WO2010047334A1 - オリビン構造を有する多元系リン酸リチウム化合物粒子、その製造方法及びこれを正極材料に用いたリチウム二次電池 - Google Patents
オリビン構造を有する多元系リン酸リチウム化合物粒子、その製造方法及びこれを正極材料に用いたリチウム二次電池 Download PDFInfo
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- WO2010047334A1 WO2010047334A1 PCT/JP2009/068074 JP2009068074W WO2010047334A1 WO 2010047334 A1 WO2010047334 A1 WO 2010047334A1 JP 2009068074 W JP2009068074 W JP 2009068074W WO 2010047334 A1 WO2010047334 A1 WO 2010047334A1
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- H—ELECTRICITY
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to multi-component lithium phosphate compound particles having an olivine structure, a method for producing the same, and a lithium secondary battery using the same as a positive electrode material.
- a lithium secondary battery using a negative electrode active material as a material capable of occluding and releasing lithium metal, a lithium alloy, or lithium ions has a high voltage and excellent reversibility.
- lithium ion secondary batteries using a composite oxide of lithium and a transition metal as a positive electrode active material and a carbon-based material as a negative electrode active material are used in conventional lead secondary batteries and nickel-cadmium secondary batteries. In comparison, it is light in weight and has a large discharge capacity, so it is widely used as a power source for various electronic devices.
- LiCoO 2 , LiNiO 2 , LiMnO 2 , or LiMn 2 O 4 is mainly used as a positive electrode active material for lithium ion secondary batteries that are generally used.
- cobalt and nickel are low in reserves and are produced only in limited areas.
- materials containing these metals are limited in terms of price and stable supply of raw materials as positive electrode active materials for lithium ion secondary batteries, for which demand is expected to increase further in the future. From the viewpoint of safety, these active materials may be problematic because of their high reactivity.
- manganese is a relatively inexpensive material, but using a substance containing manganese as a positive electrode active material has a problem in stability of cycle characteristics.
- lithium iron phosphate using iron which is expected to be inexpensive and stable supply, is used as a raw material.
- Use as a positive electrode active material is proposed in Patent Documents 1 to 3, and the like.
- lithium phosphate compounds having an olivine structure have an extremely large electric resistance compared to lithium metal oxides such as LiCoO 2 that have been conventionally used, and therefore resistance polarization increases when charging and discharging are performed.
- resistance polarization increases when charging and discharging are performed.
- a sufficient discharge capacity cannot be obtained and that acceptability is poor in charging.
- the tendency was remarkable in charge / discharge of a large current.
- lithium phosphate-based material particles having an olivine structure are miniaturized to increase the reaction area, facilitate the diffusion of lithium ions, and reduce the distance that electrons flow inside the lithium iron phosphate-based material particles. It is considered to shorten.
- the fine particles of the lithium phosphate material having an olivine structure have a characteristic that secondary aggregation is likely to occur when mixed with a conductive material such as carbon black during electrode production. When this secondary agglomeration occurs, the lithium iron phosphate material particles and the conductive agent are in contact with each other within the agglomerated particles, so that a sufficient current collecting effect cannot be obtained and the electrical resistance is very large. There was a problem of becoming. For this reason, the active material in the central part of the aggregated particles does not cause electron conduction even when the battery is charged and discharged, and the charge and discharge capacity is reduced.
- the fine particles have a large surface area, the amount of dissolution in the electrolytic solution tends to increase, and there is a problem in long-term stability.
- the amount of dispersion medium required for slurry preparation during electrode production increases, and the required coating amount is difficult to obtain, cracks are likely to occur during drying, and sufficient compression is difficult.
- carbon is used as a conductive agent, and a solution, dispersion, or suspension containing Li source, Fe source, P source, C source, and O source is sprayed into a high temperature atmosphere to form a precursor.
- a solution, dispersion, or suspension containing Li source, Fe source, P source, C source, and O source is sprayed into a high temperature atmosphere to form a precursor.
- carbon is uniformly dispersed on the surface of lithium iron phosphate particles by heat treatment in a reducing atmosphere or an inert atmosphere (see, for example, Patent Document 5).
- a lithium iron-phosphorus composite oxide carbon composite obtained by coating the surface of LiFePO 4 particles with a carbonaceous material, and the carbon composite has an average particle size of 0.5 ⁇ m.
- Those having the following physical properties are known (see, for example, Patent Document 6).
- the oxidation-reduction potential of iron in lithium phosphate is lower than that of other elements, for example, as low as 0.2 V compared to general lithium cobaltate. Therefore, for the purpose of reducing resistance and increasing potential, one or more compounds containing a metal selected from the group consisting of iron, cobalt, manganese, nickel, copper and vanadium in phosphoric acid or a solution containing phosphoric acid; It is described that one or more compounds containing lithium are reacted and then fired to a predetermined temperature (see, for example, Patent Document 7).
- Non-Patent Document 1 a method of replacing a part of lithium iron phosphate with cobalt has been proposed (for example, see Non-Patent Document 1).
- Patent Document 4 since metal particles are supported on the fine particles of the lithium iron phosphate material, the metal particles are susceptible to chemical modification and have a problem in stability. Furthermore, since the particles are connected to each other, the problem of low current collection has not been sufficiently solved.
- carbon is used as a conductive agent, and this is uniformly dispersed on the particle surface. However, even with this method, the dispersion effect is insufficient and a sufficient current collecting effect cannot be expected. .
- Patent Document 6 since the technique described in Patent Document 6 as a method for further improving the conductivity between particles requires a high level of particle size control as a battery active material, such control is extremely difficult to control. was there.
- patent document 7 and nonpatent literature 1 produces a precursor after mixing several types of metal salt aqueous solution or each raw material powder uniformly, and manufactures a multi-component olivine type compound by baking this. Is the method.
- the composition control of the precursor is complicated in order to obtain a pure olivine type compound, the crystallinity is likely to increase, sufficient conductivity cannot be obtained, and the particle size control is difficult.
- the particle surface of the olivine-type M lithium phosphate-based material (M is a metal) is considered to be amorphous because it has lower crystallinity than the bulk. For this reason, the divalent metal is oxidized by being left in the air, and changed to a trivalent phosphate having a higher resistance. As a result, a large polarization is generated at the time of initial charge, and there are problems that the neglected conditions are severe, activation becomes complicated, and resistance components remain. This problem becomes more prominent as the particle size of the active material is smaller and the surface area is larger.
- the general formula Li Y M1 1-Z M2 Z PO 4 (where M1 is one metal element selected from the group consisting of Fe, Mn, and Co, and Y is M2 is a number satisfying the formula 0.9 ⁇ Y ⁇ 1.2, and M2 is at least one metal element selected from the group consisting of Mn, Co, Mg, Ti, and Al and a metal element other than M1 Z is a number satisfying the formula 0 ⁇ Z ⁇ 0.1), and is a multi-component lithium phosphate compound particle having an olivine structure, wherein the concentration of the metal element M2 on the particle surface is at the center of the particle
- a multi-component lithium phosphate compound particle characterized in that the concentration is higher than the concentration, and the concentration of the metal element M2 continuously decreases from the particle surface toward the particle center.
- the general formula Li x M1PO 4 (wherein M1 is one metal element selected from the group consisting of Fe, Mn, and Co, and X is the formula 0.9 ⁇ X M1 lithium phosphate compound having an olivine structure represented by ⁇ 1.2 and at least one general formula Li x M2PO 4 (where M2 is Mn, Co, Mg, Ti, and Al)
- the general formula Li x M1PO 4 (wherein M1 is one metal element selected from the group consisting of Fe, Mn, and Co, and X is the formula 0.9 ⁇ X M1 lithium phosphate compound having an olivine structure represented by ⁇ 1.2 and a general formula Li x M2PO 4 (where M2 is a group consisting of Mn, Co, Mg, Ti, and Al) And a precursor of an M2 lithium phosphate compound having an olivine structure represented by the formula: 0.9 ⁇ X ⁇ 1.2.
- the general formula Li x M1PO 4 (wherein M1 is one metal element selected from the group consisting of Fe, Mn and Co, and X is the formula 0.9 ⁇ X M1 lithium phosphate compound having an olivine structure represented by ⁇ 1.2 and at least one general formula Li x M2PO 4 (where M2 is Mn, Co, Mg, Ti, and Al)
- a mixture of lithium phosphate and M2 phosphate satisfying the stoichiometry of M2 lithium phosphate is used as the precursor of the M2 lithium phosphate compound. Can be used.
- the positive electrode is a multi-component lithium phosphate compound particle having the olivine structure according to claim 1.
- a lithium secondary battery comprising at least composite particles of a multi-component lithium phosphate compound having an olivine structure according to claim 2 and carbon is provided.
- a positive electrode active material for a lithium secondary battery can be easily produced, and the conductivity inside and between the active material particles can be improved and the movement of lithium ions can be facilitated.
- a positive electrode active material and a lithium secondary battery excellent in rate charge / discharge performance can be obtained.
- FIG. 1 is an explanatory view schematically showing a state in which the concentration of M2 continuously decreases from the particle surface toward the particle central part in phosphoric acid M1M2 lithium compound particles having an olivine structure.
- FIG. 2 is an explanatory view schematically showing conventional M1M2 phosphate compound particles having an olivine structure with uniform concentrations.
- FIG. 3 shows X-ray diffraction patterns of powder A, powder D, and powder H.
- the multi-component lithium phosphate compound having an olivine structure is an M1 lithium phosphate compound having an olivine structure (where M1 is one metal selected from the group consisting of Fe, Mn, and Co) Element) and an M2 lithium phosphate compound having an olivine structure (where M2 is at least one metal selected from the group consisting of Mn, Co, Mg, Ti, and Al and a metal other than M1) Element) precursors and heat-treating them in an inert atmosphere or vacuum.
- the lithium M1 lithium compound is represented by the general formula Li X M1PO 4 (where M1 is one metal element selected from the group consisting of Fe, Mn, Co, 0.9 ⁇ X ⁇ 1.2).
- the compound M2 lithium phosphate is a compound of the general formula Li X M2PO 4 (where M2 is at least one metal selected from the group consisting of Mn, Co, Mg, Ti, Al and selected by M1) Other than metal elements, 0.9 ⁇ X ⁇ 1.2).
- the multi-component lithium phosphate compound obtained here has a general formula Li Y M1 z M2 1-z PO 4 (where M1 is one or more metal elements selected from the group consisting of Fe, Mn, and Co, Y Is a number satisfying the formula 0.9 ⁇ Y ⁇ 1.2, M2 is at least one metal selected from the group consisting of Mn, Co, Mg, Ti, and Al, and a metal element other than selected by M1, Z is represented by the formula 0 ⁇ Z ⁇ 0.1.
- the obtained multi-component lithium phosphate compound can be pulverized and classified to obtain positive electrode active material particles.
- the particle diameter of the positive electrode active material particles is preferably 20 ⁇ m or less.
- Examples of the metal species M1 include Fe, Mn, and Co, and examples of M2 include Mn, Co, Mg, Ti, and Al.
- M1 is Fe
- a phosphate mixture in which each stoichiometric ratio is combined, a mixture of various metal salts and phosphoric acid, or the like can be used.
- the metal salt include (manganese sulfate, manganese (II) nitrate, manganese carbonate (II), manganese oxide (II), etc.
- the kneading after adding various raw materials can be carried out in an aqueous or organic dispersion medium. Mix well in the medium, and the mixing can be performed by a media dispersion method such as a bead mill.
- These mixtures are sintered after drying in an inert gas atmosphere or vacuum. Drying is performed at 100 ° C. for 2 hours, for example.
- argon gas or nitrogen gas can be used as the inert gas.
- the sintering can be performed at 600 ° C. for about 3 hours.
- FIG. 1 schematically shows this state.
- the multi-component lithium phosphate compound of the present invention in which the M2 concentration is changed has a change in crystallinity as compared with a multi-component lithium phosphate compound having an olivine structure made from a conventional homogeneous solution, It is presumed that bulk conductivity and lithium ion mobility become smooth and high rate charge / discharge performance is improved.
- the inter-particle conductivity is also improved. High charge / discharge characteristics can be obtained. Moreover, it comes to have an effect of improving the coating property of the active material slurry at the time of manufacturing the electrode and improving the packing density.
- carbon used here acetylene black, ketjen black, furnace black, etc. are preferable.
- An organic compound is used as the carbon source. Examples of the organic compound include sucrose, polyvinyl alcohol, petroleum pitch, and ethylene glycol.
- a positive electrode plate obtained by using the phosphoric acid lithium compound active material having the olivine structure is an aqueous paste in which a conductive agent, a water-soluble thickener, a binder, and water as a dispersion medium are kneaded and dispersed in the active material. Is coated on a current collector and dried.
- the primary particle of the phosphoric acid lithium compound having an olivine structure as the positive electrode active material is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less.
- the conductive agent contained in the paste include conductive carbon such as acetylene black, ketjen black, furnace black, carbon fiber, and graphite, conductive polymer, and metal powder, and conductive carbon is particularly preferable. These conductive agents are preferably used in an amount of 20 parts by weight or less based on 100 parts by weight of the positive electrode active material. A more preferable use amount is 10 parts by weight or less and 1 part by weight or more.
- water-soluble thickeners examples include carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and polyethylene oxide. These water-soluble thickeners are preferably used in an amount of 0.1 to 4.0 parts by weight or less based on 100 parts by weight of the positive electrode active material. A more preferable use amount is 0.5 to 3.0 parts by weight or less. If the amount of the water-soluble thickener exceeds the above range, the battery resistance of the obtained secondary battery is increased and the rate characteristics are lowered. Conversely, if the amount is less than the above range, the aqueous paste is aggregated.
- the water-soluble thickener may be used in the form of an aqueous solution, and in that case, it is preferably used as an aqueous solution of 0.5 to 3% by weight.
- binder examples include a fluorine-based binder, acrylic rubber, modified acrylic rubber, styrene-butadiene rubber, acrylic polymer, vinyl polymer, or a mixture of two or more of these, It can be used as a coalescence. It is more preferable to use an acrylic polymer because oxidation resistance, sufficient adhesion with a small amount, and flexibility in the electrode plate can be obtained.
- the blending ratio is 1 for 100 parts by weight of the positive electrode active material. The amount is preferably from 10 parts by weight to 10 parts by weight, and more preferably from 2 parts by weight to 7 parts by weight.
- water is used as a dispersion medium.
- an alcohol solvent for the purpose of improving the drying property of the active material layer and the wettability with the current collector, an alcohol solvent, an amine solvent, a carboxylic acid solvent, A water-soluble solvent such as a ketone solvent may be contained.
- an aqueous paste containing a phosphate-type lithium-based material having an olivine structure, a conductive agent, a water-soluble thickener, a binder, and a dispersion medium is used for the purpose of further improving coating properties and leveling properties.
- Leveling agents such as surfactants and water-soluble oligomers may be added.
- the dispersion of the aqueous paste can be performed using a known disperser such as a planetary mixer, a disper mixer, a bead mill, a sand mill, an ultrasonic disperser, a homogenizer, and a hensil mixer.
- a media dispersion method that can use a dispersion medium having a small particle diameter such as a bead mill or a sand mill is more preferable.
- the produced paste can maintain the porosity suitable for the coating film formed by coating and drying.
- the aqueous paste for coating of the positive electrode active material mixture thus prepared is coated on a current collector made of metal foil.
- a metal foil such as copper, aluminum, nickel, and stainless steel is used, and among them, aluminum is preferable for the positive electrode current collector.
- aqueous paste to current collector metal foil includes gravure coat, gravure reverse coat, roll coat, Meyer bar coat, blade coat, knife coat, air knife coat, commat coat, slot die coat, slide die coat, dip coat
- gravure coat gravure reverse coat
- roll coat Meyer bar coat
- blade coat knife coat
- air knife coat commat coat
- slot die coat slide die coat
- dip coat A known coating method selected from the above can be used.
- the aqueous paste is uniformly applied so that the dry weight is in the range of 2 to 10 mg / cm 2 , more preferably 3 to 8 mg / cm 2 .
- the drying method is not particularly limited.
- the drying can be performed with warm air, drying with hot air, vacuum drying, a far-infrared heater, or the like, and the drying temperature can be in the range of about 30 to 130 ° C.
- the drying is finished. Then, it is preferable to press this with a flat plate press or a roll press.
- an active material that can be doped or dedoped with lithium may be used.
- coke such as pyrolytic carbons, pitch coke, needle coke, petroleum coke, graphite, glassy carbon, organic polymer compound sintered body (phenol resin, furan resin, etc. are sintered at an appropriate temperature.
- Carbon fibers such as carbon fibers and activated carbon
- alloy materials such as metallic lithium, lithium alloys and Sn compounds
- other polymers such as polyacetylene can also be used.
- a negative electrode paste obtained by kneading and dispersing these negative electrode active materials, a binder, and, if necessary, a conductive additive in a dispersion medium is applied to a current collector, dried and rolled to produce a negative electrode plate.
- a current collector for example, copper, nickel, stainless steel and the like can be used, but a copper foil is preferable.
- the electrolytic solution is not particularly limited, but a nonaqueous electrolytic solution is preferable.
- non-aqueous electrolyte those conventionally used for lithium secondary batteries are used without limitation.
- LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , LiCl, LiBr and other inorganic lithium salts LiBOB, LiB (C 6 H 5 ) 4 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 , at least one of organic lithium salts such as LiOSO 2 CF 3 , propylene carbonate, ethylene carbonate, butylene carbonate, ⁇ -butyrolactone, vinylene carbonate, 2-methyl- ⁇ -butyrolactone, acetyl- ⁇ -butyrolactone, ⁇ -valerolactone, etc.
- Examples thereof include those dissolved in at least one solvent selected from chain esters such as ethers, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, propionic acid alkyl ester, meronic acid dialkyl ester, and acetic acid alkyl ester.
- chain esters such as ethers, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, propionic acid alkyl ester, meronic acid dialkyl ester, and acetic acid alkyl ester.
- LiBF 4 , LiPF 6, LiBOB, or a mixture thereof is preferably dissolved in at least one organic solvent.
- the separator is not particularly limited as long as it is insoluble in the above-mentioned electrolyte component, but a single layer or a multilayer of a polyolefin-based microporous film such as polypropylene or polyethylene is used, and a multilayer is particularly preferable.
- a non-aqueous electrolyte secondary battery can be manufactured by using the above-described positive electrode plate of the present invention and combining it with a known negative electrode for non-aqueous electrolyte, an electrolyte, a separator, and the like.
- the shape of the battery is not particularly limited, and any shape such as a coin shape, a button shape, a laminate shape, a cylindrical shape, a square shape, or a flat shape may be used.
- Example 1 In the following, various embodiments of the present invention will be described. In addition, this invention is not limited only to a following example.
- M1 lithium phosphate compound having an olivine structure in which M1 is Fe was synthesized by the hydrothermal method as follows.
- lithium M2 phosphate compound precursor having an olivine structure in which M2 is Mn was synthesized as follows.
- the amount of Mn of the obtained product was measured using ICP emission spectroscopic analysis, it was found to contain 79.1% Mn 3 (PO 4 ) 2 . Moreover, from observation with a scanning electron microscope (SEM), the particle size of the product was 1 ⁇ m or less, and it was confirmed to be an amorphous crystal.
- SEM scanning electron microscope
- the amount of Li was measured for the obtained product using ICP emission spectroscopic analysis, it was found to contain 99.3% Li 3 PO 4 . Further, from observation with a scanning electron microscope (SEM), the particle size of the product was 1 ⁇ m or less, and it was confirmed that the product was a needle-like crystal.
- SEM scanning electron microscope
- the powder A When the powder A was analyzed with an X-ray diffractometer, it was a single-phase olivine type compound. Further, ICP emission analysis confirmed that each element had the same composition as that at the time of introduction. In the measurement of the particle size distribution by SEM, it was confirmed that the particle size was larger than that before sintering, and the primary particles were about 0.7 to 3 ⁇ m.
- this powder B was analyzed with an X-ray diffractometer, it was a single-phase olivine type compound. Further, ICP emission spectroscopic analysis confirmed that each element had the same composition as that at the time of introduction. Further, it was confirmed by thermogravimetric analysis that the amount of carbon was 4% by weight. In the measurement of the particle size distribution by SEM, it was found that the particle size was larger than before sintering, and the primary particles were about 0.7 to 3 ⁇ m.
- this powder C was analyzed with an X-ray diffractometer, it was a single-phase olivine type compound. Further, ICP emission spectroscopic analysis revealed that each element had the same composition as that at the time of introduction. Further, it was confirmed by thermogravimetric analysis that the total amount of carbon was 6% by weight. In the measurement of the particle size distribution by SEM, the particle size was larger than that before sintering, and the primary particles were about 0.7 to 3 ⁇ m.
- this powder D was analyzed by an X-ray diffractometer, it was a single-phase olivine type compound. Further, it was confirmed by ICP that each element had a composition ratio represented by LiFe 0.9 Mn 0.1 PO 4 . In the particle size distribution measurement by SEM, the particle size was about 20 to 100 nm.
- Powder E had a total carbon content of 6 wt% by thermogravimetric analysis.
- the obtained powder was found to be a single-phase olivine type compound by an X-ray diffraction pattern. Furthermore, it was confirmed by ICP emission spectroscopic analysis that each element had a composition ratio represented by LiFe 0.9 Mn 0.1 PO 4 . The particle size distribution measured by SEM was about 20 to 100 nm. This powder was designated as powder F.
- a solution prepared by dissolving 1 g of sucrose in ion-exchanged water was added to 10 g of powder F and sufficiently kneaded in a mortar to obtain a slurry.
- the slurry was put into a graphite crucible, dried at 100 ° C. for 2 hours, and then put into a vacuum gas replacement furnace. Next, after sufficiently replacing with nitrogen gas, the treatment was performed at 600 ° C. for 3 hours under vacuum. Thereafter, after cooling to room temperature, the crucible was taken out and a sample inside was collected.
- the sample was a black brittle lump, which was pulverized with a coffee mill and classified into aggregated particles of 20 ⁇ m or less with a sieve. This was designated as powder G.
- LiFePO 4 obtained by the hydrothermal method was used as powder I.
- a solution prepared by dissolving 1 g of sucrose in ion-exchanged water was added to 10 g of powder I, and then sufficiently kneaded in a mortar to obtain a slurry.
- This slurry was put into a graphite crucible, dried at 100 ° C. for 2 hours, and further put into a vacuum gas replacement furnace. Next, the gas was sufficiently replaced with nitrogen gas, and then a vacuum treatment was performed at 600 ° C. for 3 hours. Then, after standing to cool to room temperature, the crucible was taken out and the sample inside was collected.
- the sample was a black brittle mass, which was pulverized with a coffee mill and then classified into aggregated particles of 20 ⁇ m or less with a sieve. This was designated as powder J. When this was analyzed with an X-ray diffractometer, it was confirmed to be a single-phase olivine type compound. The amount of carbon was 4% by weight by thermogravimetric analysis. In the measurement of the particle size distribution by SEM, it was found that the particle size was larger than that before sintering, and the primary particles were about 0.7 to 3 ⁇ m.
- the powder H which is a mixed powder of LiFePO 4 and LiMnPO 4 , did not show clear peak separation.
- the powder AC had a redox peak due to Mn broadly and had a concentration gradient.
- G no redox piece due to Mn was observed.
- D the redox peak resulting from Mn was sharply seen.
- acetylene black was mixed as a conductive agent so that the total carbon amount was 10% by weight.
- the mixed powder and polyvinylidene fluoride (PVdF) as a binder are mixed at a weight ratio of 95: 5, and N-methyl-2-pyrrolidone (NMP) is added and kneaded sufficiently to obtain a positive electrode slurry. It was.
- This positive electrode slurry was applied to an aluminum foil current collector with a thickness of 15 ⁇ m at a coating amount of 100 g / m 2 and dried at 120 ° C. for 30 minutes. Then, it was rolled to a density of 1.8 g / cc with a roll press and punched into a 2 cm 2 disk shape to obtain a positive electrode.
- the positive electrodes made of the powders A to J are referred to as positive electrodes A to J, respectively. Each specification is summarized in Table 1 below.
- C + AB in the chemical formula of powder C means that carbon C derived from sucrose and carbon of acetylene black (AB) exist.
- a three-electrode cell (single electrode cell) was prepared.
- the positive electrode A to the positive electrode J produced as the positive electrode were mixed with a lithium metal electrode as the negative electrode and the reference electrode, and ethylene-carbonate and diethyl carbonate mixed at a volume ratio of 1: 1 as the electrolyte.
- the positive electrode A to the positive electrode C according to the present invention are particularly excellent in high rate charge / discharge performance of 5 CA or more. This is presumed to be because the Mn concentration of the binary active material of Fe and Mn is continuously changing inside the particle, so that the conductivity inside the particle is improved and the Li ion migration is smooth.
- the positive electrode B using the powder treated with the carbon source and further the positive electrode C were able to obtain better characteristics because the conductivity between the particles was improved.
- the positive electrode D to the positive electrode G using a binary active material having a uniform composition of Fe and Mn can obtain the effect of carbon, but at a current of 5 CA or more, the resistance including the reaction resistance is large, and the capacity reduction is remarkable. It was. It is estimated that the positive electrode H, which is a mixed positive electrode of LiFePO 4 and LiMnPO 4 , is affected by LiMnPO 4 having a large particle resistance, and the overall performance is lowered.
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Abstract
Description
以下に、本発明の種々の実施例を説明する。なお、本発明は以下の実施例のみに限定されるものではない。
実施例1で得られたものと同じLiFePO4とLiMnPO4前駆体を用い、Li:Fe:Mn=1.0:0.9:0.1になるように、5.12gのLiFePO4と0.67gのLiMnPO4前駆体を混合した。次に、0.512gのショ糖を10mlのイオン交換水に溶解した溶液を上記の混合粉と混ぜて乳鉢で十分に混合し、スラリーを得た。このスラリーを黒鉛坩堝に投入した後、100℃で2時間の乾燥を行ない、更に、真空ガス置換炉に投入した。
実施例1で得られたものと同じLiFePO4とLiMnPO4前駆体を用い、Li:Fe:Mn=1.0:0.9:0.1になるように、5.12gのLiFePO4と0.67gのLiMnPO4前駆体を混合し、更に0.100gのアセチレンブラックを加えた。これに0.512gのショ糖を10mlのイオン交換水に溶解した溶液を混合粉と混ぜて、乳鉢で十分に混合してスラリーとした。このスラリーを黒鉛坩堝に投入した後、100℃で2時間の乾燥を行ない、更に、真空ガス置換炉に投入した。
65.99gのCH3COOLi、156.56gのFe(CH3COO)2、17.30gのMn(CH3COO)2、115.29gの85%H3PO4を秤量した混合物を、イオン交換水1000mlに加えて溶解させ、十分に攪拌して均一溶液とした。次に、この溶液を150℃で乾燥した後、得られた物質を電気炉に入れ、アルゴン-水素(92:8,v/v)中で400℃、8時間の焼成を行なった。その後、室温まで冷却して前駆体の塊を得た。これを再度粉砕して、また電気炉に入れ、同雰囲気中で600℃、24時間の焼成をして粉体Dを得た。
リン酸リチウム486g、2価の鉄化合物としての2価の塩化鉄4水和物716g、および2価のマンガン化合物としての2価の塩化マンガン2水和物65gを、鉄耐圧容器(オートクレーブ)中に蒸留水2000mlとともに入れ、アルゴンガスで置換した後に密閉した。この耐圧容器を180℃のオイルバス中で48時間反応させた。その後、室温まで放冷した後、内容物を取出し、100℃で乾燥させて粉末試料を得た。
LiMnPO4前駆体を適量のイオン交換水と混ぜて、乳鉢で十分に混合してスラリーを得た。このスラリーを黒鉛坩堝に投入した後、100℃で2時間の乾燥を行ない、更に真空ガス置換炉に投入した。窒素ガスで十分に置換した後、真空状態にして、600℃で3時間処理した。次いで、室温まで放冷した後に坩堝を取出して、中の試料を採取した。試料は脆い塊状であり、これをコーヒーミルで粉砕した後に篩で20μm以下の凝集粒子に分級した。
水熱法で得られたLiFePO4を粉体Iとした。1gのショ糖をイオン交換水に溶解した溶液を10gの粉体Iに加えた後、乳鉢で十分に混練してスラリーを得た。このスラリーを黒鉛坩堝に投入した後、100℃で2時間の乾燥を行ない、更に、真空ガス置換炉に投入した。次いで、窒素ガスで十分に置換した後、真空状態にして600℃で3時間の処理を実施した。その後、室温まで放冷した後に、坩堝を取出して中の試料を採取した。
何れもFe:Mn=9:1の組成をもつ粉体A、粉体D、粉体HのX線回折パターンを図3に示した。図3から、何れの粉体も基本的なオリビン構造を有するリン酸型リチウム系化合物の特徴的なパターンを示した。LiFePO4とLiMnPO4の混合粉である粉体Hは明確なピーク分離は見られなかった。
実施例及び比較例で得られた各々の粉体A~Jに、導電剤としてアセチレンブラックを全炭素量が10重量%になるように混合した。混合粉末と結着剤であるポリフッ化ビニリデン(PVdF)を、重量比95:5の割合で混合し、さらにN-メチル-2-ピロリドン(NMP)を加えて十分混練して、正極スラリーを得た。
電気化学的特性を確認するために、三電極式セル(単極セル)を作製した。正極として作製した正極A~正極Jを、負極および参照電極として金属リチウム電極を使用し、電解液としてエチレン-カーボネート及びジエチルカーボネートを体積比1:1の割合で混合したものを用いた。
Claims (7)
- 一般式LiYM11-ZM2ZPO4(但し、M1はFe、Mn、及びCoからなる群から選択される1種の金属元素であり、Yは式0.9≦Y≦1.2を満たす数であり、M2はMn、Co、Mg、Ti、及びAlからなる群から選択される少なくとも1種の金属元素でかつM1以外の金属元素であり、Zは式0<Z≦0.1を満たす数である)で表される、オリビン構造を有する多元系リン酸リチウム化合物粒子であって、粒子表面の金属元素M2の濃度が粒子中心部の濃度よりも高く、かつ金属元素M2の濃度が粒子表面から粒子中心部へ向かって連続的に低下していることを特徴とする多元系リン酸リチウム化合物粒子。
- 一般式LixM1PO4(但し、M1はFe、Mn、及びCoからなる群から選択される1種の金属元素であり、Xは式0.9≦X≦1.2を満たす数である)で表されるオリビン構造を有するリン酸M1リチウム化合物と、1種以上の一般式LixM2PO4(但し、M2はMn、Co、Mg、Ti、及びAlからなる群から選択される少なくとも1種の金属元素であり、Xは式0.9≦X≦1.2を満たす数である)で表されるオリビン構造を有するリン酸M2リチウム化合物の前駆体と、炭素または炭素源とを混合し、これを不活性雰囲気または真空中で熱処理することによって得られた、オリビン構造を有する多元系リン酸リチウム化合物とカーボンとの複合体粒子であって、粒子表面の金属元素M2の濃度が粒子中心部の濃度よりも高く、かつ金属元素M2の濃度が粒子表面から粒子中心部へ向かって連続的に低下している、一般式LiYM11-ZM2ZPO4(但し、M1はFe、Mn、及びCoからなる群から選択される1種の金属元素であり、Yは式0.9≦Y≦1.2を満たす数であり、M2はMn、Co、Mg、Ti、及びAlからなる群から選択される少なくとも1種の金属元素でかつM1で選択した以外の金属元素であり、Zは式0<Z≦0.1を満たす数である)で表されるオリビン構造を有する多元系リン酸リチウム化合物とカーボンとの複合体粒子。
- 一般式LixM1PO4(但し、M1はFe、Mn、及びCoからなる群から選択される1種の金属元素であり、Xは式0.9≦X≦1.2を満たす数である)で表されるオリビン構造を有するリン酸M1リチウム化合物と、一般式LixM2PO4(但し、M2はMn、Co、Mg、Ti、及びAlからなる群から選択される少なくとも1種の金属元素であり、Xは式0.9≦X≦1.2を満たす数である)で表されるオリビン構造を有するリン酸M2リチウム化合物の前駆体とを混合する工程、及び
前記混合物を不活性雰囲気または真空中で熱処理し、粒子表面付近の金属元素M2の濃度が粒子中心部の濃度よりも高く、かつ金属元素M2の濃度が粒子表面から粒子中心部へ向かって連続的に低下している、一般式LiYM11-ZM2ZPO4(但し、M1はFe、Mn、及びCoからなる群から選択される1種の金属元素であり、Yは式0.9≦Y≦1.2を満たす数であり、M2はMn、Co、Mg、Ti、及びAlからなる群から選択される少なくとも1種の金属元素でかつM1で選択した以外の金属元素であり、Zは式0<Z≦0.1を満たす数である)で表されるオリビン構造を有する多元系リン酸リチウム化合物粒子を得る工程
を具備することを特徴とするオリビン構造を有する多元系リン酸リチウム化合物粒子の製造方法。 - 前記リン酸M2リチウム化合物の前駆体が、リン酸M2リチウムの化学量論を満足するリン酸リチウム及びM2リン酸塩の混合物であることを特徴とする請求項3に記載の方法。
- 一般式LixM1PO4(但し、M1はFe、Mn、及びCoからなる群から選択される1種の金属元素であり、Xは式0.9≦X≦1.2を満たす数である)で表されるオリビン構造を有するリン酸M1リチウム化合物と、1種以上の一般式LixM2PO4(但し、M2はMn、Co、Mg、Ti、及びAlからなる群から選択される少なくとも1種の金属元素であり、Xは式0.9≦X≦1.2を満たす数である)で表されるオリビン構造を有するリン酸M2リチウム化合物の前駆体と、炭素または炭素源とを混合する工程、及び
前記混合物を不活性雰囲気または真空中で熱処理し、粒子表面付近の金属元素M2の濃度が粒子中心部の濃度よりも高く、かつ金属元素M2の濃度が粒子表面から粒子中心部へ向かって連続的に低下している、一般式LiYM11-ZM2ZPO4(但し、M1はFe、Mn、及びCoからなる群から選択される1種の金属元素であり、Yは式0.9≦Y≦1.2を満たす数であり、M2はMn、Co、Mg、Ti、及びAlからなる群から選択される少なくとも1種の金属元素でかつM1で選択した以外の金属元素であり、Zは式0<Z≦0.1を満たす数である)で表されるオリビン構造を有する多元系リン酸リチウム化合物とカーボンとの複合体粒子を得る工程
を具備することを特徴とするオリビン構造を有する多元系リン酸リチウム化合物とカーボンとの複合体粒子の製造方法。 - 前記リン酸M2リチウム化合物の前駆体が、リン酸M2リチウムの化学量論を満足するリン酸リチウム及びM2リン酸塩の混合物であることを特徴とする請求項5に記載の方法。
- 正極、負極及びリチウム塩を含む電解液を備えたリチウム二次電池において、前記正極は、請求項1に記載のオリビン構造を有する多元系リン酸リチウム化合物粒子または請求項2に記載のオリビン構造を有する多元系リン酸リチウム化合物とカーボンとの複合体粒子を少なくとも含むことを特徴とするリチウム二次電池。
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US20140353555A1 (en) | 2014-12-04 |
US9337488B2 (en) | 2016-05-10 |
EP2360119A4 (en) | 2013-01-23 |
KR101300304B1 (ko) | 2013-08-28 |
EP2360119A1 (en) | 2011-08-24 |
JP2010095432A (ja) | 2010-04-30 |
US20110195304A1 (en) | 2011-08-11 |
JP5376894B2 (ja) | 2013-12-25 |
KR20110088504A (ko) | 2011-08-03 |
CN102186770B (zh) | 2013-12-18 |
CA2741406C (en) | 2014-08-19 |
EP2360119B1 (en) | 2014-03-19 |
CN102186770A (zh) | 2011-09-14 |
US8841023B2 (en) | 2014-09-23 |
CA2741406A1 (en) | 2010-04-29 |
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