WO2013038516A1 - Phosphate de manganèse-fer-ammonium, son procédé de production, matière active d'électrode positive pour batteries rechargeables au lithium mettant en œuvre du phosphate de manganèse-fer-ammonium, procédé de production de matière active d'électrode positive pour batteries rechargeables au lithium mettant en œuvre du phosphate de manganèse-fer-ammonium, et batterie rechargeable au lithium mettant en œuvre une matière active d'électrode positive pour batteries rechargeables au lithium mettant en œuvre du phosphate de manganèse-fer-ammonium - Google Patents

Phosphate de manganèse-fer-ammonium, son procédé de production, matière active d'électrode positive pour batteries rechargeables au lithium mettant en œuvre du phosphate de manganèse-fer-ammonium, procédé de production de matière active d'électrode positive pour batteries rechargeables au lithium mettant en œuvre du phosphate de manganèse-fer-ammonium, et batterie rechargeable au lithium mettant en œuvre une matière active d'électrode positive pour batteries rechargeables au lithium mettant en œuvre du phosphate de manganèse-fer-ammonium Download PDF

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WO2013038516A1
WO2013038516A1 PCT/JP2011/070944 JP2011070944W WO2013038516A1 WO 2013038516 A1 WO2013038516 A1 WO 2013038516A1 JP 2011070944 W JP2011070944 W JP 2011070944W WO 2013038516 A1 WO2013038516 A1 WO 2013038516A1
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Prior art keywords
positive electrode
active material
electrode active
lithium secondary
manganese iron
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PCT/JP2011/070944
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English (en)
Japanese (ja)
Inventor
遼介 岡本
法道 米里
建作 森
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住友金属鉱山株式会社
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Priority to PCT/JP2011/070944 priority Critical patent/WO2013038516A1/fr
Priority to JP2013533394A priority patent/JP5835334B2/ja
Publication of WO2013038516A1 publication Critical patent/WO2013038516A1/fr

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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
    • 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
    • H01M4/04—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to ammonium manganese iron phosphate as a precursor of a positive electrode active material for a lithium secondary battery, a method for producing the same, a positive electrode active material for a lithium secondary battery using the ammonium manganese iron phosphate as a precursor, and The present invention relates to a production method and a lithium secondary battery using the positive electrode active material using the positive electrode active material.
  • Lithium secondary batteries are lightweight and have high energy density, so they are widely used in small batteries such as mobile phones, notebook computers, and other IT devices. For these applications, LiCoO 2 and LiCo 1/3 are mainly used. Layered rock salt compound positive electrode active materials such as Ni 1/3 Mn 1/3 O 2 and LiNiO 2 are used. With the development and popularization of IT equipment, the demand is still growing on a global scale. In addition to these small batteries, industrial large batteries can also be used for hybrid vehicles (HEV), plug-in hybrid vehicles (PHEV), electric vehicles (EV), power leveling, power storage, and more. The demand is expected to expand in the direction, and research and development are also actively conducted.
  • HEV hybrid vehicles
  • PHEV plug-in hybrid vehicles
  • EV electric vehicles
  • power leveling power storage, and more. The demand is expected to expand in the direction, and research and development are also actively conducted.
  • an olivine-type positive electrode active material has attracted attention as an alternative positive electrode active material such as LiCoO 2 or LiCo 1/3 Ni 1/3 Mn 1/3 O 2 . .
  • the olivine-type positive electrode active material has a theoretical capacity of about 170 mAh / g and all O is covalently bonded to P. Therefore, even if the battery generates heat, there is a risk of ignition without releasing oxygen.
  • the structure is low and the structure is stable due to the skeleton of phosphoric acid, so that the electrode is not easily deteriorated even after repeated charge and discharge, and the cycle life is long.
  • LiFePO 4 lithium iron phosphate
  • LiFePO 4 is a material that can be synthesized from low-priced raw materials with low resource constraints because all the constituent elements, except for Li, are at the top of the number of Clarkes, and realizes a capacity close to the theoretical capacity with high efficiency. Due to its long life, it has been industrially produced and put into practical use as a positive electrode active material for lithium secondary batteries.
  • LiFePO 4 also has some disadvantages. One is a problem that electron conductivity and Li ion conductivity are low as compared with a conventional layered rock salt compound positive electrode active material.
  • LiFePO 4 particles finer to several tens to several hundreds of nanometers have been improved by making LiFePO 4 particles finer to several tens to several hundreds of nanometers, and further coating and combining with a conductive material such as graphite to impart conductivity.
  • the other is a problem that the weight energy density is low because the potential with respect to Li metal is 3.3 V, which is lower than the layered rock salt compound positive electrode active material. This is an essential property of the material and is difficult to improve.
  • LiMnPO 4 lithium manganese phosphate
  • Fe of LiFePO 4 has Mn, but this shows 4.1 V against Li metal and the same potential as the layered rock salt compound positive electrode active material, and high weight energy density is expected.
  • LiMnPO 4 has a problem that its electronic conductivity and Li ion conductivity are lower than LiFePO 4 .
  • LiMnPO 4 Even when LiMnPO 4 is subjected to the same particle refinement as LiFePO 4 and treatment with graphite or the like, unlike LiFePO 4 , it hardly shows charge / discharge capacity as a secondary battery. For this reason, LiMnPO 4 has not yet been put into practical use despite a great deal of effort in development.
  • LiFePO 4 and LiMnPO 4 have been studied to combine LiFePO 4 and LiMnPO 4 to compensate for their shortcomings.
  • LiMn 0.6 Fe 0.4 PO 4 that is, lithium manganese iron composite phosphate in which 60 mol% of LiFePO 4 Fe is replaced with Mn is used as the positive electrode active material, so that the initial discharge capacity is about 160 mAh / g.
  • the discharge of 4V is realized with the capacity of more than half (for example, refer nonpatent literature 1).
  • olivine type positive electrode active material Since synthesis of an olivine-type positive electrode active material containing Fe is unstable because divalent Fe is easily oxidized, various methods have been studied. Moreover, since the olivine type positive electrode active material has low electron conductivity as described above, good electrode characteristics cannot be obtained with particles of several microns or more. For this reason, it is known that fine particles can be refined to several tens to several hundreds of nanometers, and further, conductivity can be imparted by coating / compositing with a conductive material such as graphite, and good characteristics can be obtained. Yes. However, the additional processing increases the production cost of the olivine type positive electrode active material, resulting in the loss of material superiority.
  • olivine particles can be obtained by a method as simple as possible and can be combined with a conductive material.
  • a hydrothermal synthesis method a spray pyrolysis method, a sol-gel method, and the like for the synthesis of the olivine-type positive electrode active material.
  • the solid-phase reaction method is generally used.
  • a method for producing LiFePO 4 for example, it has a mixing step of mixing a plurality of substances to be a synthetic raw material to make a precursor, and a heating step of heating and reacting the precursor.
  • a manufacturing method using at least iron oxalate has been proposed (see, for example, Patent Document 1).
  • iron oxalate which is one of the raw materials, is toxic and unfavorable for the human body and the environment, and is expensive, and thus is inappropriate as a raw material for battery positive electrode active materials that require mass production.
  • a manganese source in the mixing step, but a separate lithium source and manganese source can be mixed with a uniform lithium manganese iron complex phosphate (LiMn In order to synthesize x Fe 1-x PO 4 ), a long pulverization and mixing before firing and a high firing temperature are required. For this reason, since the sintering between the particles proceeds, in order to make a fine powder, it must be strongly pulverized again, resulting in a very costly manufacturing process.
  • ferrous ammonium phosphate is produced from ferrous sulfate (FeSO 4 ), a phosphoric acid source such as ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), and ammonia (NH 4 OH).
  • FeSO 4 ferrous sulfate
  • a phosphoric acid source such as ammonium dihydrogen phosphate (NH 4 H 2 PO 4 )
  • ammonia NH 4 OH
  • a lithium raw material such as lithium hydroxide (LiOH) or lithium carbonate (Li 2 CO 3 )
  • LiFePO 4 A method for producing iron phosphate (LiFePO 4 ) has been proposed (see, for example, Patent Document 2).
  • Non-Patent Document 1 even when attempted synthesis of LiMn x Fe 1-x PO 4 is replaced iron raw material NH 4 FePO 4 ⁇ H 2 O , still uniform LiMn x Fe 1- to synthesize the x PO 4 is prolonged grinding and mixing and high temperature firing temperature before firing is required.
  • the object of the present invention is a lithium manganese iron composite phosphate having a fine particle size and high battery capacity and high output when used as a positive electrode active material.
  • a positive electrode active material for lithium secondary battery a method for producing a positive electrode active material for lithium secondary battery using a uniform and fine composition of ammonium manganese iron phosphate as a precursor, and further comprising the positive electrode active material It is to provide a lithium secondary battery having good characteristics when used.
  • the present inventors have made extensive studies on a lithium manganese iron composite phosphate that is uniformly mixed and has a fine particle diameter.
  • the present inventors have a structure similar to NH 4 FePO 4 .H 2 O. NH 4 MnPO 4 ⁇ H 2 O that substance is present, by mixing the respective source of iron, manganese-raw material by firing at a low temperature, to obtain a knowledge that the lithium manganese iron composite phosphate is obtained.
  • the knowledge that the precursor of the said lithium manganese iron complex phosphate in which manganese, iron, and phosphorus were mixed by the atomic level was obtained by co-precipitating both and synthesizing simultaneously was acquired.
  • the present invention has been completed based on these findings.
  • a method for producing a precursor of a positive electrode active material for a lithium secondary battery A mixed solution preparation step for preparing a mixed solution of divalent Mn ions and Fe ions and phosphoric oxide ions, and co-precipitation by adding ammonia to adjust the pH of the mixed solution to a range of 7-9. And a crystallization step for obtaining ammonium manganese iron phosphate represented by the general formula: NH 4 Mn x Fe 1-x PO 4 .H 2 O (0 ⁇ x ⁇ 1) A method for producing manganese iron is provided.
  • the mixed solution preparation step at least one selected from sulfates or chloride salts is used as a feedstock for Mn ions and Fe ions.
  • a method for producing ammonium manganese iron phosphate is provided, wherein a water-soluble metal salt is used.
  • the mixed solution preparation step at least one selected from phosphoric acid or ammonium dihydrogen phosphate as a feedstock of phosphoric acid ions.
  • a method for producing ammonium manganese iron phosphate is provided, wherein a water-soluble salt is used.
  • the method for producing ammonium manganese iron phosphate according to any one of the first to third aspects, wherein the crystallization step is performed in a non-oxidizing atmosphere.
  • the crystallization step is characterized in that the liquid temperature of the pH adjusted mixed solution is maintained at 25 to 60 ° C.
  • a method for producing ammonium manganese iron phosphate is provided.
  • a mixed solution of divalent Mn ions and phosphate ions, and Fe ions in addition to individually preparing mixed solutions with phosphate oxide ions, in the crystallization step, the pH of each mixed solution was individually adjusted and coprecipitated, and the resulting ammonium manganese phosphate and ammonium iron phosphate were respectively obtained.
  • a method for producing ammonium manganese iron phosphate characterized by mixing.
  • a precursor for a positive electrode active material for a lithium secondary battery obtained by the production method according to any one of the first to sixth aspects, It is represented by the general formula: NH 4 Mn x Fe 1-x PO 4 .H 2 O (0 ⁇ x ⁇ 1), and the sodium content is 0.01% by mass or less. Is provided.
  • a heat treatment step of heat-treating at 200 to 500 ° C. in an inert or reducing atmosphere after mixing the ammonium manganese iron phosphate and the lithium salt according to the seventh aspect A compound serving as a carbon source was mixed with LiMn x Fe 1-x PO 4 (0 ⁇ x ⁇ 1) obtained by the heat treatment step so that the carbon content after firing was 1 to 5% by mass.
  • a positive electrode active for a lithium secondary battery comprising: a carbon source mixing step for obtaining a carbon source mixture; and a firing step for firing the carbon source mixture at 500 to 800 ° C. in an inert or reducing atmosphere.
  • a method of manufacturing a material is provided.
  • the positive electrode active material for a lithium secondary battery wherein the pulverization is simultaneously performed when mixing the ammonium manganese iron phosphate and the lithium salt.
  • a manufacturing method is provided.
  • a lithium secondary battery comprising an olivine-type lithium manganese iron composite phosphate represented by the general formula: LiMn x Fe 1-x PO 4 (0 ⁇ x ⁇ 1)
  • a positive electrode active material for a lithium secondary battery is provided.
  • the battery characteristics having an initial discharge capacity of 150 mAh / g or more and an energy efficiency of 85% or more.
  • a positive electrode active material for a lithium secondary battery is provided.
  • a lithium secondary battery comprising a positive electrode composed of a positive electrode active material for a lithium secondary battery according to the tenth or eleventh invention.
  • a precursor of a positive electrode active material for an olivine-type lithium secondary battery in which Mn and Fe are uniformly mixed at an atomic level can be obtained, and the positive electrode active material obtained using the precursor is
  • the lithium secondary battery using the positive electrode active material exhibits excellent battery characteristics with high capacity and high output. Further, the production method is easy and suitable for industrial scale production without using toxic compounds, and its industrial value is extremely high.
  • Ammonium manganese iron phosphate is a precursor of a positive electrode active material for a lithium secondary battery, and the manufacturing method of ammonium manganese iron phosphate of the present invention is divalent.
  • a mixed solution of divalent Mn ions, Fe ions and phosphoric oxide ions is prepared. Since the composition of manganese iron phosphate obtained in the crystallization process of the next step matches the composition ratio of the mixed solution, the ratio of Mn ions and Fe ions contained in the mixed solution to the phosphate ions is represented by the following general formula ( The divalent Mn salt, Fe salt and phosphorous oxide are dissolved in water so as to achieve the composition ratio of 1).
  • the total amount of Mn and Fe and the molar ratio of phosphorus oxide is 1: 1 in terms of stoichiometry, but considering the yield during crystallization, the total amount of Mn and Fe with respect to the phosphorus oxide Can be in the range of 0.9 to 1.1.
  • the molar ratio is 0.90 or less, the yield of phosphate ions deteriorates, while when it is 1.1 or more, impurities such as Fe 2 O 3 and MnO 2 are likely to be generated. It is preferably dissolved so as to be 0.95 to 1.05.
  • the molar ratio of Mn and Fe may be the molar ratio of the ammonium manganese iron phosphate to be obtained.
  • water-soluble salts can be widely used, but divalent inorganic salts are preferred. Specifically, it is preferable to use one or more water-soluble metal salts selected from sulfates or chloride salts as a feedstock for Mn ions and Fe ions.
  • a water-soluble one can be used.
  • phosphoric acid or ammonium dihydrogen phosphate Is preferably used.
  • a pH range it is important to use a pH range to be controlled and ammonia. If the pH is less than 7, ammonia, metal ions and phosphate ions do not completely react and remain in the mixed solution, resulting in a decrease in yield and compositional deviation. When the pH is 9 or more, oxidation of Mn and Fe is unlikely to occur, and impurities such as Fe 3 O 4 and MnO 2 are generated and remain as heterogeneous phases after being mixed with a lithium salt and heat-treated to deteriorate characteristics. .
  • an alkali metal hydroxide or the like can be used. However, when an alkali metal hydroxide is used, the alkali metal remains in the coprecipitate.
  • the crystallization step it is preferable to coprecipitate in an inert atmosphere.
  • an inert atmosphere it is possible to suppress the formation of impurities such as Fe 3 O 4 and MnO 2 by oxidation.
  • the inert atmosphere is preferably an inert gas atmosphere such as nitrogen gas.
  • the liquid temperature of the mixed solution is preferably maintained at 25 to 60 ° C. When the liquid temperature is less than 25 ° C., the solubility of metal ions in the mixed solution is low, and a difference in precipitation rate of Mn and Fe may occur, resulting in a composition shift.
  • the solubility of metal ions in the mixed solution increases, and the crystallinity of ammonium manganese iron phosphate obtained by decreasing the precipitation rate becomes too high.
  • the positive electrode active material to be produced may become coarse.
  • a reaction vessel with a stirrer is preferable in order to cause the reaction to occur uniformly, and in order to control the atmosphere during crystallization, it is preferable to have a sealed structure. preferable.
  • solid-liquid separation is performed by filtration, centrifugation, etc., and in order to remove impurities, the ammonium manganese iron phosphate obtained in the crystallization step is sufficiently washed and then dried.
  • impurities such as sodium can be easily removed by washing with water.
  • the ammonium manganese iron phosphate obtained in the crystallization step is easily oxidized during drying, and Mn or Fe may be oxidized to leave a foreign phase as an impurity. For this reason, drying after washing is performed in a non-oxidizing atmosphere. Although it will not specifically limit if it is in a non-oxidizing atmosphere, It is preferable to carry out in an inert atmosphere or a vacuum atmosphere. Moreover, the drying temperature should just be the range which can suppress oxidation, it is preferable to set it as 250 degrees C or less, and it is more preferable to set it as 150 degrees C or less. On the other hand, if it is less than 60 ° C., it takes time to dry, which is not preferable.
  • a mixed solution of divalent Mn ions and Fe ions and phosphoric oxide ions is prepared, and Mn, Fe and phosphorous oxide are co-precipitated simultaneously.
  • a mixed solution of product ions and a mixed solution of Fe ions and phosphate ions are prepared individually, and also in the crystallization step, each mixed solution is individually pH-adjusted and coprecipitated, and the molar ratio of Mn and Fe It is good also as a precursor by mixing. Since ammonium manganese phosphate and iron iron phosphate have similar structures, a lithium manganese iron composite phosphate having a uniform composition can be obtained even by low-temperature heat treatment by thoroughly mixing each of them.
  • ammonium manganese iron phosphate of the present invention is a precursor of a positive electrode active material for a lithium secondary battery, and is obtained by the above production method.
  • the sodium content is 0.01% by mass or less.
  • the ammonium manganese iron phosphate of the present invention is a precursor of a positive electrode active material for a lithium secondary battery, and is obtained by the above production method, so that Mn and Fe are uniformly mixed at an atomic level. .
  • the composition can be made uniform by a low-temperature heat treatment after mixing with the lithium salt, and a lithium manganese iron composite phosphate having a fine particle diameter can be obtained.
  • sodium content is 0.01 mass% or less, and sufficient characteristics are acquired with the positive electrode active material obtained. When the sodium content exceeds 0.01% by mass, the movement of Li ions in the olivine structure is inhibited by Na, so that the positive electrode performance using the obtained positive electrode active material is deteriorated.
  • the method for producing a positive electrode active material for lithium secondary battery according to the present invention is a positive electrode active material for lithium secondary battery (hereinafter sometimes simply referred to as a positive electrode active material).
  • a positive electrode active material for lithium secondary battery
  • After mixing the ammonium manganese iron phosphate and the lithium salt, which are precursors of the above, heat treatment at 200 to 500 ° C. in an inert or reducing atmosphere, and a carbon content of 1 after firing the compound serving as the carbon source A carbon source mixing step of mixing to obtain 5% by mass to obtain a carbon source mixture, and a baking step of baking the carbon source mixture at 500 to 800 ° C. in an inert or reducing atmosphere.
  • the lithium salt is not particularly limited, and general lithium salts such as lithium hydroxide, lithium carbonate, and lithium acetate can be used.
  • a mixing method a mixer capable of sufficiently mixing ammonium manganese iron phosphate and a lithium salt may be used.
  • a shaker mixer, a dry type using an alumina or zirconia sphere, a wet mill or the like can be used.
  • a mill such as a ball mill, a planetary mill, a vibration mill, a bead mill or the like is preferable because pulverization can be performed simultaneously with mixing.
  • the mixture After mixing with the lithium salt, the mixture is heat-treated at 200 to 500 ° C., preferably 300 to 500 ° C. in an inert or reducing atmosphere. Since the manganese manganese iron phosphate of the present invention is in a state in which Mn and Fe are uniformly mixed at the atomic level, Mn and Fe are uniformly mixed even in the heat treatment in the above temperature range, and good crystallinity. LiMn x Fe 1-x PO 4 (0 ⁇ x ⁇ 1) can be obtained. When the heat treatment temperature is less than 200 ° C., lithium carbonate as a reaction raw material may remain.
  • the conductivity of the active material is reduced.
  • the reducing atmosphere is preferably a mixed gas of an inert gas and hydrogen gas in order to suppress the mixing of impurities, and the hydrogen gas content in the mixed gas is preferably 1 to 20% by volume.
  • the carbon source mixing step is a compound that becomes a carbon source for imparting conductivity to LiMn x Fe 1-x PO 4 (0 ⁇ x ⁇ 1) obtained by the heat treatment step.
  • a carbon source is a step of mixing so that the carbon content is 1 to 5 mass% after firing.
  • the carbon source is not particularly limited as long as it is graphitized by firing to become a conductive carbonaceous material.
  • Graphite such as natural graphite and artificial graphite, carbon black such as acetylene black and ketjen black , Carbon fibers, common hydrocarbons such as sucrose, ascorbic acid, and other organic compounds that generate carbonaceous matter by decomposition can be widely used.
  • the amount of carbon atoms contained in the carbon source tends to be smaller than that of the carbon source by firing.
  • the blending amount of the carbon source is preferably increased by 40 to 120%, more preferably by 50 to 120% by mass ratio with respect to the amount of carbon contained after firing.
  • the mixing is performed using a shaker mixer or a dry or wet mill using alumina or zirconia spheres so that the LiMn x Fe 1-x PO 4 (0 ⁇ x ⁇ 1) and the carbon source are uniformly mixed. It is preferable to carry out sufficiently. Even in the carbon source mixing step, LiMn x Fe 1-x PO 4 (0 ⁇ x ⁇ 1) obtained in the heat treatment step is pulverized to atomize the positive electrode active material finally obtained and uniformly form particles. Can be coated with a conductive carbonaceous material, it is preferable to grind at the same time as mixing. For this reason, it is preferable to use a mill such as a ball mill, a planetary mill, a vibration mill, or a bead mill.
  • a mill such as a ball mill, a planetary mill, a vibration mill, or a bead mill.
  • LiMn x Fe 1-x PO 4 (0 ⁇ x ⁇ 1) mixed with the carbon source in the carbon source mixing step is 600 to 800 ° C. in an inert or reducing atmosphere, preferably 600
  • LiMn x Fe 1-x PO 4 (0 ⁇ x ⁇ 1) that is complex with the carbonaceous material and has good conductivity, that is, a positive electrode active material for a lithium secondary battery is obtained.
  • the firing temperature is less than 600 ° C., graphitization of carbon does not proceed, and sufficient conductivity cannot be obtained for the positive electrode active material.
  • the firing temperature exceeds 800 ° C. the sintering of the particles proceeds and becomes coarse, and the conductivity of the positive electrode active material is lowered.
  • a furnace in the heat treatment step and the firing step for example, a general heat treatment furnace / firing furnace such as a batch furnace, a roller hearth kiln, a pusher furnace, a rotary kiln, or a fluidized bed furnace can be used.
  • a reducing atmosphere of an inert gas such as nitrogen or argon or a mixed gas of nitrogen and hydrogen is preferably used.
  • the positive electrode active material is composed of uniform fine primary particles, which can be used after being pulverized and classified according to the necessity of the battery electrode manufacturing process.
  • the cathode active material of the present invention is an olivine-type lithium manganese compound represented by the above general formula (2) composed of uniform fine primary particles, compounded with a carbonaceous material. It consists of iron complex phosphate.
  • x is preferably 0.6 ⁇ x ⁇ 0.8.
  • x is less than 0.6, the ratio of Fe 2+ / Fe 3+ redox with a Li potential of about 3.45 occupies the battery reaction, and the average potential when a lithium secondary battery is formed decreases. Charge / discharge efficiency decreases.
  • the primary particle diameter was evaluated using the crystallite diameter determined by the Scherrer formula from the half-width of the crystal plane peak of the X-ray diffraction profile that can be quantitatively evaluated.
  • the crystallite size is a structural unit of particles composed of a single crystal, and the primary particles may be aggregates thereof, and thus are not necessarily equal, but if the primary particles are sufficiently fine, The child diameter and the primary particle diameter are considered to be in a proportional relationship, and the primary particle diameter can be evaluated.
  • the crystallite diameter determined from the (131) plane in the X-ray diffraction of the positive electrode active material of the present invention is 50 nm or less.
  • the crystallite diameter is larger than 50 nm, lithium ions and electrons inside the LiMn x Fe 1-x PO 4 (0 ⁇ x ⁇ 1) particles having a low electron conductivity and a low resistance are generated in the battery reaction. The distance traveled by the battery increases, the reaction rate of the battery becomes extremely slow, the battery resistance increases, and sufficient conductivity cannot be obtained.
  • the crystallite diameter is preferably 10 nm or more. When the crystallite diameter is less than 10 nm, the bulk density of the positive electrode active material decreases, and the battery capacity per unit volume when configured as a battery may not be sufficiently obtained.
  • the positive electrode active material of the present invention has a BET specific surface area of 15 m 2 / g or more and a carbon content of 1 to 5% by mass, and good battery characteristics can be obtained when used as a positive electrode active material of a battery. It is done.
  • the BET specific surface area is less than 15 m 2 / g, when the positive electrode of the battery is constructed, sufficient contact with the electrolytic solution cannot be obtained, resulting in an increase in battery resistance and a decrease in conductivity.
  • the upper limit of the BET specific surface area is not particularly limited, but is preferably 40 m 2 / g or less. If it exceeds 40 m 2 / g, the bulk density will be low, and the battery capacity per unit volume may be too low.
  • the positive electrode active material of the present invention has a carbon content of less than 1% by mass, sufficient conductivity of the positive electrode active material cannot be obtained.
  • the carbon content exceeds 5% by mass, LiMn in the positive electrode active material can be obtained.
  • x Fe 1-x PO 4 (0 ⁇ x ⁇ 1) decreases and the battery capacity decreases.
  • the positive electrode active material of the present invention exhibits good battery characteristics such as an initial discharge capacity of 150 mAh / g or more and an energy efficiency of 85% or more when used as a positive electrode active material of a C2023 type coin battery. Suitable for batteries.
  • the lithium secondary battery according to the present invention is composed of the same constituent elements as a general lithium secondary battery, such as a positive electrode, a negative electrode, and a nonaqueous electrolyte.
  • a general lithium secondary battery such as a positive electrode, a negative electrode, and a nonaqueous electrolyte.
  • the embodiment of the lithium secondary battery of the present invention will be described in detail by dividing into its components, uses, etc., but the following embodiments are merely examples, and the lithium secondary battery of the present invention is In addition to the embodiments described in the present specification, various modifications and improvements can be made based on the knowledge of those skilled in the art.
  • a positive electrode is formed from the positive electrode compound material containing the positive electrode active material of this invention, the electrically conductive material, and the binder. Specifically, a powdered positive electrode active material and a conductive material are mixed, a binder is added thereto, and if necessary, a solvent for viscosity adjustment is further added to adjust the positive electrode mixture paste, For example, the positive electrode mixture paste is applied to the surface of a current collector made of aluminum foil, dried, and pressurized as necessary to produce a sheet-like positive electrode.
  • the conductive material is for ensuring the electrical conductivity of the positive electrode, and for example, a material obtained by mixing one or more carbon material powders such as carbon black, acetylene black, and graphite can be used.
  • the binder plays a role of anchoring the active material particles.
  • a fluorine-containing resin such as polytetrafluoroethylene, polyvinylidene fluoride, and fluorine rubber, a thermoplastic resin such as polypropylene and polyethylene, and other suitable materials. Can be used.
  • an organic solvent such as N-methyl-2-pyrrolidone is used as a solvent to be added to the positive electrode mixture as needed, that is, as a solvent for dispersing the active material, conductive material and activated carbon and dissolving the binder. be able to. Activated carbon can also be added to increase the electric double layer capacity.
  • Such a positive electrode active material, a conductive material, and a binder are mixed, and if necessary, activated carbon and a solvent are added and kneaded to prepare a positive electrode mixture paste.
  • Each mixing ratio in the positive electrode mixture can also be an important factor that determines the performance of the lithium ion secondary battery.
  • the total solid content (meaning excluding solvent) of the positive electrode mixture is 100% by mass
  • the positive electrode active material is 60 to 95% by mass
  • the conductive material is 1 to It is desirable that the content is 20% by mass and the binder is 1 to 20% by mass.
  • the above-mentioned positively mixed positive electrode mixture paste is applied and dried to disperse the solvent, and if necessary, a roll press to increase the electrode density thereafter
  • the positive electrode can be formed into a sheet shape by compressing with the above.
  • the sheet-like positive electrode can be cut into an appropriate size according to the intended battery and used for battery production.
  • Negative electrode For the negative electrode, metallic lithium, lithium alloy, or the like, and a negative electrode mixture made by mixing a binder with a negative electrode active material capable of inserting and extracting lithium ions and adding a suitable solvent to form a paste. , And applied to the surface of a current collector of a metal foil such as copper, dried, and compressed to increase the electrode density as necessary.
  • a fired organic compound such as natural graphite, artificial graphite, or a phenol resin, or a powdery carbon material such as coke can be used.
  • the negative electrode binder is a fluorine-containing resin such as polyvinylidene fluoride as in the positive electrode, and the negative electrode active material and the binder are dispersed in a solvent such as N-methyl-2-pyrrolidone.
  • Organic solvents can be used.
  • (C) Separator A separator is sandwiched and loaded between the positive electrode and the negative electrode. The separator separates the positive electrode and the negative electrode and retains the electrolyte, and a thin microporous film such as polyethylene or polypropylene can be used.
  • Non-aqueous electrolyte The non-aqueous electrolyte is obtained by dissolving a lithium salt as a supporting salt in an organic solvent.
  • the organic solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and trifluoropropylene carbonate, chain carbonates such as diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, and dipropyl carbonate, tetrahydrofuran, 2- One kind selected from ether compounds such as methyltetrahydrofuran and dimethoxyethane, sulfur compounds such as ethylmethylsulfone and butanesultone, phosphorous compounds such as triethyl phosphate, triethyl phosphate and trioctyl phosphate alone, or two or more kinds It can be used by mixing.
  • the non-aqueous electrolyte may contain a radical scavenger, a surfactant, a flame retardant, and the like.
  • the lithium secondary battery of the present invention configured as described above can have various shapes such as a cylindrical type and a stacked type. Even if any shape is adopted, the positive electrode and the negative electrode are laminated via a separator to form an electrode body, and between the positive electrode current collector and the negative electrode current collector to the positive electrode terminal and the negative electrode terminal, A current collecting lead or the like is used for connection, the electrode body is impregnated with the nonaqueous electrolyte, and the battery case is sealed to complete the battery.
  • the lithium secondary battery of the present invention includes a positive electrode using the positive electrode active material for a lithium secondary battery of the present invention as a positive electrode material, and is charged and discharged at a potential of 3.0 to 4.5 V, It is possible to industrially realize a lithium secondary battery that is extremely safer than conventional lithium metal composite oxides and also has a high capacity.
  • the chemical analysis method of the metal used in the Example is as follows.
  • An ICP emission analysis method (Varian, 725ES) was used for ICP emission analysis.
  • This mixture was applied onto an aluminum foil, dried at 80 ° C., punched to an electrode size of 11 mm ⁇ , and pressed at a press pressure of 98 MPa (1.0 tonf / cm 2 ) to produce an electrode.
  • a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DEC) containing metal Li as a negative electrode and 1 mol / L of electrolyte LiPF 6 as an electrolytic solution in a glove box (EC: DEC volume ratio) 7: 3)
  • EC: DEC volume ratio
  • the battery was charged and discharged under the conditions of charge 0.2 mA / cm 2 , 4.5 V, rest 60 minutes, discharge 0.2 mA / cm 2 , 2.0 V, 25 ° C., and the discharge capacity at the first cycle was Used as an evaluation value.
  • Example 1 Iron sulfate heptahydrate (special grade manufactured by Wako Co., Ltd .: purity 99.5% by mass) 0.375 mol (104.8 g) and manganese sulfate n-hydrate (Chuo Electric Works: 99.9% by mass) 1.125 mol (191.9 g) and phosphoric acid (manufactured by Wako Co., Ltd .: purity 85.0% by mass or more) 1.5 mol (172.9 g) were made up to 3 L with distilled water, stirred with a stirrer for 1 hour, did. Moreover, 25 mass% ammonia aqueous solution was used as pH adjustment solution.
  • the mixture obtained by using an electric furnace was heated at 10 ° C./min while purging a mixed gas of 98 vol% nitrogen and 2 vol% hydrogen into the furnace at a flow rate of 1 L / min, and then 350 ° C. for 5 hours. Baked.
  • the fired product was analyzed by X-ray diffraction, it was identified as LiMn 0.75 Fe 0.25 PO 4 and it was confirmed that lithium manganese iron composite phosphate was obtained.
  • the composition of Li: Fe: Mn: P of this positive electrode active material was 1.00: 0.75: 0.25: 1.00 in terms of molar ratio, and the carbon content was 2.2 mass%.
  • X-ray diffraction analysis confirmed that it was a single phase of olivine-type lithium manganese iron complex phosphate, and the crystallite size of the (131) plane was found from the X-ray diffraction analysis profile using the Scherrer equation. It was. When observed with a scanning electron microscope (SEM), the primary particle size was 100 to 200 nm.
  • the specific surface area of the positive electrode active material determined by the BET method was 24.3 m 2 / g. Furthermore, when the battery evaluation of the positive electrode active material was performed, the initial charge capacity was 156 mAh / g, the initial discharge capacity was 152 mAh / g, and the initial efficiency was 97%.
  • Example 2 In the same manner as in Example 1, coprecipitates of Mn and P and Fe and P were separately prepared so as to have a molar ratio of 1: 1, and when mixed with lithium carbonate by a planetary ball mill, LiMn 0.
  • a positive electrode active material was obtained in the same manner as in Example 1 except that mixing was performed so that the composition ratio was 75 Fe 0.25 PO 4 .
  • the obtained positive electrode active material was an olivine type lithium manganese iron composite phosphate single phase, and the molar ratio of Li: Mn: Fe: P was 1.00: 0.75. : 0.25: 1.00, and the carbon content was 2.2% by mass.
  • the crystallite size of the (131) plane was 49 nm, the primary particle size was 100 to 200 nm, and the BET specific surface area was 23.8 m 2 / g. Moreover, the initial charge capacity by battery evaluation was 155 mAh / g, the initial discharge capacity was 150 mAh / g, and the initial efficiency was 97%.
  • Example 1 The crystallization step was performed in the same manner as in Example 1 except that the pH was controlled to 6 to 6.2 in the crystallization step. When the amounts of Fe, Mn, and P in the filtrate, which were separated into solid and liquid after the crystallization reaction, were measured, the reaction raw materials of Fe, Mn, and P in a molar ratio of 10% or more remained unreacted. The rest was interrupted.
  • Example 2 The crystallization step was performed in the same manner as in Example 1 except that the pH was controlled to 9.1 to 9.3 in the crystallization step.
  • the ammonium manganese iron phosphate obtained in the crystallization process was analyzed by X-ray diffraction, many different phases such as Fe 3 O 4 , Fe 2 O 3 , and MnO 2 were detected.
  • a positive electrode active material was obtained in the same manner as in Example 1 except that MnCO 2 and (NH 4 ) 2 HPO 4 were used in place of the ammonium manganese iron phosphate obtained in the crystallization step.
  • MnCO 2 and (NH 4 ) 2 HPO 4 were used in place of the ammonium manganese iron phosphate obtained in the crystallization step.
  • LiMn 0.75 Fe 0.25 PO 4 different phases such as Li 3 PO 4 , MnO 2 and Fe 3 O 4 are found. Observed. These different phases remained up to the positive electrode active material, but the molar ratio of Li: Fe: Mn: P was 1.00: 0.75: 0.25: 1.00, and the carbon content was 2.4% by mass. Met.
  • the primary particle size was 100 to 200 nm, and the BET specific surface area was 24.1 m 2 / g.
  • the initial charge capacity was 112 mAh / g
  • the initial discharge capacity was 98 mAh / g
  • the initial efficiency was 88%.
  • the method for producing ammonium manganese iron phosphate according to the present invention is a method for producing a precursor of a positive electrode active material for a lithium secondary battery, in which Mn and Fe are uniformly mixed at the atomic level.
  • a positive electrode active material precursor for a lithium-type lithium secondary battery can be obtained, and the positive electrode active material obtained using the precursor has a fine particle size and is uniform in composition.
  • the lithium secondary battery used exhibits excellent battery characteristics with high capacity and high output. Therefore, the industrial applicability is extremely large.

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Abstract

Cette invention concerne une matière active d'électrode positive pour batteries rechargeables au lithium, formée à partir d'un phosphate composite de lithium-manganèse-fer dont le diamètre des particules est réduit et présentant d'excellentes caractéristiques de batterie telles qu'une haute capacité et un haut rendement quand elle est utilisée en tant que matière active d'électrode positive. L'invention concerne en outre un procédé de production d'une matière active d'électrode positive pour batteries rechargeables au lithium, mettant en œuvre, en tant que précurseur, un phosphate de manganèse-fer-ammonium à particules fines présentant une composition uniforme. Le procédé de production d'un précurseur de matière active d'électrode positive pour batteries rechargeables au lithium, qui est un procédé de production d'un phosphate de manganèse-fer-ammonium, est caractérisé en ce qu'il comprend : une étape de préparation de solution mélangée à laquelle est préparée une solution d'un mélange d'ions divalents de Mn, d'ions de Ge et d'ions de phosphate ; et une étape de cristallisation à laquelle un phosphate de manganèse-fer-ammonium représenté par la formule générale NH4MnxFe1-xPO4∙H2O (où 0 < x < 1) est obtenu par coprécipitation par ajout d'ammoniac à la solution mélangée de façon à régler son pH dans la plage allant de 7 à 9.
PCT/JP2011/070944 2011-09-14 2011-09-14 Phosphate de manganèse-fer-ammonium, son procédé de production, matière active d'électrode positive pour batteries rechargeables au lithium mettant en œuvre du phosphate de manganèse-fer-ammonium, procédé de production de matière active d'électrode positive pour batteries rechargeables au lithium mettant en œuvre du phosphate de manganèse-fer-ammonium, et batterie rechargeable au lithium mettant en œuvre une matière active d'électrode positive pour batteries rechargeables au lithium mettant en œuvre du phosphate de manganèse-fer-ammonium WO2013038516A1 (fr)

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PCT/JP2011/070944 WO2013038516A1 (fr) 2011-09-14 2011-09-14 Phosphate de manganèse-fer-ammonium, son procédé de production, matière active d'électrode positive pour batteries rechargeables au lithium mettant en œuvre du phosphate de manganèse-fer-ammonium, procédé de production de matière active d'électrode positive pour batteries rechargeables au lithium mettant en œuvre du phosphate de manganèse-fer-ammonium, et batterie rechargeable au lithium mettant en œuvre une matière active d'électrode positive pour batteries rechargeables au lithium mettant en œuvre du phosphate de manganèse-fer-ammonium
JP2013533394A JP5835334B2 (ja) 2011-09-14 2011-09-14 リン酸アンモニウムマンガン鉄とその製造方法、および該リン酸アンモニウムマンガン鉄を用いたリチウム二次電池用正極活物質の製造方法

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KR101938462B1 (ko) * 2013-07-09 2019-01-14 다우 글로벌 테크놀로지스 엘엘씨 리튬 금속 산화물 및 리튬 금속 포스페이트를 포함하는 혼합된 양성 활성 물질
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WO2024000840A1 (fr) * 2022-06-28 2024-01-04 广东邦普循环科技有限公司 Méthode de préparation de phosphate d'ammonium-manganèse-fer, et phosphate de lithium-manganèse-fer et utilisation associée
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CN115231544A (zh) * 2022-08-09 2022-10-25 湖北万润新能源科技股份有限公司 一种磷酸锰铵的制备方法和锂离子电池正极材料
CN115744861B (zh) * 2022-11-21 2024-03-15 南通金通储能动力新材料有限公司 高压实磷酸锰铁锂前驱体、磷酸锰铁锂正极材料及前驱体的制备方法
CN115744861A (zh) * 2022-11-21 2023-03-07 南通金通储能动力新材料有限公司 高压实磷酸锰铁锂前驱体、磷酸锰铁锂正极材料及前驱体的制备方法
CN116924377B (zh) * 2023-09-18 2024-01-02 宁波容百新能源科技股份有限公司 磷酸锰铁铵、磷酸锰铁锂及其制备方法和应用
CN116924377A (zh) * 2023-09-18 2023-10-24 宁波容百新能源科技股份有限公司 磷酸锰铁铵、磷酸锰铁锂及其制备方法和应用

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