dispersed and dissolved in a solvent during preparation of a paste containing a positive electrode active material for forming a positive electrode, a binder, and a solvent. This dispersion / dissolution increases the surface area of the particles.
  • this effect can be maximized by using a positive electrode active material defined by a particle size distribution D10 of 4 to 10 ⁇ m and a particle size distribution D50 of 11 to 30 ⁇ m.
  • D10 is less than 4 [mu] m, if D50 is 11 ⁇ m smaller, the proportion of Li-rich phase is increased relative to Li x M y P a Si z O 4 represented by the general formula (1), the proportion that can contribute to the capacitance
  • the battery capacity may be reduced.
  • D10 is greater than 10 [mu] m
  • D50 is decreased the proportion of Li-rich phase to the Li x M y P a Si z O 4 , represented by case 30 ⁇ m greater, general formula (1), the inhibitory effect of volume reduction It may not be obtained sufficiently.
  • D10 is 4 ⁇ 10 [mu] m
  • D50 is by using Li x M y P a Si z O 4 , represented by the general formula 11 ⁇ 30 ⁇ m (1), can be suppressed to maximize the reduction of battery capacity.
  • D10 is preferably 4.5 to 10 ⁇ m, and more preferably 4.8 to 10 ⁇ m.
  • D50 is preferably 12 to 30 ⁇ m, and more preferably 14 to 30 ⁇ m.
  • D90 is preferably 40 to 60 ⁇ m, and more preferably 40 to 58 ⁇ m.
  • the particle size distribution is a value measured by a laser diffraction / scattering particle size distribution measuring device (LMS-2000e manufactured by Seishin Enterprise Co., Ltd.).
  • LMS-2000e manufactured by Seishin Enterprise Co., Ltd.
  • the surface of the lithium-containing metal oxide may be coated with carbon in order to improve conductivity.
  • the coating may be the entire surface of the lithium-containing metal oxide or a part thereof.
  • Lithium-containing metal oxide is prepared by using carbonate, hydroxide, chloride, sulfate, acetate, oxide, oxalate, nitrate, alkoxide of each element as a raw material. It can manufacture by using the combination of these.
  • the raw material may contain hydration water.
  • methods such as a firing method, a solid phase method, a sol-gel method, a melt quench method, a mechanochemical method, a coprecipitation method, a hydrothermal method, and a spray pyrolysis method can be used.
  • a firing method under an inert atmosphere for example, a nitrogen atmosphere (firing conditions are 400 to 650 ° C. for 1 to 24 hours) is convenient.
  • the obtained lithium-containing metal oxide is adjusted to a desired particle size distribution by being subjected to a known pulverization method and sieving method.
  • a known pulverization method and sieving method As an example, an airflow classifier is used. Fine particles and coarse particles are separated, and a desired particle size distribution can be obtained by the mixing ratio.
  • the positive electrode includes a current collector and a positive electrode active material layer on the current collector.
  • A Positive electrode active material layer It is preferable that the positive electrode active material layer contains the said positive electrode active material and a binder.
  • the binder include (meth) acrylic resin, styrene butadiene rubber (SBR), polyvinylidene fluoride (PVDF), and the like.
  • the binder may include 1 to 8 parts by weight with respect to 100 parts by weight of the positive electrode active material. When the binder content is less than 1 part by weight, the binding ability may be insufficient. When the binder content is more than 8 parts by weight, the amount of active material contained in the positive electrode decreases, and the resistance or polarization of the positive electrode increases. The discharge capacity may be reduced.
  • a conductive material and a thickening material may be included.
  • the conductive material acetylene black, carbon, graphite, natural graphite, artificial graphite, needle coke, or the like can be used.
  • the thickener carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone and the like can be used.
  • the contents of the thickener and the conductive material are preferably about 0.5 to 5 parts by weight for the thickener and about 1 to 6 parts by weight for the conductive material with respect to 100 parts by weight of the positive electrode active material. If the content of the thickener is less than 0.5 parts by weight, the thickening ability may be insufficient.
  • the amount of the active material contained in the positive electrode decreases, and the positive electrode resistance or Polarization and the like may increase and the discharge capacity may decrease. If the content of the conductive material is less than 1 part by weight, the resistance or polarization of the positive electrode may increase and the discharge capacity may decrease, and if it exceeds about 6 parts by weight, the amount of active material contained in the positive electrode will decrease. As a result, the discharge capacity as the positive electrode may be reduced.
  • the thickness of the positive electrode active material layer is preferably about 0.01 to 2 mm. If it is too thick, the conductivity is lowered, and if it is too thin, the capacity per unit area is lowered.
  • the positive electrode active material layer obtained by coating and drying may be subjected to press treatment in order to increase the packing density of the lithium-containing metal oxide.
  • the positive electrode active material layer can be produced, for example, by a known method such as applying a slurry obtained by mixing a positive electrode active material and a binder together with a thickener and a conductive material in a solvent to a current collector.
  • Solvents include water, N-methyl-2-pyrrolidone, toluene, cyclohexane, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, methyl acrylate, diethyltriamine, NN-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran, etc.
  • Organic solvents can be used.
  • (B) Current collector As the current collector, foamed (porous) metal having continuous pores, metal formed in a honeycomb shape, sintered metal, expanded metal, non-woven fabric, plate, foil, perforated plate or foil Etc. can be used.
  • the positive electrode current collector is usually made of aluminum.
  • the lithium ion secondary battery of this invention is equipped with the positive electrode, the negative electrode, and the separator located between a positive electrode and a negative electrode.
  • the negative electrode preferably has a capacity per unit area 1.1 to 2.0 times that of the positive electrode.
  • the reason why it is preferable to adjust the capacity is as follows. (1)
  • the capacity (mAh / g) per gram of active material of the positive electrode active material of the present invention in which LiFePO 4 is elementally substituted may be reduced depending on the amount of substitution.
  • the positive electrode active material of the present invention in which LiFePO 4 is elementally substituted is different from LiFePO 4 in the diffusion rate of lithium in the active material.
  • the positive electrode of the present invention can be used as the positive electrode.
  • a negative electrode having a negative electrode active material layer on a current collector can be used.
  • the negative electrode active material layer can be produced by a known method. Specifically, it can be produced in the same manner as described in the method for producing the positive electrode active material layer.
  • the negative electrode active material layer can be obtained by molding the molded body into a sheet shape and press-bonding the obtained molded body to stainless steel and a current collector. Further, as described in the method for producing the positive electrode active material layer, the mixed powder can be produced by applying a slurry obtained by mixing with a known solvent on a current collector. A known material can be used as the negative electrode active material.
  • SBR styrene butadiene rubber
  • PVDF polyvinylidene fluoride
  • the potential for lithium insertion / extraction is close to the deposition / dissolution potential of metallic lithium.
  • a typical example is natural or artificial graphite in the form of particles (scale-like, lump-like, fibrous, whisker-like, spherical, pulverized particles, etc.).
  • lithium transition metal oxide, lithium transition metal nitride, transition metal oxide, silicon oxide, and the like can be used as the negative electrode active material.
  • graphite is preferable from the viewpoint of cycle.
  • Examples of the artificial graphite include graphite obtained by graphitizing mesocarbon microbeads, mesophase pitch powder, isotropic pitch powder, and the like. Also, graphite particles having amorphous carbon attached to the surface can be used. Among these, natural graphite is more preferable because it is inexpensive, close to the redox potential of lithium, and can constitute a high energy density battery.
  • As the current collector a foamed (porous) metal having continuous pores, a metal formed in a honeycomb shape, a sintered metal, an expanded metal, a nonwoven fabric, a plate, a foil, a perforated plate or a foil can be used. .
  • the negative electrode current collector is usually made of copper.
  • (C) Separator As the separator, a porous material or a nonwoven fabric can be used singly or in combination. As a material for the separator, a material that does not dissolve or swell with respect to an organic solvent contained in the electrolyte described later is preferable. Specific examples include polyester polymers, polyolefin polymers (for example, polyethylene and polypropylene), ether polymers, aramid polymers, and inorganic materials such as glass.
  • Nonaqueous electrolyte A lithium ion secondary battery usually includes a nonaqueous electrolyte between a positive electrode and a negative electrode.
  • a nonaqueous electrolyte for example, an organic electrolyte, a gel electrolyte, a polymer solid electrolyte, an inorganic solid electrolyte, a molten salt, or the like can be used.
  • organic electrolytes are generally used from the viewpoint of battery manufacturability.
  • the organic electrolyte contains an electrolyte salt and an organic solvent.
  • organic solvents examples include cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC) and butylene carbonate, and chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate, and dipropyl carbonate.
  • cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC) and butylene carbonate
  • chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate, and dipropyl carbonate.
  • Lactones such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone, furans such as tetrahydrofuran and 2-methyltetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane, Examples include ethers such as dioxane, dimethyl sulfoxide, sulfolane, methyl sulfolane, acetonitrile, methyl formate, and methyl acetate. One or more of these can be used in combination.
  • Examples of the electrolyte salt include lithium borofluoride (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium trifluoroacetate (LiCF 3 COO), lithium bis (trifluoro) Examples thereof include lithium salts such as romethanesulfone) imide (LiN (CF 3 SO 2 ) 2 ), and one or more of these may be used in combination.
  • the salt concentration of the electrolytic solution is preferably 0.5 to 3 mol / l.
  • Other members Various materials used for conventionally known lithium ion secondary batteries can be used for other members such as battery containers, and there is no particular limitation.
  • the lithium ion secondary battery is provided with the laminated body which consists of a positive electrode, a negative electrode, and the separator pinched
  • the laminate may have, for example, a strip-like planar shape.
  • the laminate may be wound.
  • One or more of the laminates are inserted into the battery container.
  • the positive electrode and the negative electrode are connected to the external conductive terminal of the battery.
  • the battery container is sealed to block the positive electrode, the negative electrode, and the separator from the outside air.
  • the sealing method is generally a method in which a lid having a resin packing is fitted into the opening of the battery container and the battery container and the lid are caulked.
  • a method of attaching a lid called a metallic sealing plate to the opening and performing welding can be used.
  • a method of sealing with a binder and a method of fixing with a bolt via a gasket can also be used.
  • a method of sealing with a laminate film in which a thermoplastic resin is attached to a metal foil can also be used. An opening for electrolyte injection may be provided at the time of sealing.
  • Example 1 (Synthesis of positive electrode active material) Positive electrode active material LiCH 3 COO as a lithium source as a starting material, Fe (NO 3 ) 3 .9H 2 O as an iron source, ZrCl 4 as a zirconium source, H 3 PO 4 (85%) as a phosphorus source, Si (as a silicon source) OC 2 H 5 ) 4 was used.
  • the obtained powder was pressed into a pellet. This was calcined at 500 ° C. for 12 hours in a nitrogen atmosphere, and subjected to classification treatment to obtain a positive electrode active material having a particle size distribution (D10, D50, D90) shown in Table 1.
  • the classification process uses an airflow classifier to separate fine particles and coarse particles, and a desired particle size distribution can be obtained by the mixing ratio.
  • the obtained positive electrode active material had an Li amount of 1.02, an Fe amount of 0.95, a Zr amount of 0.05, a P amount of 0.94, and an Si amount of 0.05.
  • Li, Fe, Zr, P, and Si are results obtained by a calibration curve method using an ICP mass spectrometer (ICP-MS 7500CS manufactured by Agilent Technologies).
  • the particle size distribution is a value measured using a laser diffraction / scattering type particle size distribution measuring device (LMS-2000e manufactured by Seishin Enterprise Co., Ltd.).
  • the above positive electrode active material acetylene black (conductive material, manufactured by Denki Kagaku Kogyo), acrylic resin (binder, manufactured by JSR), carboxymethylcellulose (thickener, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
  • the aqueous positive electrode paste was prepared by stirring and mixing with 103 parts by weight of water with respect to the positive electrode active material 100 at room temperature at a weight ratio of 1.2 using Fillmix 80-40 (manufactured by Primex) at room temperature. Obtained.
  • This positive electrode paste was applied on one side of a rolled aluminum foil (thickness: 20 ⁇ m) using a die coater.
  • the coating was performed under the condition that the coating amount of the positive electrode active material was 17 mg / cm 2 .
  • the obtained coating film was dried in air at 100 ° C. for 30 minutes and pressed to provide a positive electrode having a positive electrode active material layer having a thickness of 113 ⁇ m on the current collector (coating surface size: 28 mm (vertical) ⁇ 28 mm (horizontal)) was obtained.
  • the obtained coating film was dried in air at 100 ° C. for 30 minutes and pressed to have an electrode density of 1.2 to 1.4 g / cm 3 , thereby providing a negative electrode active material layer on the current collector.
  • a negative electrode (coating surface size: 30 mm (vertical) ⁇ 30 mm (horizontal)) was obtained.
  • the produced positive electrode 1 and negative electrode 2 were dried under reduced pressure at 130 ° C. for 24 hours, and then placed in a glow box under a dry Ar atmosphere.
  • an aluminum tab lead 4 with an adhesive film was ultrasonically welded to the positive electrode 1
  • a nickel tab lead 6 with an adhesive film was ultrasonically welded to the negative electrode 2.
  • a polyethylene microporous film size: 30 mm (length) ⁇ 30 cm (width), thickness 25 ⁇ m, porosity 55%) was loaded as the separator 9 so that the coated surface of the negative electrode 2 was hidden.
  • the single cell 10 was produced by superimposing the positive electrode 1 on the microporous film so that the coated surface overlapped with the center.
  • the single cell 10 was sandwiched between the aluminum laminate films 11 and 12, and the three sides of the aluminum laminate films 11 and 12 were thermally welded so that the adhesive films of the tab leads 4 and 6 were sandwiched.
  • an electrolytic solution in which LiPF 6 was dissolved was poured into a solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at a volume ratio of 1: 2 so as to be 1 mol / l.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the last one side of the aluminum laminate films 11 and 12 is heat-sealed under a reduced pressure of 10 kPa, and the lithium ion secondary battery 14 shown in FIG. 1 (13 in FIG. 1 indicates a heat-sealed part). Obtained.
  • the amount of the electrolyte solution injected was appropriately determined according to the thickness of the electrode used in the battery, and the amount was sufficient to allow the electrolyte solution to permeate the positive and negative electrodes and the separator
  • Examples 2 to 21 and Comparative Examples 1 to 13 A lithium ion secondary battery was obtained in the same manner as in Example 1 except that the positive electrode active material having the composition and particle size distribution shown in Tables 1 and 2 was used and the positive electrode and the negative electrode were obtained with the actual coating amounts shown in Table 1.
  • Tables 1 and 2 also show the ratio of the negative electrode capacity to the positive electrode capacity per unit area, the initial discharge efficiency at 0.1 C, and the capacity retention rate after 7000 cycles. The initial charge / discharge efficiency and capacity retention rate were measured by the following procedure.
  • the integrated value (A) ⁇ (B) was used as an index for evaluating the performance of the positive electrode active material for an electricity storage device requiring a life of several thousand cycles. Specifically, no matter how good the capacity retention rate (B) after 7000 cycles, if the initial charge / discharge efficiency (A) is poor, the energy density is low, resulting in a very large battery size.
  • FIG. 5 shows the relationship between the integrated value (A) ⁇ (B) and the ratio between the negative electrode capacity and the positive electrode capacity per unit area.
  • the dotted line circle is a plot of the positive electrode active material not substituted with Zr and Si
  • the solid line circle is a plot of the positive electrode active material whose capacity ratio between the positive electrode and the negative electrode is outside the range of 1.3 to 1.8.
  • D90 has the same tendency as D10 and D50.
  • the capacity ratio of the negative electrode to the positive electrode is 1.3 to When it is 1.8 times, it turns out that the first-time charging / discharging efficiency and capacity maintenance rate are improving more.
  • FIG. 5 shows that the positive electrode active material substituted with Zr and Si has improved initial charge / discharge efficiency and capacity retention rate than the non-substituted positive electrode active material, and the negative electrode to positive electrode capacity ratio is 1.3 to In the case of 1.8 times, it can be seen that the initial charge / discharge efficiency and the capacity retention rate are further improved than the other capacity ratios.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un matériau actif d'électrode positive pour des batteries secondaires au lithium-ion, qui est un mélange de particules définies par une distribution granulométrique (D10) comprise entre 4 μm et 10 μm et une distribution granulométrique (D50) comprise entre 11 μm et 30 μm et qui est un oxyde métallique contenant du lithium, représenté par la formule générale (1) : LixMyPaSizO4 (M comprenant au moins du Fe ou du Mn, 0 < x ≤ 2, 0,8 ≤ y ≤ 1,2, 0 < z ≤ 1 et 0 < a ≤ 1,1).
PCT/JP2014/069455 2013-08-08 2014-07-23 Matériau actif d'électrode positive, électrode positive et batterie secondaire au lithium-ion WO2015019851A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015530788A JPWO2015019851A1 (ja) 2013-08-08 2014-07-23 正極活物質、正極及びリチウムイオン二次電池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013165159 2013-08-08
JP2013-165159 2013-08-08

Publications (1)

Publication Number Publication Date
WO2015019851A1 true WO2015019851A1 (fr) 2015-02-12

Family

ID=52461190

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/069455 WO2015019851A1 (fr) 2013-08-08 2014-07-23 Matériau actif d'électrode positive, électrode positive et batterie secondaire au lithium-ion

Country Status (2)

Country Link
JP (1) JPWO2015019851A1 (fr)
WO (1) WO2015019851A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017056734A1 (fr) * 2015-09-29 2017-04-06 株式会社日立製作所 Pile rechargeable au lithium
JP2022032207A (ja) * 2020-08-11 2022-02-25 プライムプラネットエナジー＆ソリューションズ株式会社 非水電解質二次電池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002117833A (ja) * 2000-10-06 2002-04-19 Sony Corp 非水電解質二次電池
WO2004051771A1 (fr) * 2002-11-29 2004-06-17 Seimi Chemical Co., Ltd. Procede de preparation de materiau actif d'electrode positive pour accumulateur au lithium
WO2009123232A1 (fr) * 2008-03-31 2009-10-08 日本ゼオン株式会社 Plaque positive pour une batterie secondaire, procédé de fabrication de cette plaque et batterie secondaire équipée de cette plaque
WO2010134579A1 (fr) * 2009-05-22 2010-11-25 シャープ株式会社 Matériau actif de pôle positif, pôle positif et accumulateur non aqueux
WO2011152455A1 (fr) * 2010-06-02 2011-12-08 シャープ株式会社 Procédé de production d'un oxyde complexe contenant du lithium

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10162826A (ja) * 1996-11-28 1998-06-19 Sanyo Electric Co Ltd 非水電解液二次電池
JP4061530B2 (ja) * 2002-05-24 2008-03-19 株式会社ジーエス・ユアサコーポレーション 非水電解質二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002117833A (ja) * 2000-10-06 2002-04-19 Sony Corp 非水電解質二次電池
WO2004051771A1 (fr) * 2002-11-29 2004-06-17 Seimi Chemical Co., Ltd. Procede de preparation de materiau actif d'electrode positive pour accumulateur au lithium
WO2009123232A1 (fr) * 2008-03-31 2009-10-08 日本ゼオン株式会社 Plaque positive pour une batterie secondaire, procédé de fabrication de cette plaque et batterie secondaire équipée de cette plaque
WO2010134579A1 (fr) * 2009-05-22 2010-11-25 シャープ株式会社 Matériau actif de pôle positif, pôle positif et accumulateur non aqueux
WO2011152455A1 (fr) * 2010-06-02 2011-12-08 シャープ株式会社 Procédé de production d'un oxyde complexe contenant du lithium

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017056734A1 (fr) * 2015-09-29 2017-04-06 株式会社日立製作所 Pile rechargeable au lithium
JP2022032207A (ja) * 2020-08-11 2022-02-25 プライムプラネットエナジー＆ソリューションズ株式会社 非水電解質二次電池
JP7213208B2 (ja) 2020-08-11 2023-01-26 プライムプラネットエナジー＆ソリューションズ株式会社 非水電解質二次電池
US11769904B2 (en) 2020-08-11 2023-09-26 Prime Planet Energy & Solutions, Inc. Nonaqueous electrolyte secondary battery

Also Published As

Publication number Publication date
JPWO2015019851A1 (ja) 2017-03-02

Similar Documents

Publication Publication Date Title
CN107710466B (zh) 负极活性物质及二次电池、以及负极材料的制造方法
JP6236197B2 (ja) リチウム電池用正極及びリチウム電池
KR102183992B1 (ko) 양극 활물질, 이를 채용한 양극과 리튬 전지, 및 상기 양극 활물질의 제조방법
JP5843766B2 (ja) 正極活物質、正極及び非水系二次電池
US10651458B2 (en) Negative electrode for lithium secondary battery and lithium secondary battery
CN108701824B (zh) 负极活性物质、混合负极活性物质、二次电池用负极、二次电池、及负极活性物质的制造
EP3279148B1 (fr) Oxyde composite à base de cobalt et de lithium pour batterie secondaire au lithium et batterie secondaire au lithium comportant une électrode positive le comprenant
WO2014010476A1 (fr) Électrode destinée à une batterie rechargeable au lithium, son procédé de fabrication, batterie rechargeable au lithium et son procédé de fabrication
JP5683890B2 (ja) 正極材料、その製造方法、正極及び非水電解質二次電池
WO2018008260A1 (fr) Matériau actif d&#39;électrode négative, électrode négative, batterie secondaire lithium-ion, procédé d&#39;utilisation de batterie secondaire lithium-ion, procédé de production de matériau actif d&#39;électrode négative et procédé de production de batterie secondaire lithium-ion
US20180254486A1 (en) Negative electrode active material, negative electrode and lithium ion secondary battery
US20140011083A1 (en) Electrode for non-aqueous electrolyte secondary batteries and non-aqueous electrolyte secondary battery including the same
WO2016185663A1 (fr) Matériau actif d&#39;électrode négative pour piles rechargeables à électrolyte non aqueux, pile rechargeable à électrolyte non aqueux, et procédé de production de matériau actif d&#39;électrode négative pour piles rechargeables à électrolyte non aqueux
KR20170025874A (ko) 리튬 이차전지 및 그의 구동방법
JPWO2018179934A1 (ja) 負極材料および非水電解質二次電池
JP2001076727A (ja) 非水電解質電池用正極活物質及び非水電解質電池
CN106558725B (zh) 锂离子二次电池
JP2014093145A (ja) 非水電解質二次電池及びその負極
JP2012204003A (ja) 正極活物質、正極及び非水系二次電池
JP2023025888A (ja) リチウムイオン二次電池用負極活物質、その製造方法、及びリチウムイオン二次電池用負極電極
JP7144536B2 (ja) 二次電池用負極活物質、それを含む電極及びその製造方法
JP2012234778A (ja) 正極活物質、正極及び非水系二次電池
JP7116518B1 (ja) リチウムイオン二次電池用負極活物質、その製造方法、及びリチウムイオン二次電池用負極電極
WO2015019851A1 (fr) Matériau actif d&#39;électrode positive, électrode positive et batterie secondaire au lithium-ion
WO2014175350A1 (fr) Batterie secondaire au lithium-ion

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14834594

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015530788

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14834594

Country of ref document: EP

Kind code of ref document: A1