WO2010053174A1 - リチウム二次電池用正極及びリチウム二次電池 - Google Patents
リチウム二次電池用正極及びリチウム二次電池 Download PDFInfo
- Publication number
- WO2010053174A1 WO2010053174A1 PCT/JP2009/069046 JP2009069046W WO2010053174A1 WO 2010053174 A1 WO2010053174 A1 WO 2010053174A1 JP 2009069046 W JP2009069046 W JP 2009069046W WO 2010053174 A1 WO2010053174 A1 WO 2010053174A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- positive electrode
- secondary battery
- manganese
- lithium secondary
- Prior art date
Links
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
- H01M4/36—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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a positive electrode for a lithium secondary battery and a lithium secondary battery provided with the positive electrode for a lithium secondary battery.
- lithium secondary batteries having a relatively high energy density and being difficult to self-discharge and excellent in cycle performance have attracted attention as power sources for portable devices such as mobile phones and notebook computers or electric vehicles.
- lithium secondary batteries are mainly used for small-sized consumer devices, mainly for mobile phones having a battery capacity of 2 Ah or less.
- the positive electrode active material of the positive electrode in the lithium secondary battery for small consumer for example, lithium cobalt oxide of the working potential of 4V near (LiCoO 2), lithium nickel oxide (LiNiO 2), or lithium manganese having a spinel structure
- Lithium-containing transition metal oxides such as oxides (LiMn 2 O 4 ) are known.
- lithium-containing transition metal oxides are excellent in charge / discharge performance and energy density, so lithium cobalt oxide (LiCoO 2 ) is widely used in small-sized consumer lithium secondary batteries up to a battery capacity of 2 Ah.
- a capacitor that can be used for a long time even in a high temperature environment is a capacitor, but the capacitor does not satisfy the user's requirement in that the energy density is not sufficient. Therefore, a battery having a sufficient energy density while maintaining safety is required.
- a polyanionic positive electrode active material having excellent thermal stability has attracted attention. Since the polyanion positive electrode active material is immobilized by covalently bonding oxygen to an element other than the transition metal, it is difficult to release oxygen even at high temperatures, and the safety of the lithium secondary battery can be improved. Conceivable.
- lithium iron phosphate (LiFePO 4 ) having an olivine structure has been actively studied.
- lithium iron phosphate (LiFePO 4 ) not only has a relatively low theoretical capacity of 170 mAh / g, but also inserts and desorbs lithium at a base potential of 3.4 V (vs. Li / Li + ). Therefore, the energy density is smaller than that of the lithium-containing transition metal oxide. Therefore, in the polyanionic positive electrode active material, a part of or all of Fe of lithium iron phosphate (LiFePO 4 ) is replaced with Mn to have a reversible potential in the vicinity of 4 V (vs. Li / Li + ). Further, lithium iron manganese phosphate (LiMn x Fe (1-x) PO 4 ) or lithium manganese phosphate (LiMnPO 4 ) has been studied.
- lithium iron manganese phosphate or lithium manganese phosphate has insufficient electrical conductivity and insufficient lithium ion conductivity, the utilization rate of the active material is relatively low, and the high rate charge / discharge characteristics are also low. It is not satisfactory.
- the lithium-containing transition metal oxide and the polyanionic positive electrode active material are used for the purpose of enhancing the safety of the lithium secondary battery including the positive electrode including the lithium-containing transition metal oxide.
- Patent Documents 1 to 7 have been proposed (for example, Patent Documents 1 to 7).
- this type of positive electrode active material can increase the safety of the battery as compared with the case where the positive electrode active material is a lithium-containing transition metal oxide alone, the safety of the battery is higher than that of a polyanionic positive electrode active material alone. Lower.
- this type of positive electrode active material has a problem that the initial Coulomb efficiency indicating the ratio of the initial discharge capacity to the initial charge capacity is not always satisfactory.
- An object of the present invention is to provide a positive electrode for a lithium secondary battery that can improve the initial coulomb efficiency while keeping the safety of the lithium secondary battery relatively high. It is expected that the energy density of the lithium secondary battery will be excellent due to the excellent initial Coulomb efficiency of the lithium secondary battery.
- the positive electrode for a lithium secondary battery according to the present invention includes lithium manganese iron phosphate and lithium nickel manganese cobalt composite oxide.
- the positive electrode for a lithium secondary battery according to the present invention has a mass ratio (A: B) of the lithium manganese manganese phosphate (A) and the lithium nickel manganese cobalt composite oxide (B) of 10:90 to 70. : 30 is preferable.
- the number of manganese atoms contained in the lithium manganese iron phosphate is more than 50% and less than 100% with respect to the total number of manganese atoms and iron atoms.
- the number of cobalt atoms contained in the lithium nickel manganese cobalt composite oxide is preferably more than 0% and 67% or less with respect to the total number of nickel atoms, manganese atoms, and cobalt atoms.
- a lithium secondary battery according to the present invention includes the above-described positive electrode for a lithium secondary battery, a negative electrode, and a nonaqueous electrolyte.
- the positive electrode for a lithium secondary battery according to the present invention has an effect that the initial coulomb efficiency can be improved while keeping the safety of the lithium secondary battery relatively high.
- the positive electrode for a lithium secondary battery of this embodiment contains lithium manganese iron phosphate and lithium nickel manganese cobalt composite oxide. Moreover, a conductive agent and a binder are usually included. The lithium manganese iron phosphate and the lithium nickel manganese cobalt composite oxide can exhibit the function of a positive electrode active material in a positive electrode for a lithium secondary battery.
- the lithium manganese iron phosphate is a phosphate compound containing a lithium atom, a manganese atom, and an iron atom. Further, it has an olivine type crystal structure classified as orthorhombic, and manganese atoms and iron atoms are in solid solution with each other.
- As said lithium manganese iron phosphate it is preferable to use the compound represented by following General formula (1). LiMn x Fe (1-x) PO 4 (0 ⁇ x ⁇ 1) ⁇ formula (1)
- the compound represented by the general formula (1) may contain a small amount of a transition metal element other than Mn or Fe or a typical element such as Al, for example, within a range where the basic properties of the compound do not change. In this case, an element not represented by the general formula (1) is included in the lithium iron manganese phosphate.
- examples of the transition metal element other than Mn or Fe include cobalt and nickel.
- the number of manganese atoms is preferably more than 50% and less than 100% with respect to the total number of manganese atoms and iron atoms, more than 50% and less than 80%. More preferably. That is, in the above general formula (1), 0.5 ⁇ x ⁇ 1 is preferably satisfied, and 0.5 ⁇ x ⁇ 0.8 is more preferable.
- the number of manganese atoms is 50% of the total number of manganese atoms and iron atoms in that the initial coulomb efficiency of the battery can be further improved. It is preferably more than 100% and more preferably more than 50% and 80% or less.
- the number of manganese atoms exceeds 50% with respect to the sum of the number of manganese atoms and the number of iron atoms in that the discharge potential can be increased, and the electrode resistance does not become too high.
- the number of manganese atoms is preferably less than 100% and more preferably 90% or less in that good high rate charge / discharge characteristics can be obtained.
- the average particle size of the secondary particles is preferably 100 ⁇ m or less, and a particulate material is preferably used for the positive electrode for a lithium secondary battery.
- the average particle diameter of the secondary particles of particulate lithium iron manganese phosphate is preferably 0.1 ⁇ m to 20 ⁇ m, and the particle diameter of the primary particles constituting the secondary particles is preferably 1 nm to 500 nm.
- the average particle diameter of the secondary particles of lithium manganese iron phosphate and the average particle diameter of the primary particles are determined by image analysis of the results of transmission electron microscope (TEM) observation.
- the BET specific surface area of the lithium iron manganese phosphate particles is preferably 1 to 100 m 2 / g, preferably 5 to 100 m 2 / g in that the high rate charge / discharge characteristics of the positive electrode can be improved. More preferred.
- the lithium iron manganese phosphate particles are preferably provided with carbon supported on the surface from the viewpoint that electrical conductivity can be enhanced.
- the carbon may be partially provided on the surface of the lithium iron manganese phosphate particles or may be provided so as to cover the whole.
- the lithium nickel manganese cobalt composite oxide is an oxide containing a lithium atom, a nickel atom, a manganese atom, and a cobalt atom. Further, it has an ⁇ -NaFeO 2 type crystal structure classified as a hexagonal crystal, and nickel atoms, manganese atoms, and cobalt atoms are in solid solution with each other.
- a compound represented by the following general formula (2) is preferably used as the lithium nickel manganese cobalt composite oxide.
- the compound represented by the general formula (2) may contain a small amount of a transition metal element other than Mn, Ni, Co, or a typical element such as Al, as long as the basic properties of the compound are not changed. In this case, an element not represented by the general formula (2) is included in the lithium nickel manganese cobalt composite oxide.
- the number of cobalt atoms is preferably more than 0% and 67% or less with respect to the total of the number of nickel atoms, the number of manganese atoms, and the number of cobalt atoms. That is, in the general formula (2), it is preferable to satisfy 0 ⁇ y + z ⁇ 0.67.
- the initial Coulomb efficiency can be further improved.
- the number of cobalt atoms is less than the sum of the number of nickel atoms, the number of manganese atoms and the number of cobalt atoms in that good high rate charge / discharge characteristics can be obtained without excessively increasing the electrode resistance in the battery. It is preferably over 10%, more preferably 30% or more. Further, the number of cobalt atoms is preferably 67% or less in that the thermal stability of the positive electrode can be excellent. In the composite oxide, the number of nickel atoms and the number of manganese atoms are preferably approximately equal, and more preferably the same.
- the average particle size of secondary particles is preferably 100 ⁇ m or less, and a particulate material is preferably used for a positive electrode for a lithium secondary battery.
- the average particle diameter of the secondary particles of the particulate lithium nickel manganese cobalt composite oxide is preferably 0.1 ⁇ m to 100 ⁇ m, and more preferably 0.5 ⁇ m to 20 ⁇ m.
- the average particle diameter of the secondary particles of the lithium nickel manganese cobalt composite oxide is dispersed by ultrasonic irradiation with ion-exchanged water after sufficiently mixing the composite oxide particles and the surfactant. Then, the value of D 50 obtained by measuring at 20 ° C. using a laser diffraction / scattering particle size distribution measuring device (device name “SALD-2000J” manufactured by Shimadzu Corporation) is adopted.
- the BET specific surface area of the lithium nickel manganese cobalt composite oxide particles is preferably 0.1 to 10 m 2 / g from the viewpoint of improving the high rate charge / discharge characteristics of the positive electrode, and preferably 0.5 to 5 m 2. / G is more preferable.
- the mass ratio is in such a range, there is an advantage that the initial coulomb efficiency of the battery is further increased.
- the BET specific surface area of the lithium iron manganese phosphate particles is preferably larger than the BET specific surface area of the lithium nickel manganese cobalt composite oxide particles.
- the average particle size of lithium manganese manganese cobalt composite oxide particles is that the average particle size of lithium iron manganese phosphate particles can increase the packing density of the positive electrode by mixing those having different particle sizes. Is preferably smaller. Moreover, there is an advantage that the thermal stability of the positive electrode in a charged state can be increased by using a lithium nickel manganese cobalt composite oxide having a larger particle size.
- lithium manganese iron phosphate with a smaller particle size, the conduction path length of electrons in the solid phase and the diffusion path length of Li ions can be shortened, so the high rate charge / discharge characteristics of lithium manganese iron phosphate can be improved. There is an advantage that it can be greatly improved.
- conductive agent and the binder conventionally known ones can be used in general compounding amounts.
- the conductive agent is not limited as long as it is an electron conductive material that does not adversely affect the battery performance.
- natural graphite scale-like graphite, scale-like graphite, earth-like graphite, etc.
- artificial graphite carbon black, acetylene black , Ketjen Black, carbon whisker, carbon fiber, one type of electronic conductive material such as conductive ceramic material, or a mixture thereof.
- binder examples include thermoplastic resins such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene, and polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, and styrene butadiene.
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- EPDM ethylene-propylene-diene terpolymer
- SBR rubber
- fluororubber fluororubber
- the lithium manganese manganese phosphate or the lithium nickel manganese cobalt composite oxide contains a lithium atom, a manganese atom, an iron atom, a phosphorus atom, a nickel atom, a cobalt atom, etc., and its content is confirmed by ICP analysis can do.
- the fact that the metal atoms in the lithium iron manganese phosphate or the lithium nickel manganese cobalt composite oxide are in solid solution with each other, and that they have an olivine type or ⁇ -NaFeO 2 type crystal structure indicates that the X of the particle or electrode It can be confirmed by X-ray diffraction analysis (XRD). Further, more detailed analysis can be performed by electron microscope observation (TEM), scanning electron microscopic X-ray analysis (EPMA), high-resolution electron microscope analysis (HRAEM), or the like.
- TEM electron microscope observation
- EPMA scanning electron microscopic X-ray analysis
- HRAEM high-resolution electron microscope analysis
- the positive electrode active material may contain an intentionally mixed impurity for the purpose of improving various performances of the positive electrode active material.
- the positive electrode for a secondary battery is prepared, for example, by synthesizing the particles of lithium iron manganese phosphate and the particles of lithium nickel manganese cobalt composite oxide, and then preparing a paste containing these particles. It can be manufactured by drying the paste after coating on the electric body.
- a method for synthesizing the lithium manganese iron phosphate is not particularly limited, and becomes a phosphoric acid source and a raw material containing a metal element (Li, Mn, Fe) so as to have a composition ratio of a positive electrode active material to be synthesized. It can be obtained by mixing raw materials and firing the mixture.
- the method for synthesizing the lithium iron manganese phosphate for example, a particulate raw material containing a metal element (Li, Mn, Fe) and a particulate raw material serving as a phosphoric acid source are mixed and mixed. It is possible to employ a solid phase method of firing the mixed raw material. Further, for example, a liquid phase method for synthesizing lithium manganese iron phosphate from an aqueous solution containing a raw material containing a metal element (Li, Mn, Fe) and a raw material to be a phosphoric acid source can be employed. As the liquid phase method, a sol-gel method, a polyol method, a hydrothermal method, or the like can be employed.
- lithium manganese iron phosphate it is preferable to mechanically adhere or coat carbon on the surface of lithium manganese iron phosphate particles for the purpose of increasing the electrical conductivity of lithium manganese iron phosphate. Or it is preferable to adhere or coat carbon on the surface of lithium iron manganese phosphate particles by thermal decomposition of organic matter.
- the composition of the synthesized composite oxide is calculated from the composition ratio of raw materials. It can be slightly different. In order to bring the composition ratio of the raw materials close to the composition ratio of the synthesized composite oxide, in the synthesis of the composite oxide, it is preferable to sinter the material charged with a large amount of Li source.
- Ni compound, Mn compound and Co compound as raw materials are mixed with Li compound and fired.
- a coprecipitation precursor Ni-Mn-Co coprecipitation precursor described later
- a co-precipitation precursor Ni-Mn-Co co-precipitation precursor described later
- a co-precipitation precursor prepared by co-precipitation is mixed with a Li compound and fired because it can synthesize a more homogeneous composite oxide. It is preferable to do.
- the method for preparing the Ni—Mn—Co coprecipitation precursor includes Ni, Mn and Co in that Ni, Mn and Co are uniformly mixed in the prepared Ni—Mn—Co coprecipitation precursor. It is preferable to employ a coprecipitation method in which an acidic aqueous solution of Co is precipitated with an alkaline aqueous solution such as an aqueous sodium hydroxide solution.
- an acidic aqueous solution of Co is precipitated with an alkaline aqueous solution such as an aqueous sodium hydroxide solution.
- homogeneous and bulky coprecipitation precursor particles can be prepared, so that the nucleus of crystal growth is present in the presence of a larger number of ammonium ions than the total number of metal ions of Ni, Mn, and Co. Is preferably generated. Due to the presence of an excessive amount of ammonium ions, the rate of the precipitation reaction is moderated by going through the metal-ammine complex formation reaction. Therefore, there is an advantage that a precipitate having good crystal orientation and bulky and developed primary particle crystals can be produced. In the absence of ammonium ions, these metal ions rapidly form precipitates by an acid-base reaction, so that the crystal orientation tends to be disordered and precipitates with insufficient bulk density can be formed.
- the apparatus factors such as the reactor shape and the type of rotor blade, the time that the precipitate stays in the reaction vessel, the reaction vessel temperature, the total ion amount, the liquid pH, the ammonia ion concentration, the oxidation number adjusting agent By appropriately adjusting various factors such as the concentration, the physical properties such as the particle shape, bulk density, and surface area of the coprecipitation precursor particles can be controlled.
- the firing method in the synthesis of the lithium manganese iron phosphate is not particularly limited, and specifically, for example, a method of firing at 400 to 900 ° C., preferably 500 to 800 ° C. for 1 to 24 hours. Is preferred.
- the firing method in the synthesis of the lithium nickel manganese cobalt composite oxide is not particularly limited. Specifically, for example, the firing is performed at 700 to 1100 ° C., preferably 800 to 1000 ° C. for 1 to 24 hours. The method is preferred.
- a pulverizer or a classifier can be used to obtain particles of lithium manganese iron phosphate or lithium nickel manganese cobalt composite oxide in a predetermined shape.
- pulverizer for example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a planetary ball mill, a jet mill, a counter jet mill, a swirling air flow type jet mill or the like can be used.
- wet pulverization in which an organic solvent such as alcohol, hexane, or water coexists may be employed.
- a sieve or an air classifier can be used. The classification method is not particularly limited, and a dry or wet method using a sieve or an air classifier can be employed.
- the paste is made by mixing particles of lithium iron manganese phosphate or lithium nickel manganese cobalt composite oxide and a solvent.
- the solvent is not particularly limited, and for example, an organic solvent such as N-methyl-2-pyrrolidone (NMP), toluene, or alcohol, water, or the like can be used.
- Examples of the material for the current collector include aluminum, calcined carbon, conductive polymer, conductive glass, and the like. Among these, aluminum is preferable.
- Examples of the shape of the current collector include a sheet shape and a net shape.
- the thickness of the current collector is not particularly limited, but usually 1 to 500 ⁇ m.
- roller coating such as applicator roll, screen coating, blade coating, spin coating, and bar coating can be employed, but are not limited thereto.
- the amount of water contained in the positive electrode is preferably as small as possible, specifically less than 1000 ppm.
- a method of drying the positive electrode in a high temperature / depressurized environment or a method of electrochemically decomposing water contained in the positive electrode is suitable.
- the lithium secondary battery of the present embodiment includes at least the above-described positive electrode for a lithium secondary battery, a negative electrode, and a non-aqueous electrolyte containing an electrolyte salt in a non-aqueous solvent.
- a separator is provided between the positive electrode and the negative electrode, and an outer package for packaging the positive electrode, the negative electrode, the nonaqueous electrolyte, and the separator is provided.
- the material of the negative electrode is not particularly limited, and lithium metal, lithium alloy (lithium metal such as lithium-aluminum, lithium-lead, lithium-tin, lithium-aluminum-tin, lithium-gallium, and wood alloy) Alloys), alloys capable of occluding and releasing lithium, carbon materials (eg, graphite, hard carbon, low temperature fired carbon, amorphous carbon, etc.), lithium metal oxides (Li 4 Ti 5 O 12 etc.), etc. A metal oxide, a polyanion compound, etc. are mentioned. Among these, graphite is preferable in that it has an operating potential very close to that of metallic lithium and can realize charge and discharge at a high operating voltage.
- graphite for example, artificial graphite and natural graphite are preferable.
- graphite in which the surface of the negative electrode active material particles is modified with amorphous carbon or the like is more preferable in that gas generation during charging is small.
- the thickness of the electrode mixture layer constituting the electrode such as the positive electrode or the negative electrode is preferably 20 ⁇ m or more and 500 ⁇ m or less in that the energy density does not become too small while having a sufficient energy density.
- the thickness of the electrode is represented by the sum of the thickness of the current collector and the thickness of the electrode mixture layer.
- Nonaqueous solvents contained in the nonaqueous electrolyte include cyclic carbonates such as propylene carbonate and ethylene carbonate; cyclic esters such as ⁇ -butyrolactone and ⁇ -valerolactone; dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate.
- Chain carbonates such as neat; chain esters such as methyl formate, methyl acetate, methyl butyrate; tetrahydrofuran or derivatives thereof; 1,3-dioxane, 1,4-dioxane, 1,2-dimethoxyethane, 1 Ethers such as 1,4-dibutoxyethane and methyldiglyme; Nitriles such as acetonitrile and benzonitrile; Dioxolane or derivatives thereof; Ethylene sulfide, sulfolane, sultone or derivatives thereof.
- the non-aqueous solvent include, but are not limited to, one kind alone or a mixture of two or more kinds.
- Examples of the electrolyte salt contained in the non-aqueous electrolyte include ionic compounds such as LiBF 4 and LiPF 6 .
- the electrolyte salt one of these ionic compounds can be used alone, or two or more of them can be mixed and used.
- the concentration of the electrolyte salt in the non-aqueous electrolyte is preferably 0.5 mol / l or more and 5 mol / l or less in order to reliably obtain a non-aqueous electrolyte battery having high battery characteristics, and is 1 mol / l or more and 2.5 mol / l. The following is more preferable.
- Examples of the material for the separator include polyolefin resins typified by polyethylene and polypropylene, polyester resins typified by polyethylene terephthalate and polybutylene terephthalate, polyimide, polyvinylidene fluoride, and vinylidene fluoride-hexafluoropropylene. A polymer etc. can be mentioned.
- Examples of the material of the exterior body include nickel-plated iron, stainless steel, aluminum, metal resin composite film, and glass.
- the lithium secondary battery of this embodiment can be manufactured by a conventionally known general method.
- the lithium secondary battery positive electrode and the lithium secondary battery of the present embodiment are as illustrated above, but the present invention is not limited to the lithium secondary battery positive electrode and the lithium secondary battery illustrated above. That is, various modes used in a general lithium secondary battery positive electrode and a lithium secondary battery can be adopted as long as the effects of the present invention are not impaired.
- Example 1 A positive electrode active material having the following composition was prepared as follows, and a positive electrode for a lithium secondary battery was manufactured using the positive electrode active material.
- (Synthesis of LiMn 0.8 Fe 0.2 PO 4 ) 25 g of manganese acetate tetrahydrate (Mn (CH 3 COO) 2 .4H 2 O) and 7.09 g of iron sulfate heptahydrate (FeSO 4 .7H 2 O) were dissolved in 125 ml of purified water and mixed.
- a liquid was prepared.
- a phosphoric acid diluted solution obtained by diluting 14.55 g of phosphoric acid (H 3 PO 4 ) having a purity of 85% to 70 ml with purified water, and 151 ml of lithium hydroxide monohydrate (LiOH ⁇ H 2 O) 16.05 g And an aqueous lithium hydroxide solution dissolved in purified water.
- the phosphoric acid dilution solution was dripped at this liquid mixture, stirring the liquid mixture of manganese acetate tetrahydrate and iron sulfate heptahydrate.
- a precursor solution was prepared by dropping a lithium hydroxide aqueous solution in the same manner. Further, the precursor solution was heated and stirred for 1 hour on a 190 ° C. hot stirrer, and after cooling, the precursor was recovered by filtration and vacuum drying (100 ° C.).
- particles of a lithium secondary battery positive electrode active material LiMn 0.8 Fe 0.2 PO 4 having carbon supported on the surface were prepared.
- the positive electrode active material particles had a BET specific surface area of 34.6 m 2 / g.
- the primary particle diameter obtained by carrying out image analysis of the result of transmission electron microscope (TEM) observation was about 100 nm, and the secondary particle diameter was about 10 ⁇ m.
- the carbon on the active material surface is generated by thermal decomposition of sucrose added before mixing by a ball mill.
- manganese sulfate pentahydrate 0.585 mol / l
- nickel sulfate hexahydrate 0.585 mol / l
- cobalt sulfate heptahydrate 0.588 mol / l
- hydrazine monohydrate A raw material solution in which 0.0101 mol / l was dissolved was prepared. Subsequently, the raw material solution was continuously dropped into the reaction vessel at a flow rate of 3.17 ml / min while stirring the aqueous solution in the reaction vessel.
- a 12 mol / l aqueous ammonia solution was dropped into the reaction vessel at a flow rate of 0.22 ml / min to initiate the synthesis reaction.
- a 32% aqueous sodium hydroxide solution was intermittently added so that the pH of the aqueous solution in the reaction vessel was kept constant at 11.4.
- the heater was controlled intermittently so that the aqueous solution temperature in the reaction vessel was constant at 50 ° C.
- argon gas was blown directly into the water / night liquid in the reaction tank so that the reaction tank had a reducing atmosphere.
- the slurry was discharged out of the system using a flow pump so that the amount of the aqueous solution in the reaction tank was always a fixed amount of 3.5 liters.
- the mixture was filled in an alumina pot and heated to 1000 ° C. at a rate of 100 ° C./hr under dry air flow using an electric furnace. The temperature of 1000 ° C. was maintained for 15 hours, then cooled to 200 ° C. at a cooling rate of 100 ° C./hr, and then allowed to cool.
- particles of a positive electrode active material LiNi 0.33 Mn 0.33 Co 0.34 O 2 for a lithium secondary battery were produced.
- the average particle size (D 50 ) of the particles of this compound was 12.3 ⁇ m, and the specific surface area was 1.0 m 2 / g.
- NMP N-methyl-2-pyrrolidone
- this positive electrode paste to the single side
- the thickness of the positive electrode mixture layer after pressing was 50 ⁇ m, and the mass of the positive electrode mixture layer was about 70 mg.
- An aluminum positive electrode terminal was connected to the positive electrode by ultrasonic welding.
- diammonium hydrogen phosphate (NH 4 ) 2 HPO 4 ) and lithium hydroxide monohydrate (LiOH ⁇ H 2 O) are weighed at a molar ratio of 10:20, dissolved in purified water, and solution B was prepared.
- a hydrothermal reactor portable reactor TPR-1 type manufactured by Pressure Glass Industrial Co., Ltd.
- the obtained LiMn 0.8 Fe 0.2 PO 4 and polyvinyl alcohol (PVA) (degree of polymerization: about 1500) were weighed so as to have a mass ratio of 1: 1.14, and then ball mill (planet manufactured by FRITSCH) Mill, ball diameter 1 cm), and the mixed mixture is placed in an alumina sagger (outside dimensions 90 ⁇ 90 ⁇ 50 mm), and an atmosphere-replacement type firing furnace (a tabletop vacuum gas replacement furnace KDF- manufactured by Denken) 75) was fired under nitrogen flow (1.0 l / min).
- the firing temperature was 700 ° C.
- the firing time time for maintaining the firing temperature
- the rate of temperature increase was 5 ° C./min, and the temperature was naturally cooled.
- MnSO 4 .5H 2 O: FeSO 4 .7H 2 O: (NH 4 ) 2 HPO 4 : LiOH ⁇ H 2 O: ascorbic acid 9.5: 0.5: 10: LiMn 0.95 Fe 0.05 PO 4 was synthesized in the same manner as in Example 7 except that the molar ratio was 20: 0.025.
- Example 1 a point with a positive electrode active material LiNi 0.33 Mn 0.33 Co 0.34 O 2 produced in Example 1 as the lithium nickel manganese cobalt composite oxide, LiMn 0.95 Fe 0.05 PO 4: LiNi
- Example 1 a point with a positive electrode active material LiNi 0.33 Mn 0.33 Co 0.34 O 2 produced in Example 1 as the lithium nickel manganese cobalt composite oxide, LiMn 0.55 Fe 0.45 PO 4: LiNi
- a negative electrode was manufactured by attaching a metal lithium foil having a thickness of 100 ⁇ m onto a nickel foil current collector having a thickness of 10 ⁇ m. Moreover, the negative electrode terminal made from nickel was connected to the negative electrode by resistance welding.
- LiPF 6 as a fluorine-containing electrolyte salt is dissolved at a concentration of 1 mol / l in a mixed non-aqueous solvent in which ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate are mixed at a volume ratio of 1: 1: 1, and a non-aqueous electrolyte is obtained.
- the nonaqueous electrolyte was prepared so that the amount of water in the nonaqueous electrolyte was less than 50 ppm.
- a lithium secondary battery was assembled in a dry atmosphere with a dew point of ⁇ 40 ° C. or lower by the following procedure. That is, a positive electrode and a negative electrode, each having a water content of 500 ppm or less (measured by the Karl Fischer method) by vacuum drying at 150 ° C., face each other through a polypropylene separator having a thickness of 20 ⁇ m. It was.
- a metal resin composite film made of polyethylene terephthalate (15 ⁇ m) / aluminum foil (50 ⁇ m) / metal adhesive polypropylene film (50 ⁇ m) was used.
- a pole group composed of a positive electrode, a negative electrode, and a separator was hermetically sealed with an exterior body except for a portion serving as a liquid injection hole so that open ends of the positive electrode terminal and the negative electrode terminal were exposed to the outside. After injecting a certain amount of non-aqueous electrolyte from the injection hole, the injection hole part was heat-sealed under reduced pressure to assemble a battery.
- ⁇ Charge / discharge test> The lithium secondary batteries of each Example and each Comparative Example were subjected to a charging / discharging process of charging / discharging at a temperature of 2 cycles at 20 ° C.
- the charging conditions were a current of 0.1 ItmA (approximately 10 hour rate), a voltage of 4.3 V, and a constant current constant voltage charge of 15 hours, and the discharging conditions were a current of 0.1 ItmA (approximately 10 hour rate) and a final voltage of 2.5 V. Constant current discharge.
- Table 1 shows the results of the initial coulomb efficiency (discharge capacity / charge capacity) obtained in the first cycle in the lithium secondary batteries using the positive electrodes of Examples 1 to 6 and Comparative Examples 1 and 2.
- the initial coulombic efficiency of Examples 1 to 6 is higher than that of Comparative Examples 1 and 2. This result shows that by using a positive electrode active material containing lithium iron manganese phosphate and lithium nickel manganese cobalt composite oxide, the initial Coulomb efficiency is increased as compared with the case where each is used alone.
- the initial Coulomb efficiency is other than the ratio of lithium iron manganese phosphate and lithium nickel manganese cobalt composite oxide in the positive electrode active material in a mass ratio of 10:90 to 70:30. It can be recognized that it is higher.
- the mass of lithium manganese iron phosphate contained in the positive electrode is 10% or more and 70% or less based on the total mass of lithium manganese iron phosphate and lithium nickel manganese cobalt composite oxide. It shows that the coulomb efficiency becomes better.
- Table 2 shows the results of measuring the initial coulomb efficiency (discharge capacity / charge capacity) in the same manner as described above for the lithium secondary batteries using the positive electrodes of Examples 7 to 10 and Comparative Examples 3 to 7.
- Example 7 exceeds the prediction when compared with the results of Comparative Example 3 and Comparative Example 6. That is, in Comparative Example 3 and Comparative Example 6 using lithium iron manganese phosphate or lithium nickel manganese cobalt composite oxide alone, the initial Coulomb efficiency is 85.0% and 92.7%, respectively. In Example 7, in which lithium iron manganese oxide and lithium nickel manganese cobalt composite oxide were mixed at 50:50, the initial Coulomb efficiency is expected to be about 89%. On the other hand, the initial coulomb efficiency of Example 7 is 92.3%, which is far beyond expectations.
- Example 7 since lithium manganese iron phosphate and lithium nickel manganese cobalt composite oxide were mixed, the battery was used rather than the lithium nickel manganese cobalt composite oxide used alone as in Comparative Example 6. The safety is kept high. For the same reason, the result of Example 9 is also more than expected when compared with the results of Comparative Example 4 and Comparative Example 1. In Example 9, the safety of the battery is kept relatively high for the same reason as described above.
- the lithium secondary battery whose initial coulomb efficiency has been increased can reduce the amount of the negative electrode active material as the initial coulomb efficiency has been increased. Therefore, a lithium secondary battery having a relatively high initial Coulomb efficiency can be expected to have a relatively high energy density.
- the lithium secondary battery can be excellent in initial coulomb efficiency. Therefore, it is expected that a lithium secondary battery having a relatively high energy density can be provided by using the positive electrode for a lithium secondary battery of the present invention.
- the lithium secondary battery provided with the positive electrode for the lithium secondary battery according to the present invention is suitable for application in fields such as industrial batteries such as electric vehicles, which are required to have a high capacity and demand is increased in the future. The availability is extremely large.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
一方、今後は、リチウム二次電池を中型化又は大型化し特に大きな需要が見込まれる産業用途へ展開することが求められることから、リチウム二次電池の安全性が非常に重要視される。
また、小型民生用のリチウム二次電池が使用されないような環境下、即ち産業用途のリチウム二次電池が使用され得る高温環境下における使用においては、従来の小型民生用のリチウム二次電池は、ニッケル-カドミウム電池、鉛電池などと同様、電池寿命が非常に短いものとなる。一方、高温環境下でも長期間使用できるものとしては、キャパシターがあるものの、キャパシターはエネルギー密度が十分でないという点でユーザーの要求を満足するものではない。そこで、安全性を保ちつつ十分なエネルギー密度を有する電池が求められる。
前記リン酸マンガン鉄リチウムおよび前記リチウムニッケルマンガンコバルト複合酸化物は、リチウム二次電池用正極において、正極活物質の機能を発揮し得る。
前記リン酸マンガン鉄リチウムとしては、下記一般式(1)で表される化合物を用いることが好ましい。
LiMnxFe(1-x)PO4 (0<x<1)・・・一般式(1)
一般式(1)で表される化合物は、該化合物の基本的な性質が変わらない範囲内で、たとえばMn又はFe以外の遷移金属元素やAl等の典型元素を微量含み得る。この場合、上記一般式(1)で表されない元素が前記リン酸マンガン鉄リチウムに含まれる。なお、Mn又はFe以外の遷移金属元素としては、たとえば、コバルトやニッケルが挙げられる。
前記リチウム二次電池用正極においては、電池の初期クーロン効率がさらに優れたものとなり得るという点で、マンガン原子の数が、マンガン原子の数と鉄原子の数との合計に対して50%を超え100%未満であることが好ましく、50%を超え80%以下であることがより好ましい。また、放電電位を高くすることができるという点で、マンガン原子の数が、マンガン原子の数と鉄原子の数との合計に対して50%を超えることが好ましく、電極抵抗が高くなりすぎず良好な高率充放電特性を得ることができるという点で、上記マンガン原子の数が、100%未満であることが好ましく、90%以下であることがより好ましい。
なお、前記リン酸マンガン鉄リチウムの二次粒子の平均粒子径及び一次粒子の平均粒子径は、透過型電子顕微鏡(TEM)観察の結果を画像解析することにより求める。
前記リチウムニッケルマンガンコバルト複合酸化物としては、下記一般式(2)で表わされる化合物を用いることが好ましい。
LiaNi0.5-yMn0.5-zCoy+zO2 ・・・一般式(2)
(0<a<1.3、 0<y<0.5、 0<z<0.5、 -0.1≦y-z≦0.1)
一般式(2)で表される化合物は、該化合物の基本的な性質が変わらない範囲内で、たとえばMn、Ni又はCo以外の遷移金属元素やAl等の典型元素を微量含み得る。この場合、上記一般式(2)で表されない元素が前記リチウムニッケルマンガンコバルト複合酸化物に含まれる。
コバルト原子の数が、ニッケル原子の数とマンガン原子の数とコバルト原子の数との合計に対して0%を超え67%以下であることによって、初期クーロン効率がより優れたものとなり得る。
また、電池における電極抵抗が高くなりすぎず良好な高率充放電特性が得られるという点で、コバルト原子の数が、ニッケル原子の数とマンガン原子の数とコバルト原子の数との合計に対して10%を超えることが好ましく、30%以上であることがより好ましい。また、正極の熱安定性が優れたものになり得るという点で、上記コバルト原子の数が、67%以下であることが好ましい。
また、当該複合酸化物においては、ニッケル原子の数とマンガン原子の数とがほぼ等比であることが好ましく、同じであることがより好ましい。
なお、前記リチウムニッケルマンガンコバルト複合酸化物の二次粒子の平均粒子径は、該複合酸化物の粒子と界面活性剤とを十分に混練したのちに、イオン交換水を加えて超音波照射により分散させ、レーザー回折・散乱式の粒度分布測定装置(機器名「SALD-2000J」島津製作所社製)を用いて20℃において測定して得られるD50の値を採用したものである。
リン酸マンガン鉄リチウムの粒子の平均粒子径は、異なる粒子径を有するものを混合することにより正極の充填密度を高めることができるという点で、リチウムニッケルマンガンコバルト複合酸化物の粒子の平均粒子径よりも小さいことが好ましい。また、より粒子径の大きいリチウムニッケルマンガンコバルト複合酸化物を用いることにより、充電状態における正極の熱安定性が高まり得るという利点がある。また、より粒子径の小さいリン酸マンガン鉄リチウムを用いることにより、固相内の電子の伝導経路長やLiイオンの拡散経路長を短くできるため、リン酸マンガン鉄リチウムの高率充放電特性を大幅に改善することができるという利点がある。
前記リチウムニッケルマンガンコバルト複合酸化物の合成においては、Li源の一部が焼成中に揮発し得ることなどから、合成された複合酸化物の組成が、原料の仕込み組成比から計算される組成と若干異なることがあり得る。原料の仕込み組成比と合成された複合酸化物の組成比とを近づけるべく、該複合酸化物の合成においては、Li源を多めに仕込んだものを焼成することが好ましい。
前記Ni-Mn-Co共沈前駆体の調製方法において該共沈製法を採用することにより、共沈前駆体におけるNi、Mn、及びCoの混合状態が均質となり、電池の充放電によるLiの脱離・挿入によっても正極活物質に含まれる結晶構造が安定したものとなり得る。従って、該共沈前駆体を経て得られたリチウムニッケルマンガンコバルト複合酸化物を用いたリチウム二次電池は、優れた電池性能を有することができる。
前記リチウムニッケルマンガンコバルト複合酸化物の合成における焼成方法としては、特に限定されるものではなく、具体的には例えば、700~1100℃、好ましくは800~1000℃において、1~24時間で焼成する方法が好適である。
前記分級機としては、篩や風力分級機などを用いることができる。分級方法としては、特に限定されず、篩や風力分級機などを用いた乾式あるいは湿式の方法を採用することができる。
該集電体の形状としては、シート状、ネット状等が挙げられる。また、該集電体の厚さは特に限定されないが、通常、1~500μmのものが採用される。
前記非水電解質における電解質塩の濃度としては、高い電池特性を有する非水電解質電池を確実に得るために、0.5mol/l以上5mol/l以下が好ましく、1mol/l以上2.5mol/l以下がさらに好ましい。
即ち、一般的なリチウム二次電池正極及びリチウム二次電池において用いられる種々の態様を、本発明の効果を損ねない範囲において、採用することができる。
以下のようにして、下記組成の正極活物質を作製し、該正極活物質を用いてリチウム二次電池用正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=20:80]
(LiMn0.8Fe0.2PO4の合成)
酢酸マンガン四水和物(Mn(CH3COO)2・4H2O)25gと、硫酸鉄七水和物(FeSO4・7H2O)7.09gとを125mlの精製水に溶解させて混合液を調製した。
一方、純度85%のリン酸(H3PO4)14.55gを精製水で70mlに希釈したリン酸希釈溶液と、水酸化リチウム一水和物(LiOH・H2O)16.05gを151mlの精製水に溶解させた水酸化リチウム水溶液とをそれぞれ調製した。
次に、酢酸マンガン四水和物と硫酸鉄七水和物との混合液を撹拌しつつ、この混合液にリン酸希釈溶液を滴下した。続いて、水酸化リチウム水溶液を同様にして滴下して前駆体溶液を調製した。
さらに、前駆体溶液を190℃のホットスターラー上で1時間加熱及び撹拌を行い、冷却後、ろ過と真空乾燥(100℃)をおこなうことにより前駆体を回収した。
以上のようにして、表面にカーボンが担持されて設けられたリチウム二次電池用正極活物質LiMn0.8Fe0.2PO4の粒子を作製した。この正極活物質の粒子のBET比表面積は34.6m2/gであった。また、透過型電子顕微鏡(TEM)観察の結果を画像解析することにより得られた一次粒子径は、100nm程度であり、二次粒子径は、10μm程度であった。なお、活物質表面のカーボンは、ボールミルによる混合の前に加えたショ糖が熱分解して生成したものである。
まず、密閉型反応槽に水を3.5リットル入れた。次に、水のpHがpH=11.6となるように32%水酸化ナトリウム水溶液を水に加え水溶液を調製した。パドルタイプの撹拌羽根を備えた撹拌機を用いて、pH調整した水溶液を1200rpmの回転速度で撹拌しつつ、外部ヒーターにより反応槽内の水溶液の温度を50℃に保った。また、反応槽内の水溶液にアルゴンガスを吹き込んで、水溶液内の溶存酸素を除去した。
一方、硫酸マンガン五水和物(0.585mol/l)と硫酸ニッケル六水和物(0.585mol/l)と硫酸コバルト七水和物(0.588mol/l)とヒドラジン一水和物(0.0101mol/l)とが溶解している原料溶液を調製した。
続いて、反応槽内の水溶液を撹拌しつつ、該原料溶液を3.17ml/minの流量で反応槽に連続的に滴下した。同時に、12mol/lのアンモニア水溶液を0.22ml/minの流量で反応槽に滴下して合成反応を開始した。
合成反応中、反応槽内の水溶液のpHが11.4と一定になるように32%水酸化ナトリウム水溶液を断続的に投入した。また、反応槽内の水溶液温度が50℃で一定になるよう断続的にヒーターを制御した。また、反応槽内が還元雰囲気となるようにアルゴンガスを反応槽内の水夜液中に直接吹き込んだ。また、反応槽内の水溶液量が常に3.5リットルの一定量となるようにフローポンプを使ってスラリーを系外に排出した。
反応開始から60時間経過した時点から5時間の間に、反応晶析物であるNi-Mn-Co複合酸化物のスラリーを採取した。採取したスラリーを水洗、ろ過し、80℃で一晩乾燥させ、Ni-Mn-Co共沈前駆体の乾燥粉末を得た。
以上のようにして、リチウム二次電池用正極活物質LiNi0.33Mn0.33Co0.34O2の粒子を作製した。この化合物の粒子の平均粒子径(D50)は12.3μm、比表面積は1.0m2/gであった。
作製したそれぞれの正極活物質をLiMn0.8Fe0.2PO4:LiNi0.33Mn0.33Co0.34O2=20:80の質量比率で混合して混合正極活物質を調製した。次に、該混合正極活物質と、導電剤としてのアセチレンブラックと、結着剤としてのポリフッ化ビニリデン(PVdF)とを混合正極活物質:導電剤:結着剤=90:5:5の質量比で含有し、さらに溶媒としてN-メチル-2-ピロリドン(NMP)を含有する正極ペーストを調製した。そして、該正極ペーストを厚さ20μmのアルミニウム箔集電体上の片面に塗布し乾燥した後、プレス加工を行い、正極を製造した。プレス後の正極合剤層の厚さは50μmであり、正極合剤層の質量は70mg程度であった。該正極には、アルミニウム製の正極端子を超音波溶接により接続した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=10:90]
正極の製造において、LiMn0.8Fe0.2PO4:LiNi0.33Mn0.33Co0.34O2=10:90となるように混合した正極活物質を用いた点以外は、実施例1と同様にしてリチウム二次電池用正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=30:70]
正極の製造において、LiMn0.8Fe0.2PO4:LiNi0.33Mn0.33Co0.34O2=30:70となるように混合した正極活物質を用いた点以外は、実施例1と同様にしてリチウム二次電池用正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=50:50]
正極の製造において、LiMn0.8Fe0.2PO4:LiNi0.33Mn0.33Co0.34O2=50:50となるように混合した正極活物質を用いた点以外は、実施例1と同様にしてリチウム二次電池用正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=70:30]
正極の製造において、LiMn0.8Fe0.2PO4:LiNi0.33Mn0.33Co0.34O2=70:30となるように混合した正極活物質を用いた点以外は、実施例1と同様にしてリチウム二次電池用正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=80:20]
正極の製造において、LiMn0.8Fe0.2PO4:LiNi0.33Mn0.33Co0.34O2=80:20となるように混合した正極活物質を用いた点以外は、実施例1と同様にしてリチウム二次電池用正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=0:100]
正極の製造において、LiNi0.33Mn0.33Co0.34O2のみを正極活物質として用いた点以外は、実施例1と同様にしてリチウム二次電池用正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=100:0]
正極の製造において、LiMn0.8Fe0.2PO4のみを正極活物質として用いた点以外は、実施例1と同様にしてリチウム二次電池用正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=50:50]
(LiMn0.8Fe0.2PO4の合成)
硫酸マンガン五水和物(MnSO4・5H2O)と、硫酸鉄七水和物(FeSO4・7H2O)とアスコルビン酸とをモル比で8:2:0.025の比となるように秤量し、精製水に溶解させて溶液Aを調製した。
一方、リン酸水素二アンモニウム((NH4)2HPO4)と水酸化リチウム一水和物(LiOH・H2O)を10:20のモル比で秤量し、精製水に溶解させて溶液Bを調製した。
次に、溶液A及び溶液Bを混合して前駆体溶液を調製した。この前駆体溶液をポリテトラフルオロエチレン製の反応容器に移した。なお、ここまでの作業については窒素ボックス中で実施した。
続いて、前駆体溶液が入った反応容器を水熱反応装置(耐圧硝子工業株式会社製ポータブルリアクターTPR-1型)にセットし、容器内を窒素置換した後に、170℃で15時間の水熱反応による合成(水熱法)を実施した。水熱反応中、100rpmの回転速度で容器内の撹拌を行った。
そして、水熱反応により生じた生成物に対して、濾過、洗浄及び真空乾燥をおこなうことによりLiMn0.8Fe0.2PO4を得た。
このようにして、表面にカーボンが担持されて設けられたLiMn0.8Fe0.2PO4の粒子を作製した。これを正極活物質として用いた。
(LiNi0.165Mn0.165Co0.67O2の合成)
リチウムニッケルマンガンコバルト複合酸化物の作製において、硫酸マンガン五水和物(0.290mol/l)と硫酸ニッケル六水和物(0.290mol/l)と硫酸コバルト七水和物(1.178mol/l)とヒドラジン1水和物(0.0101mol/l)とが溶解している原料溶液を調製した点以外は、実施例1と同様にしてLiNi0.165Mn0.165Co0.67O2を合成した。
(正極の製造)
作製したそれぞれの正極活物質をLiMn0.8Fe0.2PO4:LiNi0.165Mn0.165Co0.67O2=50:50の質量比率で混合した点以外は、実施例1と同様にして正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=50:50]
(LiNi0.45Mn0.45Co0.10O2の合成)
リチウムニッケルマンガンコバルト複合酸化物の作製において、硫酸マンガン五水和物(0.791mol/l)と硫酸ニッケル六水和物(0.791mol/l)と硫酸コバルト七水和物(0.176mol/l)とヒドラジン1水和物(0.0101mol/l)とが溶解している原料溶液を調製した点以外は、実施例1と同様にしてLiNi0.45Mn0.45Co0.10O2を合成した。
そして、リン酸マンガン鉄リチウムとして実施例7で作製した正極活物質LiMn0.8Fe0.2PO4を用いた点、LiMn0.8Fe0.2PO4:LiNi0.45Mn0.45Co0.10O2=50:50の質量比率で混合した点以外は、実施例1と同様にして正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=50:50]
(LiMn0.95Fe0.05PO4 の合成)
リン酸マンガン鉄リチウムの作製において、MnSO4・5H2O:FeSO4・7H2O:(NH4)2HPO4:LiOH・H2O:アスコルビン酸=9.5:0.5:10:20:0.025のモル比となるように秤量した点以外は、実施例7と同様にしてLiMn0.95Fe0.05PO4を合成した。
そして、リチウムニッケルマンガンコバルト複合酸化物として実施例1で作製した正極活物質LiNi0.33Mn0.33Co0.34O2を用いた点、LiMn0.95Fe0.05PO4:LiNi0.33Mn0.33Co0.34O2=50:50の質量比率で混合した点以外は、実施例1と同様にして正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=50:50]
(LiMn0.55Fe0.45PO4の合成)
リン酸マンガン鉄リチウムの作製において、MnSO4・5H2O:FeSO4・7H2O:(NH4)2HPO4:LiOH・H2O:アスコルビン酸=5.5:4.5:10:20:0.025のモル比となるように秤量した点以外は、実施例7と同様にしてLiMn0.55Fe0.45PO4を合成した。
そして、リチウムニッケルマンガンコバルト複合酸化物として実施例1で作製した正極活物質LiNi0.33Mn0.33Co0.34O2を用いた点、LiMn0.55Fe0.45PO4:LiNi0.33Mn0.33Co0.34O2=50:50の質量比率で混合した点以外は、実施例1と同様にして正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=100:0]
正極の製造において、実施例7で用いたLiMn0.8Fe0.2PO4のみを正極活物質として用いた点以外は、実施例1と同様にしてリチウム二次電池用正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=100:0]
正極の製造において、実施例9で用いたLiMn0.95Fe0.05PO4のみを正極活物質として用いた点以外は、実施例1と同様にしてリチウム二次電池用正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=100:0]
正極の製造において、実施例10で用いたLiMn0.55Fe0.45PO4のみを正極活物質として用いた点以外は、実施例1と同様にしてリチウム二次電池用正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=0:100]
正極の製造において、実施例7で用いたLiNi0.165Mn0.165Co0.67O2のみを正極活物質として用いた点以外は、実施例1と同様にしてリチウム二次電池用正極を製造した。
[LiMnxFe(1-x)PO4:LiaNi0.5-yMn0.5-zCoy+zO2=0:100]
正極の製造において、実施例8で用いたLiNi0.45Mn0.45Co0.10O2のみを正極活物質として用いた点以外は、実施例1と同様にしてリチウム二次電池用正極を製造した。
厚さ100μmの金属リチウム箔を厚さ10μmのニッケル箔集電体上に貼り付けることにより負極を製造した。また、負極には、ニッケル製の負極端子を抵抗溶接により接続した。
エチレンカーボネート、ジメチルカーボネート及びメチルエチルカーボネートを体積比1:1:1の割合で混合した混合非水溶媒に、含フッ素系電解質塩としてのLiPF6を1mol/lの濃度で溶解させ、非水電解質を調製した。なお、該非水電解質中の水分量が50ppm未満となるように非水電解質を調製した。
各実施例、各比較例の正極を用い、下記の手順により、露点-40℃以下の乾燥雰囲気下においてリチウム二次電池を組み立てた。
即ち、150℃の真空乾燥をおこなうことにより含有水分量を500ppm以下(カールフィッシャー法により測定)とした正極と、負極とを各1枚、厚さ20μmのポリプロピレン製セパレ-タを介して対向させた。また、外装体としては、ポリエチレンテレフタレ-ト(15μm)/アルミニウム箔(50μm)/金属接着性ポリプロピレンフィルム(50μm)からなる金属樹脂複合フィルムを用いた。正極と負極とセパレータからなる極群を、正極端子及び負極端子の開放端部が外部露出するように、注液孔となる部分以外を外装体によって気密封止した。注液孔から一定量の非水電解質を注液後、減圧状態で注液孔部分を熱封口し、電池を組み立てた。
各実施例、各比較例のリチウム二次電池を20℃において、温度2サイクルの充放電を行う充放電工程に供した。充電条件は、電流0.1ItmA(約10時間率)、電圧4.3V、15時間の定電流定電圧充電とし、放電条件は、電流0.1ItmA(約10時間率)、終止電圧2.5Vの定電流放電とした。
同様の理由により、実施例9の結果も、比較例4及び比較例1の結果と比較すると予測を超えるものである。また、実施例9においては、上述の理由と同様の理由により、電池の安全性が比較的高く保たれている。
本発明のリチウム二次電池用正極を備えたリチウム二次電池は、特に高容量化が求められ今後需要が高まる電気自動車等の産業用電池などの分野への応用に適しており、産業上の利用可能性は極めて大きい。
Claims (4)
- リン酸マンガン鉄リチウムとリチウムニッケルマンガンコバルト複合酸化物とを含むことを特徴とするリチウム二次電池用正極。
- 前記リン酸マンガン鉄リチウム(A)と前記リチウムニッケルマンガンコバルト複合酸化物(B)との質量比率(A:B)が10:90~70:30である請求項1記載のリチウム二次電池用正極。
- 前記リン酸マンガン鉄リチウムに含まれるマンガン原子の数は、マンガン原子及び鉄原子の数の合計に対して50%を超え100%未満であり、前記リチウムニッケルマンガンコバルト複合酸化物に含まれるコバルト原子の数は、ニッケル原子、マンガン原子、及びコバルト原子の数の合計に対して0%を超え67%以下である請求項1又は2記載のリチウム二次電池用正極。
- 請求項1~3のいずれかに記載のリチウム二次電池用正極と、負極と、非水電解質とを備えていることを特徴とするリチウム二次電池。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020117011569A KR20110083680A (ko) | 2008-11-06 | 2009-11-09 | 리튬 2차 전지용 양극 및 리튬 2차 전지 |
EP09824871.9A EP2357693B1 (en) | 2008-11-06 | 2009-11-09 | Positive electrode for lithium secondary battery, and lithium secondary battery |
JP2010536811A JP5574239B2 (ja) | 2008-11-06 | 2009-11-09 | リチウム二次電池用正極及びリチウム二次電池 |
CN200980144517.5A CN102210047B (zh) | 2008-11-06 | 2009-11-09 | 锂二次电池用正极及锂二次电池 |
US13/127,980 US20110223482A1 (en) | 2008-11-06 | 2009-11-09 | Positive electrode for lithium secondary battery and lithium secondary battery |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008285989A JP5381024B2 (ja) | 2008-11-06 | 2008-11-06 | リチウム二次電池用正極及びリチウム二次電池 |
JP2008-285989 | 2008-11-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010053174A1 true WO2010053174A1 (ja) | 2010-05-14 |
Family
ID=42152979
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/069046 WO2010053174A1 (ja) | 2008-11-06 | 2009-11-09 | リチウム二次電池用正極及びリチウム二次電池 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20110223482A1 (ja) |
EP (1) | EP2357693B1 (ja) |
JP (2) | JP5381024B2 (ja) |
KR (1) | KR20110083680A (ja) |
CN (1) | CN102210047B (ja) |
WO (1) | WO2010053174A1 (ja) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012190786A (ja) * | 2011-03-09 | 2012-10-04 | Samsung Sdi Co Ltd | 正極活物質、並びにそれを採用した正極及びリチウム電池 |
JP2012211072A (ja) * | 2011-03-18 | 2012-11-01 | Semiconductor Energy Lab Co Ltd | リチウム含有複合酸化物の作製方法 |
JP2013125712A (ja) * | 2011-12-15 | 2013-06-24 | Gs Yuasa Corp | 非水電解質電池用正極、それを用いた非水電解質電池、及び、その電池を搭載したプラグインハイブリッド自動車 |
US20140065462A1 (en) * | 2012-08-29 | 2014-03-06 | Apple Inc. | Increased energy density and swelling control in batteries for portable electronic devices |
JP2015162322A (ja) * | 2014-02-27 | 2015-09-07 | 住友金属鉱山株式会社 | 非水電解質二次電池用正極活物質の前駆体とその製造方法、及び非水電解質二次電池用正極活物質の製造方法 |
JP2015170464A (ja) * | 2014-03-06 | 2015-09-28 | 旭化成株式会社 | 非水電解質二次電池 |
JP2015195172A (ja) * | 2014-03-24 | 2015-11-05 | 株式会社デンソー | リチウムイオン二次電池 |
JP2016524307A (ja) * | 2013-07-09 | 2016-08-12 | ダウ グローバル テクノロジーズ エルエルシー | リチウム金属酸化物及びリチウム金属リン酸塩を含む混合正活性材料 |
WO2016139957A1 (ja) * | 2015-03-04 | 2016-09-09 | 株式会社豊田自動織機 | リチウムイオン二次電池用正極及びその製造方法並びにリチウムイオン二次電池 |
WO2017013827A1 (ja) * | 2015-07-22 | 2017-01-26 | 株式会社豊田自動織機 | リチウムイオン二次電池 |
JP2017073343A (ja) * | 2015-10-09 | 2017-04-13 | 株式会社デンソー | 充放電制御装置及び組電池装置 |
US10541408B2 (en) * | 2012-04-24 | 2020-01-21 | Lg Chem, Ltd. | Active material for lithium secondary battery composite electrode for improving output and lithium secondary battery including the active material |
WO2020066909A1 (ja) * | 2018-09-25 | 2020-04-02 | 東レ株式会社 | 二次電池用電極およびリチウムイオン二次電池 |
WO2020116160A1 (ja) | 2018-12-05 | 2020-06-11 | 東レ株式会社 | リチウムイオン二次電池用正極電極、リチウムイオン二次電池用電極ペースト、リチウムイオン二次電池 |
JP2020100555A (ja) * | 2011-08-31 | 2020-07-02 | 株式会社半導体エネルギー研究所 | 複合酸化物の作製方法 |
US11108038B2 (en) | 2012-08-27 | 2021-08-31 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode for secondary battery, secondary battery, and method for fabricating positive electrode for secondary battery |
US11728475B2 (en) | 2020-02-18 | 2023-08-15 | Honda Motor Co., Ltd. | Lithium-ion secondary battery positive electrode active material complex, lithium-ion secondary battery positive electrode, and lithium-ion secondary battery |
Families Citing this family (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5159681B2 (ja) | 2009-03-25 | 2013-03-06 | 株式会社東芝 | 非水電解質電池 |
KR20120030774A (ko) * | 2010-09-20 | 2012-03-29 | 삼성에스디아이 주식회사 | 양극 활물질, 이의 제조방법 및 이를 이용한 리튬 전지 |
KR102131859B1 (ko) | 2011-03-25 | 2020-07-08 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 리튬 이온 2차 전지 |
JP6052168B2 (ja) * | 2011-04-28 | 2016-12-27 | 日本電気株式会社 | リチウム二次電池 |
JP6396799B2 (ja) | 2011-07-25 | 2018-09-26 | エイ123・システムズ・リミテッド・ライアビリティ・カンパニーA123 Systems, Llc | 混合カソード材料 |
KR102344325B1 (ko) | 2011-08-29 | 2021-12-29 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 리튬 이온 전지용 양극 활물질의 제작 방법 |
US9118077B2 (en) | 2011-08-31 | 2015-08-25 | Semiconductor Energy Laboratory Co., Ltd. | Manufacturing method of composite oxide and manufacturing method of power storage device |
CN102427123B (zh) * | 2011-11-14 | 2016-05-18 | 东莞新能源科技有限公司 | 锂离子二次电池及其正极片 |
JP5766761B2 (ja) * | 2011-11-14 | 2015-08-19 | 株式会社東芝 | 非水電解質電池 |
KR101893955B1 (ko) * | 2011-12-16 | 2018-09-03 | 삼성에스디아이 주식회사 | 금속 도핑된 결정성 철인산염, 이의 제조 방법 및 이로부터 제조된 리튬 복합금속인산화물 |
JP2013246936A (ja) * | 2012-05-24 | 2013-12-09 | Hitachi Ltd | 非水系二次電池用正極活物質 |
JP2014001110A (ja) * | 2012-06-20 | 2014-01-09 | Taiyo Yuden Co Ltd | リチウムチタン複合酸化物、その製造方法及び電池用電極 |
CA2876237A1 (en) * | 2012-06-27 | 2014-01-03 | Dow Global Technologies Llc | Low-cost method for making lithium transition metal olivines with high energy density |
KR101560862B1 (ko) * | 2012-08-02 | 2015-10-15 | 주식회사 엘지화학 | 출력 특성이 향상된 혼합 양극활물질 및 이를 포함하는 리튬이차전지 |
EP2894703B1 (en) | 2012-09-04 | 2018-10-31 | Toyota Jidosha Kabushiki Kaisha | Nonaqueous electrolyte secondary battery |
US20140134501A1 (en) * | 2012-11-12 | 2014-05-15 | Novolyte Technologies, Inc. | Non-Aqueous Electrolytic Solutions And Electrochemical Cells Comprising Same |
US9478808B2 (en) | 2012-12-12 | 2016-10-25 | Samsung Sdi Co., Ltd. | Positive active material, positive electrode and rechargeable lithium battery including same |
CN104871350A (zh) * | 2012-12-21 | 2015-08-26 | 陶氏环球技术有限责任公司 | 使用水/共溶剂混合物制造锂过渡金属橄榄石的方法 |
KR101593005B1 (ko) * | 2013-01-31 | 2016-02-11 | 주식회사 엘지화학 | 내구성이 향상된 이차전지용 양극 활물질 및 이를 포함하는 리튬 이차전지 |
CN105359311B (zh) * | 2013-07-10 | 2017-10-31 | 株式会社杰士汤浅国际 | 锂二次电池用混合活性物质、锂二次电池用电极、锂二次电池及蓄电装置 |
JP6469707B2 (ja) * | 2013-09-20 | 2019-02-13 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | リチウムイオンバッテリーのための電極材料 |
WO2015136591A1 (ja) * | 2014-03-10 | 2015-09-17 | 株式会社豊田自動織機 | 第1正極活物質及び第2正極活物質を有する正極活物質層、並びに該正極活物質層を具備する正極の製造方法 |
JP5983679B2 (ja) * | 2014-05-30 | 2016-09-06 | トヨタ自動車株式会社 | 非水電解質二次電池およびその製造方法 |
JP6287651B2 (ja) | 2014-07-10 | 2018-03-07 | トヨタ自動車株式会社 | 非水系二次電池 |
US20170338469A1 (en) * | 2014-11-28 | 2017-11-23 | Basf Se | Process for making lithiated transition metal oxides |
EP3235028B1 (en) * | 2014-12-18 | 2021-05-12 | Dow Global Technologies LLC | Lithium ion battery having improved thermal stability |
JP6596826B2 (ja) | 2015-01-15 | 2019-10-30 | 株式会社デンソー | 電極及び非水電解質二次電池 |
FR3036538B1 (fr) * | 2015-05-19 | 2017-05-19 | Accumulateurs Fixes | Electrode positive pour generateur electrochimique au lithium |
JP6151386B2 (ja) * | 2015-06-09 | 2017-06-21 | 太平洋セメント株式会社 | オリビン型リン酸リチウム系正極材料の製造方法 |
EP3352261A4 (en) | 2015-09-14 | 2019-04-17 | Kabushiki Kaisha Toshiba | NONAQUEOUS ELECTROLYTE BATTERY AND BATTERY PACK |
JP6917161B2 (ja) | 2016-03-03 | 2021-08-11 | 株式会社半導体エネルギー研究所 | リチウムイオン二次電池用の正極活物質、二次電池、電池制御ユニットおよび電子機器 |
CN105655584B (zh) * | 2016-03-07 | 2017-12-01 | 昆明理工大学 | 一种用于制备锂电池正极材料的磷酸锰铁铵的制备方法 |
CN107658432A (zh) * | 2016-07-26 | 2018-02-02 | 微宏动力系统(湖州)有限公司 | 改性金属氧化物正极材料的制备方法及其正极材料 |
EP3782214A4 (en) * | 2018-04-19 | 2022-01-12 | A123 Systems LLC | PROCESSES AND SYSTEMS FOR COATED CATHODE MATERIALS AND USE OF COATED CATHODE MATERIALS |
WO2020062046A1 (zh) * | 2018-09-28 | 2020-04-02 | 宁波致良新能源有限公司 | 正极添加剂及其制备方法、正极及其制备方法和锂离子电池 |
US11804601B2 (en) | 2019-09-12 | 2023-10-31 | Saft America | Cathode materials for lithium ion batteries |
US20210408524A1 (en) * | 2020-06-25 | 2021-12-30 | GM Global Technology Operations LLC | Cathode active material for lithium ion batteries for electric vehicles |
FR3112030B1 (fr) * | 2020-06-26 | 2022-12-16 | Accumulateurs Fixes | Utilisation d’éléments électrochimiques secondaires au lithium contenant un mélange d'un oxyde lithié de nickel et d'un phosphate lithié de manganèse et de fer pour des applications automobiles |
CN116601794A (zh) * | 2021-12-13 | 2023-08-15 | 宁德时代新能源科技股份有限公司 | 一种正极活性材料及其相关的极片、二次电池、电池模块、电池包和装置 |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001307730A (ja) | 2000-04-25 | 2001-11-02 | Sony Corp | 正極及び非水電解質電池 |
JP2002075368A (ja) | 2000-09-05 | 2002-03-15 | Sony Corp | 正極活物質及び非水電解質電池並びにそれらの製造方法 |
JP2002216755A (ja) | 2001-01-22 | 2002-08-02 | Denso Corp | 非水電解質二次電池 |
JP2002279989A (ja) | 2001-03-16 | 2002-09-27 | Sony Corp | 電 池 |
JP3632686B2 (ja) | 2002-08-27 | 2005-03-23 | ソニー株式会社 | 正極活物質及び非水電解質二次電池 |
JP2005183384A (ja) | 2003-12-23 | 2005-07-07 | Saft (Soc Accumulateurs Fixes Traction) Sa | リチウム充電式電気化学的電池の正極用の電気化学的活物質 |
JP2006252894A (ja) * | 2005-03-09 | 2006-09-21 | Sony Corp | 正極材料および電池 |
JP2006252895A (ja) * | 2005-03-09 | 2006-09-21 | Sony Corp | 電池 |
JP2006523368A (ja) * | 2003-04-03 | 2006-10-12 | ヴァレンス テクノロジー インコーポレーテッド | 混合粒子を含む電極 |
JP2007220658A (ja) * | 2006-01-18 | 2007-08-30 | Matsushita Electric Ind Co Ltd | 組電池、電源システム及び組電池の製造方法 |
JP2007234565A (ja) * | 2005-03-18 | 2007-09-13 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
JP2008525973A (ja) | 2004-12-28 | 2008-07-17 | ボストン−パワー,インコーポレイテッド | リチウムイオン二次電池 |
JP2008198542A (ja) * | 2007-02-15 | 2008-08-28 | Sony Corp | 非水電解液およびこれを用いた非水電解液二次電池 |
JP2008243662A (ja) * | 2007-03-28 | 2008-10-09 | Gs Yuasa Corporation:Kk | 非水電解質二次電池用正極活物質及びそれを用いた非水電解質二次電池 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1441395B9 (de) | 1996-06-26 | 2012-08-15 | OSRAM Opto Semiconductors GmbH | Lichtabstrahlendes Halbleiterbauelement mit Lumineszenzkonversionselement |
US20070141468A1 (en) * | 2003-04-03 | 2007-06-21 | Jeremy Barker | Electrodes Comprising Mixed Active Particles |
US8617745B2 (en) * | 2004-02-06 | 2013-12-31 | A123 Systems Llc | Lithium secondary cell with high charge and discharge rate capability and low impedance growth |
CN103531765B (zh) * | 2005-05-17 | 2017-01-11 | 索尼株式会社 | 正极活性物质,正极活性物质的制造方法和电池 |
KR102062521B1 (ko) | 2005-10-20 | 2020-01-06 | 미쯔비시 케미컬 주식회사 | 리튬 2 차 전지 및 그것에 사용하는 비수계 전해액 |
US8133616B2 (en) | 2006-02-14 | 2012-03-13 | Dow Global Technologies Llc | Lithium manganese phosphate positive material for lithium secondary battery |
JP5137312B2 (ja) * | 2006-03-17 | 2013-02-06 | 三洋電機株式会社 | 非水電解質電池 |
KR20080108222A (ko) * | 2006-04-07 | 2008-12-12 | 미쓰비시 가가꾸 가부시키가이샤 | 리튬 이차 전지 정극 재료용 리튬 천이 금속계 화합물분체, 그 제조 방법, 그 분무 건조체 및 그 소성 전구체,그리고, 그것을 사용한 리튬 이차 전지용 정극 및 리튬이차 전지 |
CA2569991A1 (en) | 2006-12-07 | 2008-06-07 | Michel Gauthier | C-treated nanoparticles and agglomerate and composite thereof as transition metal polyanion cathode materials and process for making |
KR100889622B1 (ko) | 2007-10-29 | 2009-03-20 | 대정이엠(주) | 안전성이 우수한 리튬 이차전지용 양극 활물질 및 그제조방법과 이를 포함하는 리튬 이차전지 |
EP2065887A1 (en) | 2007-11-30 | 2009-06-03 | Hitachi Global Storage Technologies Netherlands B.V. | Method for manufacturing magnetic disk unit |
CN101978534A (zh) * | 2008-03-24 | 2011-02-16 | 3M创新有限公司 | 高电压阴极组合物 |
-
2008
- 2008-11-06 JP JP2008285989A patent/JP5381024B2/ja active Active
-
2009
- 2009-11-09 EP EP09824871.9A patent/EP2357693B1/en active Active
- 2009-11-09 WO PCT/JP2009/069046 patent/WO2010053174A1/ja active Application Filing
- 2009-11-09 US US13/127,980 patent/US20110223482A1/en not_active Abandoned
- 2009-11-09 JP JP2010536811A patent/JP5574239B2/ja active Active
- 2009-11-09 KR KR1020117011569A patent/KR20110083680A/ko not_active Application Discontinuation
- 2009-11-09 CN CN200980144517.5A patent/CN102210047B/zh active Active
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001307730A (ja) | 2000-04-25 | 2001-11-02 | Sony Corp | 正極及び非水電解質電池 |
JP2002075368A (ja) | 2000-09-05 | 2002-03-15 | Sony Corp | 正極活物質及び非水電解質電池並びにそれらの製造方法 |
JP2002216755A (ja) | 2001-01-22 | 2002-08-02 | Denso Corp | 非水電解質二次電池 |
JP2002279989A (ja) | 2001-03-16 | 2002-09-27 | Sony Corp | 電 池 |
JP3632686B2 (ja) | 2002-08-27 | 2005-03-23 | ソニー株式会社 | 正極活物質及び非水電解質二次電池 |
JP2006523368A (ja) * | 2003-04-03 | 2006-10-12 | ヴァレンス テクノロジー インコーポレーテッド | 混合粒子を含む電極 |
JP2005183384A (ja) | 2003-12-23 | 2005-07-07 | Saft (Soc Accumulateurs Fixes Traction) Sa | リチウム充電式電気化学的電池の正極用の電気化学的活物質 |
JP2008525973A (ja) | 2004-12-28 | 2008-07-17 | ボストン−パワー,インコーポレイテッド | リチウムイオン二次電池 |
JP2006252894A (ja) * | 2005-03-09 | 2006-09-21 | Sony Corp | 正極材料および電池 |
JP2006252895A (ja) * | 2005-03-09 | 2006-09-21 | Sony Corp | 電池 |
JP2007234565A (ja) * | 2005-03-18 | 2007-09-13 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
JP2007220658A (ja) * | 2006-01-18 | 2007-08-30 | Matsushita Electric Ind Co Ltd | 組電池、電源システム及び組電池の製造方法 |
JP2008198542A (ja) * | 2007-02-15 | 2008-08-28 | Sony Corp | 非水電解液およびこれを用いた非水電解液二次電池 |
JP2008243662A (ja) * | 2007-03-28 | 2008-10-09 | Gs Yuasa Corporation:Kk | 非水電解質二次電池用正極活物質及びそれを用いた非水電解質二次電池 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2357693A4 * |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012190786A (ja) * | 2011-03-09 | 2012-10-04 | Samsung Sdi Co Ltd | 正極活物質、並びにそれを採用した正極及びリチウム電池 |
JP2012211072A (ja) * | 2011-03-18 | 2012-11-01 | Semiconductor Energy Lab Co Ltd | リチウム含有複合酸化物の作製方法 |
US9627686B2 (en) | 2011-03-18 | 2017-04-18 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing lithium-containing composite oxide |
US11283075B2 (en) | 2011-08-31 | 2022-03-22 | Semiconductor Energy Laboratory Co., Ltd. | Manufacturing method of composite oxide and manufacturing method of power storage device |
JP2021070627A (ja) * | 2011-08-31 | 2021-05-06 | 株式会社半導体エネルギー研究所 | 複合酸化物の作製方法 |
JP2020100555A (ja) * | 2011-08-31 | 2020-07-02 | 株式会社半導体エネルギー研究所 | 複合酸化物の作製方法 |
US11799084B2 (en) | 2011-08-31 | 2023-10-24 | Semiconductor Energy Laboratory Co., Ltd. | Method for making LiFePO4 by hydrothermal method |
JP2022179593A (ja) * | 2011-08-31 | 2022-12-02 | 株式会社半導体エネルギー研究所 | 複合酸化物の作製方法 |
JP2013125712A (ja) * | 2011-12-15 | 2013-06-24 | Gs Yuasa Corp | 非水電解質電池用正極、それを用いた非水電解質電池、及び、その電池を搭載したプラグインハイブリッド自動車 |
US10541408B2 (en) * | 2012-04-24 | 2020-01-21 | Lg Chem, Ltd. | Active material for lithium secondary battery composite electrode for improving output and lithium secondary battery including the active material |
US11108038B2 (en) | 2012-08-27 | 2021-08-31 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode for secondary battery, secondary battery, and method for fabricating positive electrode for secondary battery |
US20140065462A1 (en) * | 2012-08-29 | 2014-03-06 | Apple Inc. | Increased energy density and swelling control in batteries for portable electronic devices |
JP2016524307A (ja) * | 2013-07-09 | 2016-08-12 | ダウ グローバル テクノロジーズ エルエルシー | リチウム金属酸化物及びリチウム金属リン酸塩を含む混合正活性材料 |
KR101938462B1 (ko) * | 2013-07-09 | 2019-01-14 | 다우 글로벌 테크놀로지스 엘엘씨 | 리튬 금속 산화물 및 리튬 금속 포스페이트를 포함하는 혼합된 양성 활성 물질 |
JP2015162322A (ja) * | 2014-02-27 | 2015-09-07 | 住友金属鉱山株式会社 | 非水電解質二次電池用正極活物質の前駆体とその製造方法、及び非水電解質二次電池用正極活物質の製造方法 |
JP2015170464A (ja) * | 2014-03-06 | 2015-09-28 | 旭化成株式会社 | 非水電解質二次電池 |
JP2015195172A (ja) * | 2014-03-24 | 2015-11-05 | 株式会社デンソー | リチウムイオン二次電池 |
JPWO2016139957A1 (ja) * | 2015-03-04 | 2017-12-07 | 株式会社豊田自動織機 | リチウムイオン二次電池用正極及びその製造方法並びにリチウムイオン二次電池 |
WO2016139957A1 (ja) * | 2015-03-04 | 2016-09-09 | 株式会社豊田自動織機 | リチウムイオン二次電池用正極及びその製造方法並びにリチウムイオン二次電池 |
WO2017013827A1 (ja) * | 2015-07-22 | 2017-01-26 | 株式会社豊田自動織機 | リチウムイオン二次電池 |
JP2017073343A (ja) * | 2015-10-09 | 2017-04-13 | 株式会社デンソー | 充放電制御装置及び組電池装置 |
WO2020066909A1 (ja) * | 2018-09-25 | 2020-04-02 | 東レ株式会社 | 二次電池用電極およびリチウムイオン二次電池 |
WO2020116160A1 (ja) | 2018-12-05 | 2020-06-11 | 東レ株式会社 | リチウムイオン二次電池用正極電極、リチウムイオン二次電池用電極ペースト、リチウムイオン二次電池 |
KR20210076147A (ko) | 2018-12-05 | 2021-06-23 | 도레이 카부시키가이샤 | 리튬 이온 이차 전지용 정극 전극, 리튬 이온 이차 전지용 전극 페이스트, 리튬 이온 이차 전지 |
US11728475B2 (en) | 2020-02-18 | 2023-08-15 | Honda Motor Co., Ltd. | Lithium-ion secondary battery positive electrode active material complex, lithium-ion secondary battery positive electrode, and lithium-ion secondary battery |
Also Published As
Publication number | Publication date |
---|---|
KR20110083680A (ko) | 2011-07-20 |
US20110223482A1 (en) | 2011-09-15 |
JP2011159388A (ja) | 2011-08-18 |
EP2357693A1 (en) | 2011-08-17 |
CN102210047B (zh) | 2014-06-25 |
CN102210047A (zh) | 2011-10-05 |
JP5574239B2 (ja) | 2014-08-20 |
EP2357693B1 (en) | 2018-07-11 |
JPWO2010053174A1 (ja) | 2012-04-05 |
EP2357693A4 (en) | 2014-04-30 |
JP5381024B2 (ja) | 2014-01-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5574239B2 (ja) | リチウム二次電池用正極及びリチウム二次電池 | |
JP6596405B2 (ja) | 非水電解質二次電池用負極活物質、非水電解質二次電池、及び非水電解質二次電池用負極材の製造方法 | |
CN107710466B (zh) | 负极活性物质及二次电池、以及负极材料的制造方法 | |
CN108140823B (zh) | 负极活性物质、二次电池、负极材料和二次电池制造方法 | |
JP5272756B2 (ja) | リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池、並びに、その製造方法 | |
US9437865B2 (en) | Active material for lithium ion secondary battery, and lithium ion secondary battery | |
TWI492443B (zh) | 鋰二次電池用正極活性物質、鋰二次電池用電極以及鋰二次電池 | |
JP5103923B2 (ja) | 非水系電解質二次電池用正極活物質、その製造方法及びそれを用いた非水系電解質二次電池 | |
JP6448462B2 (ja) | 非水電解質二次電池用負極活物質及び非水電解質二次電池並びに非水電解質二次電池用負極活物質の製造方法 | |
JP5145994B2 (ja) | 非水系電解質二次電池用正極活物質とその製造方法 | |
JP2014072025A (ja) | 非水電解質二次電池及びその製造方法 | |
Hwang et al. | Mesoporous spinel LiMn2O4 nanomaterial as a cathode for high-performance lithium ion batteries | |
JP2024516811A (ja) | 正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池 | |
CA2764905A1 (en) | Cathode material for a lithium secondary battery, method for manufacturing same, and lithium secondary battery including same | |
WO2017145654A1 (ja) | 非水電解質二次電池用負極活物質、非水電解質二次電池、及び非水電解質二次電池用負極材の製造方法 | |
JP7040832B1 (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 | |
JP5483413B2 (ja) | リチウムイオン二次電池 | |
JP5141356B2 (ja) | 非水系電解質二次電池用正極活物質とその製造方法、および、これを用いた非水系電解質二次電池 | |
JP5181455B2 (ja) | 非水系電解質二次電池用正極活物質とその製造方法、および、これを用いた非水系電解質二次電池 | |
JP5045135B2 (ja) | 非水系電解質二次電池用正極活物質、その製造方法及びそれを用いた非水系電解質二次電池 | |
WO2020003692A1 (ja) | 非水電解質二次電池用負極活物質の製造方法 | |
JP2010027604A (ja) | リチウム二次電池用正極活物質及びリチウム二次電池 | |
JP7106754B2 (ja) | 電極、電池及び電池パック | |
JP2010027603A (ja) | リチウム二次電池用正極活物質およびリチウム二次電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980144517.5 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09824871 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010536811 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13127980 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20117011569 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009824871 Country of ref document: EP |