WO2013035831A1 - Procédé de production de matière d'électrode positive de batterie secondaire au lithium-ion - Google Patents

Procédé de production de matière d'électrode positive de batterie secondaire au lithium-ion Download PDF

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WO2013035831A1
WO2013035831A1 PCT/JP2012/072865 JP2012072865W WO2013035831A1 WO 2013035831 A1 WO2013035831 A1 WO 2013035831A1 JP 2012072865 W JP2012072865 W JP 2012072865W WO 2013035831 A1 WO2013035831 A1 WO 2013035831A1
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Prior art keywords
positive electrode
electrode material
ion secondary
secondary battery
lithium ion
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PCT/JP2012/072865
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English (en)
Japanese (ja)
Inventor
洋平 細田
結城　健
知浩 永金
境　哲男
金載 朴
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日本電気硝子株式会社
独立行政法人産業技術総合研究所
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Publication of WO2013035831A1 publication Critical patent/WO2013035831A1/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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a lithium ion secondary battery positive electrode material (hereinafter also simply referred to as “positive electrode material”) used in portable electronic devices, electric vehicles and the like.
  • positive electrode material a lithium ion secondary battery positive electrode material
  • Lithium ion secondary batteries have established themselves as high-capacity and lightweight power supplies that are indispensable for portable electronic terminals and electric vehicles.
  • inorganic metal oxides such as lithium cobaltate (LiCoO 2 ) and lithium manganate (LiMn 2 O 4 ) have been used as positive electrode materials for lithium ion secondary batteries.
  • LiCoO 2 lithium cobaltate
  • LiMn 2 O 4 lithium manganate
  • LiM x Fe 1 -x PO 4 (0 ⁇ x ⁇ 1, M is Nb, Ti, V, Cr, An olivine-type crystal represented by at least one selected from Mn, Co, and Ni has attracted attention, and various researches and developments are underway (for example, see Patent Document 1).
  • LiM x Fe 1-x PO 4 is superior in temperature stability to LiCoO 2 and is expected to operate safely at high temperatures.
  • it since it is a structure which has phosphoric acid as a skeleton, it has the characteristic that it is excellent in the tolerance to structural deterioration by charging / discharging reaction.
  • the positive electrode material containing LiM x Fe 1-x PO 4 has a very large internal resistance compared to lithium metal oxides such as LiCoO 2 , so that resistance polarization increases when charging / discharging, and sufficient discharge is achieved. There is a problem that it is difficult to obtain a capacity.
  • the specific surface area is increased to facilitate the diffusion of lithium ions, and the internal resistance is reduced.
  • a reduction method has been proposed.
  • a positive electrode active material powder is mixed with a resin and fired to form a carbon-containing layer on the surface of the positive electrode active material.
  • the particle diameter of the positive electrode active material powder is small, the thickness of the carbon-containing layer formed on the surface tends to be uneven. Since the movement of lithium ions is hindered in a place where the thickness of the carbon-containing layer is large, there is a problem that a desired discharge capacity cannot be obtained. Also, particularly when the current during discharge increases, there is a problem that the internal resistance of the positive electrode material increases and the output voltage decreases.
  • an object of the present invention is to provide a method for producing a positive electrode material for a lithium ion secondary battery that has a high discharge capacity and a low output voltage drop when the current during discharge is large.
  • the present invention includes (1) a step of mixing an inorganic powder containing Li, Fe, P and O and having an average particle size of 1.8 ⁇ m or less with a surfactant, and (2) heat-treating the mixture.
  • the inorganic powder is represented by the general formula LiM x Fe 1-x PO 4 (0 ⁇ x ⁇ 1, M is at least one selected from Nb, Ti, V, Cr, Mn, Co and Ni).
  • the present invention relates to a method for producing a positive electrode material for a lithium ion secondary battery, comprising the steps of precipitating olivine crystals and forming a carbon-containing layer on the surface of an inorganic powder.
  • a uniform and thin carbon-containing layer is formed on the surface of the inorganic powder by mixing the surfactant with the inorganic powder containing the elements of Li, Fe, P and O and performing heat treatment.
  • the reason why a uniform and thin carbon-containing layer can be formed on the surface of the inorganic powder is not known in detail, but the hydrophilic group of the surfactant is Li, Fe, P and O. It is presumed that this is because the surfactant molecules are easily attracted uniformly on the surface of the inorganic powder because they are electrically attracted to the hydroxyl groups existing over the entire surface of the inorganic powder containing the element.
  • the method for producing a positive electrode material for a lithium ion secondary battery according to the present invention is such that the inorganic powder has a composition of mol%, Li 2 O 20-50%, Fe 2 O 3 5-40%, and P 2 O 5. It preferably contains 20 to 50%.
  • an olivine type crystal represented by the general formula LiM x Fe 1-x PO 4 is easily obtained.
  • the method for producing a positive electrode material for a lithium ion secondary battery according to the present invention comprises: (0-a) a step of melting and vitrifying the raw material powder, and (0-b) molding the molten glass. Thereafter, it is preferably produced by a method including a step of pulverizing.
  • the surfactant is preferably a nonionic surfactant.
  • Nonionic surfactants are particularly easily adsorbed to the surface of the inorganic powder and easily form a uniform carbon-containing layer on the surface of the inorganic powder.
  • the surfactant preferably has a polyoxyalkylene chain.
  • the oxygen atom of the polyoxyalkylene chain is hydrogen bonded to the hydroxyl group on the surface of the inorganic powder, the surfactant is likely to be firmly bonded to the surface of the inorganic powder. As a result, a carbon-containing layer having a uniform thickness is easily obtained when heat treatment is performed.
  • the surfactant preferably has an HLB value of 5 to 19.
  • the HLB value of the surfactant is within the above range, it becomes easy to form a uniform carbon-containing layer on the surface of the inorganic powder.
  • the HLB value is a relative ratio between the hydrophilic group and the lipophilic group of the surfactant expressed as a numerical value from 0 to 20, and is used as an index indicating the degree of affinity for water and oil. Is done. Specifically, the lower the HLB value, the higher the lipophilicity, while the higher the HLB value, the higher the hydrophilicity.
  • the surfactant preferably has a benzene ring.
  • the carbon-containing layer formed on the surface of the inorganic powder tends to be crystalline, and the electronic conductivity tends to increase.
  • the present invention relates to a positive electrode material for a lithium ion secondary battery, which is manufactured by any one of the methods described above.
  • the ratio of 1300 ⁇ 1400 cm -1 peak intensity D to the peak intensity G of 1550 ⁇ 1650 cm -1 in Raman spectroscopy (D / G) is 1 or less
  • the ratio (F / G) of the peak intensity F of 900 to 1000 cm ⁇ 1 with respect to the peak intensity G is preferably 0.5 or less.
  • the peak intensity G is derived from crystalline carbon
  • the peak intensity D is derived from amorphous carbon. Therefore, the smaller the value of the peak intensity ratio D / G, the closer the carbon-containing layer is to crystalline, and the higher the electron conductivity.
  • the peak intensity F is derived from the LiM x Fe 1-x PO 4 crystal. Therefore, the smaller the value of the peak intensity ratio F / G, the higher the proportion of the inorganic powder surface covered with the crystalline carbon-containing layer, and the higher the electronic conductivity.
  • the present invention it is possible to produce a positive electrode material for a lithium ion secondary battery that has a high discharge capacity and a low output voltage drop when the current during discharge is large.
  • the method for producing a positive electrode material for a lithium ion secondary battery according to the present invention comprises (1) a step of mixing an inorganic powder containing Li, Fe, P and O and having an average particle size of 1.8 ⁇ m or less and a surfactant to obtain a mixture. And (2) by heat-treating the mixture, in the inorganic powder, the general formula LiM x Fe 1-x PO 4 (0 ⁇ x ⁇ 1, M is Nb, Ti, V, Cr, Mn, Co and Ni And a step of depositing a carbon-containing layer on the surface of the inorganic powder.
  • the inorganic powder containing Li, Fe, P and O is a crystal or crystal containing, as a composition, mol%, Li 2 O 20 to 50%, Fe 2 O 3 5 to 40%, P 2 O 5 20 to 50%. It is preferably a vitrified glass. The reason for limiting the composition in this way will be described below.
  • Li 2 O is the main component of LiM x Fe 1-x PO 4 crystal.
  • the Li 2 O content is preferably 20 to 50%, particularly preferably 25 to 45%.
  • LiM x Fe 1-x PO 4 crystals are difficult to precipitate.
  • Fe 2 O 3 is also a main component of the LiM x Fe 1-x PO 4 crystal.
  • the content of Fe 2 O 3 is preferably 5 to 40%, 15 to 35%, 25 to 35%, particularly 31.6 to 34%.
  • LiM x Fe 1-x PO 4 crystals are difficult to precipitate.
  • LiM x Fe 1-x PO 4 crystals are difficult to precipitate and undesired Fe 2 O 3 crystals are likely to precipitate.
  • P 2 O 5 is also a main component of the LiM x Fe 1-x PO 4 crystal.
  • the content of P 2 O 5 is preferably 20 to 50%, particularly preferably 25 to 45%. If the content of P 2 O 5 is too small or too large, LiM x Fe 1-x PO 4 crystals are difficult to precipitate.
  • Nb 2 O 5 , V 2 O 5 , SiO 2 , B 2 O 3 , GeO 2 , Al 2 O 3 , Ga 2 O 3 , Sb 2 O 3 or Bi 2 O 3 may be added as components for improving the glass forming ability.
  • the total amount of these components is preferably 0 to 25%, particularly preferably 0.1 to 25%. If the total amount of the above components is too small, it is difficult to obtain the above effect, and if it is too large, the amount of LiM x Fe 1-x PO 4 crystals precipitated tends to decrease.
  • Nb 2 O 5 is an effective component for obtaining a homogeneous glass.
  • the Nb 2 O 5 content is preferably 0.05 to 10%, 0.1 to 5%, particularly preferably 0.2 to 3%. If the content of Nb 2 O 5 is too small, it is difficult to obtain a homogeneous glass. On the other hand, when the content of Nb 2 O 5 is too large, different crystals such as iron niobate precipitate during crystallization, and the charge / discharge characteristics tend to deteriorate.
  • Inorganic powder containing Li, Fe, P and O is prepared by preparing raw material powder and using the obtained raw material powder, chemical vapor phase synthesis such as melting process, sol-gel process, spraying of solution mist into flame, etc. Obtained by processes, mechanochemical processes, etc.
  • the inorganic powder is produced by a method including (0-a) a step of melting a raw material powder to vitrify, and (0-b) a step of forming the molten glass and then pulverizing it. According to this method, it is possible to produce a homogeneous inorganic powder containing Li, Fe, P and O at a low cost.
  • the melting temperature may be appropriately adjusted so that the raw material powder is uniformly melted. Specifically, it is preferably 900 ° C. or higher, particularly 1000 ° C. or higher. Although an upper limit is not specifically limited, Since it will lead to an energy loss when too high, it is preferable that it is 1500 degrees C or less, especially 1400 degrees C or less.
  • the method for forming molten glass is not particularly limited.
  • the molten glass may be poured between a pair of cooling rolls and formed into a film shape while rapidly cooling, or the molten glass may be poured out into a mold and formed into an ingot shape.
  • the method for pulverizing the molded body in the step (0-b) is not particularly limited, and a general pulverizing apparatus such as a ball mill or a bead mill can be used.
  • the average particle size of the inorganic powder is preferably 1.8 ⁇ m or less, 1.6 ⁇ m or less, and particularly preferably 1.4 ⁇ m or less. If the average particle size of the inorganic powder is too large, the specific surface area becomes small and lithium ions are difficult to diffuse, and the internal resistance tends to increase. As a result, lithium ion conductivity at the interface between the positive electrode material and the electrolyte tends to decrease, and the discharge capacity tends to decrease.
  • the lower limit is not particularly limited, but if the average particle size of the inorganic powder is too small, the cohesive force between the positive electrode material particles becomes strong and is difficult to disperse when formed into a paste, and also tends to aggregate and become coarse particles.
  • the average particle size of the inorganic powder is preferably 0.05 ⁇ m or more, 0.1 ⁇ m or more, and particularly preferably 0.2 ⁇ m or more.
  • the average particle diameter of the inorganic powder means D50 (volume-based average particle diameter), which is a value measured by a laser diffraction scattering method.
  • any of a cationic surfactant, an anionic surfactant, an amphoteric surfactant and a nonionic surfactant may be used, and in particular, a nonionic having excellent adsorptivity to the surface of the inorganic powder.
  • a surfactant is preferred.
  • Nonionic surfactants include polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, alkyl glucoside, polyoxyalkylene alkyl glucoside, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene fatty acid Ether, polyoxyalkylene allyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyethylene polyoxypropylene ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene block copolymer, fatty acid alkanolamide, glycerin fatty acid ester, propylene glycol fatty acid Examples thereof include esters and fatty alcohol ethoxylates.
  • nonionic surfactant having a polyoxyalkylene chain such as polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, etc. It is preferable.
  • the HLB value of the surfactant is preferably 5 to 19, 8 to 19, 9 to 17, particularly 10 to 15.
  • the hydrophilic group is reduced, so that the adsorption force to the surface of the inorganic powder is inferior, and the thickness of the carbon-containing layer is likely to be uneven.
  • the surfactant is easily dissolved in a dispersion medium such as water, and the amount of the surfactant adsorbed on the surface of the inorganic powder is reduced, so that the formation of the carbon-containing layer becomes insufficient.
  • the surfactant preferably has a benzene ring in the molecular structure.
  • the carbon-containing layer on the surface of the inorganic powder tends to be crystalline, and the electronic conductivity tends to increase.
  • the said effect is easy to be acquired, so that there are many benzene rings in a surfactant molecule.
  • the weight average molecular weight of the surfactant is preferably 100 to 10,000, 200 to 5,000, particularly 300 to 3,000. If the weight average molecular weight of the surfactant is too small, the van der Waals force becomes small and the adsorption force of the surfactant to the surface of the inorganic powder becomes small, so that the thickness of the carbon-containing layer tends to be uneven. On the other hand, when the weight average molecular weight of the surfactant is too large, the steric hindrance of the molecule increases, and it becomes difficult to adsorb on the surface of the inorganic powder, and the carbon-containing layer is hardly formed.
  • the addition amount of the surfactant is preferably 0.01 to 50 parts by weight, 0.1 to 50 parts by weight, 1 to 30 parts by weight, particularly 5 to 20 parts by weight with respect to 100 parts by weight of the inorganic powder. If the addition amount of the surfactant is too small, the formation of the carbon-containing layer tends to be insufficient. On the other hand, when the addition amount of the surfactant is too large, the thickness of the carbon-containing layer is increased, the movement of lithium ions is hindered, and the discharge capacity tends to decrease. In addition, in a lithium ion secondary battery, the potential difference between the positive electrode and the negative electrode is reduced, and a desired electromotive force may not be obtained.
  • step (2) the inorganic powder containing Li, Fe, P, and O and the surfactant are heat-treated, whereby the olivine type represented by the general formula LiM x Fe 1-x PO 4 in the inorganic powder.
  • the olivine type represented by the general formula LiM x Fe 1-x PO 4 in the inorganic powder By depositing crystals and forming a carbon-containing layer on the surface of the inorganic powder, a positive electrode material made of an inorganic powder whose surface is coated with the carbon-containing layer is obtained.
  • the heat treatment temperature is preferably 550 to 900 ° C., particularly 600 to 850 ° C. If the heat treatment temperature is too low, LiM x Fe 1-x PO 4 crystals are difficult to precipitate. On the other hand, if the heat treatment temperature is too high, heterogeneous crystals are likely to precipitate, and lithium ion conductivity may be reduced.
  • the heat treatment time may be appropriately adjusted so that LiM x Fe 1-x PO 4 crystals are sufficiently precipitated, and specifically, it is preferably 10 to 180 minutes, particularly 20 to 120 minutes.
  • the heat treatment is preferably performed in an inert or reducing atmosphere.
  • the surfactant adsorbed on the surface of the inorganic powder is reduced, and a carbon-containing layer can be formed on the surface of the inorganic powder.
  • iron in the inorganic powder is reduced and the valence is easily changed to divalent, and olivine-type LiM x Fe 1-x PO 4 crystals can be obtained at a high ratio.
  • the specific surface area of the positive electrode material obtained by the production method of the present invention is preferably 5 m 2 / g or more, more preferably 15 m 2 / g or more.
  • the specific surface area of the positive electrode material is 5 m 2 / g or more, the contact area between the positive electrode material and the electrolyte is increased, lithium ions and electrons can be easily exchanged, and the discharge capacity can be improved.
  • the upper limit is not particularly limited, but if it is too large, moisture tends to be adsorbed on the surface of the positive electrode material, which may cause ignition during charging and discharging. Therefore, the specific surface area of the positive electrode material is preferably 100 m 2 / g or less, 80 m 2 / g or less, particularly 60 m 2 / g or less.
  • the proportion of the carbon-containing layer is preferably 0.01 to 10% by mass, 0.1 to 8% by mass, particularly preferably 0.5 to 5% by mass. If the amount of the carbon-containing layer is too small, the formation of the carbon-containing layer tends to be insufficient. On the other hand, when the amount of the carbon-containing layer is too large, the content of the LiM x Fe 1-x PO 4 crystal as the positive electrode active material is relatively small, and the discharge capacity per unit mass of the positive electrode material tends to be small. .
  • the carbon-containing layer is preferably a porous structure having a large number of pores because the specific surface area tends to increase.
  • the content of LiM x Fe 1-x PO 4 crystals is preferably 20% by mass or more, 50% by mass or more, and particularly preferably 70% by mass or more.
  • the discharge capacity tends to decrease.
  • it does not specifically limit about an upper limit, In reality, it is 99 mass% or less, Furthermore, it is 95 mass% or less.
  • the crystallite size of the LiM x Fe 1-x PO 4 crystal is preferably 100 nm or less, particularly preferably 80 nm or less.
  • the lower limit is not particularly limited, but is actually 1 nm or more, and further 10 nm or more.
  • the crystallite size is determined according to Scherrer's formula from the analysis result of powder X-ray diffraction.
  • the lithium ion secondary battery positive electrode material of the present invention preferably has a tap density of 0.3 g / ml or more, particularly 0.5 g / ml or more. If the tap density is too small, the electrode density decreases and the discharge capacity per unit volume of the battery tends to decrease.
  • the upper limit is approximately a value corresponding to the true specific gravity, but in consideration of the agglomeration of the powder, it is practically 5 g / ml or less, particularly 4 g / ml or less.
  • the tap density is a value measured under tapping conditions of tapping stroke: 10 mm, tapping frequency: 250 times, tapping speed: 2 times / 1 second.
  • the ratio of 1300 ⁇ 1400 cm -1 peak intensity D to the peak intensity G of 1550 ⁇ 1650 cm -1 in Raman spectroscopy (D / G) is 1 or less, particularly 0.8
  • the ratio (F / G) of the peak intensity F of 900 to 1000 cm ⁇ 1 to the peak intensity G is preferably 0.5 or less, particularly preferably 0.1 or less.
  • Example 1 (1) Preparation of inorganic powder Using lithium metaphosphate (LiPO 3 ), lithium carbonate (Li 2 CO 3 ), ferric oxide (Fe 2 O 3 ) and niobium oxide (Nb 2 O 5 ) as raw materials, Li 2 O 35.1%, Fe 2 O 3 32.2%, P 2 O 5 32.2%, Nb 2 O 5 0.5% For 1 hour in the atmosphere. Thereafter, molten glass was poured into a pair of rolls and formed into a film shape while rapidly cooling to produce crystalline glass.
  • LiPO 3 lithium metaphosphate
  • Li 2 CO 3 lithium carbonate
  • Fe 2 O 3 ferric oxide
  • Nb 2 O 5 niobium oxide
  • the obtained crystalline glass was crystallized by heat treatment at 800 ° C. for 30 minutes, followed by ball milling using Al 2 O 3 boulder with ⁇ 20 mm for 5 hours, and then in ethanol using ZrO 2 boulder with ⁇ 5 mm. Was milled for 40 hours, and bead milling in ethanol using ZrO 2 beads having a diameter of 0.3 mm for 8 hours to obtain crystallized glass powder (inorganic powder) having an average particle size of 0.4 ⁇ m.
  • the specific surface area was measured by the BET method.
  • the carbon content is 20 according to JIS K 0102 “Factory drainage test method”. “Calculated by the following method in accordance with the oxygen consumption (COD Cr ) by potassium dichromate. That is, after adding excessive potassium dichromate to the positive electrode material to completely convert the carbon component to CO 2 , The amount of oxygen consumed was calculated by back titrating potassium chromate, and the carbon content was calculated from the amount of oxygen consumed.
  • binder: conductive substance 80: 10: 10 (mass ratio).
  • a rotation / revolution mixer After being dispersed in methyl pyrrolidone, it was sufficiently agitated with a rotation / revolution mixer to form a slurry.
  • the obtained slurry was coated on a 20 ⁇ m thick aluminum foil as a positive electrode current collector, dried at 70 ° C. in a dryer, and then between a pair of rotating rollers
  • the electrode sheet was obtained by pressing at 1 t / cm 2 .
  • the electrode sheet was punched to a diameter of 11 mm with an electrode punching machine and dried at 170 ° C. for 10 hours to obtain a circular working electrode.
  • the working electrode obtained on the lower lid of the coin cell was placed with the aluminum foil side facing down, and then dried on it at 60 ° C. for 8 hours under reduced pressure, and a polypropylene porous membrane having a diameter of 16 mm (manufactured by Hoechst Celanese) A separator made of Cellguard # 2400) and metallic lithium as a counter electrode were laminated to prepare a test battery.
  • a polypropylene porous membrane having a diameter of 16 mm manufactured by Hoechst Celanese
  • a separator made of Cellguard # 2400 A separator made of Cellguard # 2400
  • metallic lithium as a counter electrode were laminated to prepare a test battery.
  • the test battery was assembled in an environment with a dew point temperature of ⁇ 60 ° C. or lower.
  • a charge / discharge test was performed using the test battery, and the discharge capacity and average output voltage at 0.1 C and 1 C rates were measured.
  • the charge / discharge test was performed as follows. Charging (release of lithium ions from the positive electrode material) was performed by CC (constant current) charging from 2V to 4.2V. The discharge (occlusion of lithium ions into the positive electrode material) was performed by discharging from 4.2V to 2V.
  • Example 2 (1) Preparation of inorganic powders In mol%, the composition of Li 2 O 33.2%, Fe 2 O 3 33.2%, P 2 O 5 33.2%, Nb 2 O 5 0.4% is obtained. A crystallized glass powder (inorganic powder) having an average particle size of 0.4 ⁇ m was prepared in the same manner as in Example 1 except that the raw material powder was prepared.
  • Example 2 Production of inorganic powder Crystalline glass was produced in the same manner as in Example 2. The obtained crystalline glass was subjected to ball milling using an Al 2 O 3 boulder with a diameter of 20 mm for 5 hours and then ball milling in ethanol using a ZrO 2 boulder with a diameter of 5 mm for an average particle diameter of 2 ⁇ m. Crystalline glass powder (inorganic powder) was obtained.
  • Comparative Example 3 (1) Production of inorganic powder In the same manner as in Comparative Example 2, a crystalline glass powder (inorganic powder) having an average particle diameter of 2 ⁇ m was produced.
  • the positive electrode materials of Examples 1 and 2 have a high discharge capacity and a small decrease in the average output voltage in the case of the 1C rate with a large current during discharge.
  • the positive electrode materials of Comparative Examples 1 to 3 have a low discharge capacity and a large decrease in average output voltage in the case of the 1C rate as compared with the Examples.
  • Example 3 15 parts by mass of polyoxyethylene nonylphenyl ether (HLB value: 5.7 weight average molecular weight: 308) (corresponding to 10 parts by mass in terms of graphite) with respect to 100 parts by mass of the crystallized glass powder obtained in Example 1
  • a positive electrode material in which a carbon-containing layer was formed on the surface of the crystallized glass powder was obtained in the same manner as in Example 1 except that 37 parts by mass of pure water was mixed.
  • a powder X-ray diffraction pattern was confirmed, a diffraction line derived from LiFePO 4 was confirmed.
  • the discharge capacity and average output voltage at 0.1 C and 1 C rates were measured in the same manner as in Example 1.
  • peak intensity ratios D / G and F / G and electron conductivity in the Raman spectrum were measured. The results are shown in Table 2.
  • RAMASCOPE made by Renishaw, which is a Raman spectrometer
  • the resulting chart subjected to baseline correction for the peak intensity of 900 ⁇ 1000 cm -1 to peak intensity of F, 1300 ⁇ 1400 cm -1 and the peak intensity of D, 1550 ⁇ 1650 cm -1 as G, calculate each peak intensity
  • the peak intensity ratios D / G and F / G were obtained.
  • the electron conductivity is obtained by putting a positive electrode material powder into a mold and pressurizing it to produce a green compact, and measuring the DC electric resistance at both ends of the green compact using a digital multimeter. Asked.
  • Example 4 With respect to 100 parts by mass of the crystallized glass powder obtained in Example 1, 17.5 parts by mass of polyoxyethylene nonylphenyl ether (HLB value: 13.3 weight average molecular weight: 660) (to 10 parts by mass in terms of graphite) Correspondingly, except that it was used, a positive electrode material in which a carbon-containing layer was formed on the surface of the crystallized glass powder was obtained in the same manner as in Example 3. When a powder X-ray diffraction pattern was confirmed, a diffraction line derived from LiFePO 4 was confirmed.
  • HLB value 13.3 weight average molecular weight: 660
  • Example 2 For the obtained positive electrode material, the discharge capacity and average output voltage at 0.1 C and 1 C rates were measured in the same manner as in Example 1. Further, the peak intensity ratios D / G and F / G and the electron conductivity in the Raman spectrum were measured in the same manner as in Example 3. The results are shown in Table 2.
  • Example 5 19 parts by mass of polyoxyethylene nonylphenyl ether (HLB value: 17.7 weight average molecular weight: 1541) with respect to 100 parts by mass of the crystallized glass powder obtained in Example 1 (corresponding to 10 parts by mass in terms of graphite)
  • HLB value 17.7 weight average molecular weight: 1541
  • a positive electrode material in which a carbon-containing layer was formed on the surface of crystallized glass powder was obtained in the same manner as Example 3 except that it was used.
  • a powder X-ray diffraction pattern was confirmed, a diffraction line derived from LiFePO 4 was confirmed.
  • Example 2 For the obtained positive electrode material, the discharge capacity and average output voltage at 0.1 C and 1 C rates were measured in the same manner as in Example 1. Further, the peak intensity ratios D / G and F / G and the electron conductivity in the Raman spectrum were measured in the same manner as in Example 3. The results are shown in Table 2.
  • Example 6 16.9 parts by mass of polyoxyethylene styrenated phenyl ether (HLB value: 12.7 weight average molecular weight: 856) (10 parts by mass in terms of graphite) with respect to 100 parts by mass of the crystallized glass powder obtained in Example 1
  • HLB value 12.7 weight average molecular weight: 856
  • graphite graphite
  • Example 2 For the obtained positive electrode material, the discharge capacity and average output voltage at 0.1 C and 1 C rates were measured in the same manner as in Example 1. Further, the peak intensity ratios D / G and F / G and the electron conductivity in the Raman spectrum were measured in the same manner as in Example 3. The results are shown in Table 2.
  • Example 7 18.7 parts by mass (corresponding to 10 parts by mass of graphite) of polyoxyethylene nonyl ether (HLB value: 15 weight average molecular weight: 585) is used with respect to 100 parts by mass of the crystallized glass powder obtained in Example 1.
  • a positive electrode material in which a carbon-containing layer was formed on the surface of crystallized glass powder was obtained in the same manner as in Example 3 except that. When a powder X-ray diffraction pattern was confirmed, a diffraction line derived from LiFePO 4 was confirmed.
  • Example 2 For the obtained positive electrode material, the discharge capacity and average output voltage at 0.1 C and 1 C rates were measured in the same manner as in Example 1. Further, the peak intensity ratios D / G and F / G and the electron conductivity in the Raman spectrum were measured in the same manner as in Example 3. The results are shown in Table 2.
  • Example 8 18.3 parts by mass of polyoxyethylene 2-ethylhexyl ether (HLB value: 13.4 weight average molecular weight: 395) (10 parts by mass in terms of graphite) with respect to 100 parts by mass of the crystallized glass powder obtained in Example 1
  • HLB value 13.4 weight average molecular weight: 395
  • a positive electrode material in which a carbon-containing layer was formed on the surface of the crystallized glass powder was obtained in the same manner as in Example 3 except that it was used.
  • a powder X-ray diffraction pattern was confirmed, a diffraction line derived from LiFePO 4 was confirmed.
  • Example 2 For the obtained positive electrode material, the discharge capacity and average output voltage at 0.1 C and 1 C rates were measured in the same manner as in Example 1. Further, the peak intensity ratios D / G and F / G and the electron conductivity in the Raman spectrum were measured in the same manner as in Example 3. The results are shown in Table 2.
  • the positive electrode materials of Examples 3 to 6 using a surfactant having a benzene ring in the molecular structure as a carbon source do not have a benzene ring in the molecular structure as a carbon source. It can be seen that the peak intensity ratios D / G and F / G in the Raman spectrum are small and the proportion of the crystalline carbon-containing layer is large as compared with the positive electrode materials of Examples 7 and 8 using the surfactant. As a result, the positive electrode materials of Examples 3 to 6 had higher electron conductivity than the positive electrode materials of Examples 7 and 8.
  • the lithium ion secondary battery positive electrode material produced by the production method of the present invention is suitable for portable electronic devices such as notebook computers and mobile phones, and electric vehicles.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention porte sur un procédé de production de matière d'électrode positive de batterie secondaire au lithium-ion, qui est caractérisé en ce qu'il comprend (1) une étape dans laquelle un mélange est obtenu par mélange d'un agent tensioactif et d'une poudre inorganique contenant Li, Fe, P et O et ayant un diamètre moyen de particule de 1,8 µm ou moins, et (2) une étape dans laquelle, par traitement thermique du mélange susmentionné, des cristaux de type olivine représentés par la formule générale LiMxFe1-xPO4 (0 ≦ x ≦ 1, M est au moins un élément choisi parmi Nb, Ti, V, Cr, Mn, Co et Ni) sont précipités dans la poudre inorganique et une couche à teneur en carbone est formée sur la surface de poudre inorganique.
PCT/JP2012/072865 2011-09-08 2012-09-07 Procédé de production de matière d'électrode positive de batterie secondaire au lithium-ion WO2013035831A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10056615B2 (en) 2013-09-20 2018-08-21 Kabushiki Kaisha Toshiba Active substance, nonaqueous electrolyte battery, and battery pack

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6547891B1 (ja) * 2018-09-27 2019-07-24 住友大阪セメント株式会社 電極材料、該電極材料の製造方法、電極、及びリチウムイオン電池
JP6593510B1 (ja) * 2018-09-27 2019-10-23 住友大阪セメント株式会社 電極材料、該電極材料の製造方法、電極、及びリチウムイオン電池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004079276A (ja) * 2002-08-13 2004-03-11 Sony Corp 正極活物質及びその製造方法
JP2005050556A (ja) * 2003-07-29 2005-02-24 Mitsubishi Chemicals Corp リチウム二次電池用正極材料、リチウム二次電池用正極及びリチウム二次電池
JP2011001242A (ja) * 2009-06-22 2011-01-06 Asahi Glass Co Ltd リン酸鉄リチウム粒子の製造方法とリン酸鉄リチウム粒子
JP2011108440A (ja) * 2009-11-16 2011-06-02 Nippon Electric Glass Co Ltd リチウムイオン二次電池正極材料の製造方法
JP2011238594A (ja) * 2010-04-13 2011-11-24 Nippon Electric Glass Co Ltd リチウムイオン二次電池正極材料およびその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004079276A (ja) * 2002-08-13 2004-03-11 Sony Corp 正極活物質及びその製造方法
JP2005050556A (ja) * 2003-07-29 2005-02-24 Mitsubishi Chemicals Corp リチウム二次電池用正極材料、リチウム二次電池用正極及びリチウム二次電池
JP2011001242A (ja) * 2009-06-22 2011-01-06 Asahi Glass Co Ltd リン酸鉄リチウム粒子の製造方法とリン酸鉄リチウム粒子
JP2011108440A (ja) * 2009-11-16 2011-06-02 Nippon Electric Glass Co Ltd リチウムイオン二次電池正極材料の製造方法
JP2011238594A (ja) * 2010-04-13 2011-11-24 Nippon Electric Glass Co Ltd リチウムイオン二次電池正極材料およびその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10056615B2 (en) 2013-09-20 2018-08-21 Kabushiki Kaisha Toshiba Active substance, nonaqueous electrolyte battery, and battery pack

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