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WO2014034775A1 - Procédé de production de poudre de particules de phosphate de fer et manganèse lithié et de fibres de carbone, poudre de particules de phosphate de fer et manganèse lithié et de fibres de carbone, et batterie secondaire à électrolyte non aqueux utilisant la poudre de particules de phosphate de fer et manganèse lithié et de fibres de carbone - Google Patents

Procédé de production de poudre de particules de phosphate de fer et manganèse lithié et de fibres de carbone, poudre de particules de phosphate de fer et manganèse lithié et de fibres de carbone, et batterie secondaire à électrolyte non aqueux utilisant la poudre de particules de phosphate de fer et manganèse lithié et de fibres de carbone Download PDF

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Publication number
WO2014034775A1
WO2014034775A1 PCT/JP2013/073132 JP2013073132W WO2014034775A1 WO 2014034775 A1 WO2014034775 A1 WO 2014034775A1 JP 2013073132 W JP2013073132 W JP 2013073132W WO 2014034775 A1 WO2014034775 A1 WO 2014034775A1
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Prior art keywords
carbon composite
composite lithium
lithium manganese
iron phosphate
particle powder
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PCT/JP2013/073132
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English (en)
Japanese (ja)
Inventor
祐司 三島
尊久 西尾
琢磨 北條
貞村　英昭
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Toda Kogyo Corp
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Toda Kogyo Corp
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Priority to JP2014533075A priority Critical patent/JP6260535B2/ja
Publication of WO2014034775A1 publication Critical patent/WO2014034775A1/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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 is a carbon composite that is excellent in low-temperature current load characteristics and excellent in high-temperature repeatability.
  • lithium iron manganese phosphate particles Provided are lithium iron manganese phosphate particles and a secondary battery using the same.
  • LiMnPO 4 of 4.1 V class has attracted attention as a positive electrode active material useful for a high energy density type lithium ion secondary battery.
  • LiMnPO 4 is less liable to enter and exit Li than LiFePO 4 , it is required to improve the charge / discharge characteristics and the repetition characteristics thereof.
  • LiMnPO 4 having an olivine structure is composed of a strong phosphoric acid tetrahedral skeleton, an oxygen octahedron centered on manganese ions that contribute to redox, and lithium ions that are current carriers.
  • it is preferable to coat the particle surface of the positive electrode active material with carbon.
  • it functions as an electrode of a secondary battery, and at the time of charge / discharge using Li as a negative electrode, it is said that the following two-phase reaction is followed due to the presence of a plateau region in charge / discharge characteristics indicated by capacity and voltage.
  • LiMn 1-x Fe x PO 4 having an olivine structure the charge / discharge characteristics at low current are better as the particle surface is covered with carbon. Moreover, the charge / discharge characteristics under a high current load tended to be better as the fine particles having a crystallite size of less than 100 nm were satisfied. Moreover, in order to obtain a high molded body density as an electrode, each aggregate is formed so that they form a network with appropriately aggregated secondary particles and a conductive auxiliary agent such as carbon having a high graphitization rate. The state needs to be controlled. However, the positive electrode combined with a large amount of carbon is bulky, and there is a disadvantage that the substantial lithium ion density that can be filled per unit volume is lowered.
  • LiMn 1-x Fe x PO 4 that is fine and moderately coated with carbon is obtained, and a high density is obtained through a small amount of conductive auxiliary agent. There is a need to form aggregates.
  • LiMnPO 4 particles and carbon are mechanically mixed
  • a mechanochemical method in which LiMnPO 4 particles and carbon are mechanically mixed is generally known as a means for compounding LiMnPO 4 particles and carbon to increase the capacity.
  • LiMn 1-x Fe x PO 4 has a catalytic effect of Fe, and carbon is deposited on the particle surface by a reaction in an inert gas of an organic substance, thereby improving its electric resistance.
  • the degree of carbon coating is insufficient compared to LiFePO 4 , and further surface modification of the particles is required (Non-Patent Documents 1 to 7).
  • Patent Document 1 a technique for obtaining a high capacity by compounding with carbon having a high specific surface area
  • Patent Document 2 a technique for adding different metal elements to reduce electric resistance
  • Patent Document 3 a technique for synthesizing by a hydrothermal method, a sol-gel method
  • the most demanding method for producing particle powder at low cost and low environmental load is currently in demand, but has not yet been established.
  • LiMn 1-x Fe x PO 4 (0.02 ⁇ x ⁇ 0) having low electric resistance, high filling property, and excellent charge / discharge repetition characteristics. .5) Particle powder cannot be obtained industrially.
  • Patent Document 1 is a technique for improving the capacity when LiMn 1-x Fe x PO 4 particle powder is used as a positive electrode, and it touches on the filling property to the electrode and the control of the secondary aggregate state. Absent.
  • Patent Document 2 The technique described in Patent Document 2 is not a technique for obtaining high electronic conductivity by combining LiMnPO 4 particle powder and carbon, and it is difficult to say that a high-capacity positive electrode active material can be obtained.
  • Patent Document 3 The technique described in Patent Document 3 is a production method using a solid-phase reaction method, and since it has two heat treatments, it is difficult to say that the cost is low.
  • Patent Document 6 the main component adjustment method of Li, Mn, Fe, and P described in Patent Document 6 requires fine pulverization and high dispersion to nano-size with an apparatus such as a ball mill in order to mix adjustment additives in a dry manner. From the viewpoint of mass productivity, it was difficult to say that it was industrial.
  • the present invention improves the crystallinity and surface properties of the positive electrode active material obtained after firing by optimizing the adjustment method of the main component composition ratio before firing, and has low electrical resistance and high fillability.
  • Another object of the present invention is to provide a carbon composite lithium manganese iron phosphate particle powder that is excellent in repetitive characteristics of charge and discharge at a high temperature and a secondary battery using the same.
  • the carbon composite lithium manganese phosphate particle powder which consists of the 3rd process of baking the precursor mixed powder obtained by the 2nd process
  • the aqueous suspension or water-containing product in the first step is 0.98 ⁇ Li / (Mn + Fe) ⁇ 1.20, 0.98 ⁇ P / (Mn + Fe) ⁇ 1.20 in terms of mol ratio.
  • the present invention provides a carbon composite lithium manganese iron phosphate particle powder in which the organic substance is a water-soluble organic substance in the first step of the method for producing the carbon composite lithium iron manganese phosphate particle powder described in the present invention 1.
  • This is a manufacturing method (Invention 2).
  • the present invention provides a polyhydric alcohol, a sugar, or an organic substance in which the organic substance contains a hydroxy group (—OH) or a carboxyl group (—COOH). It is a manufacturing method of this invention 1 or 2 which is the organic substance which belongs to an acid (this invention 3).
  • the present invention is the production method according to any one of the present inventions 1 to 3, wherein the drying temperature in the second step of the method for producing the carbon composite lithium manganese iron phosphate particle powder is 40 ° C. to 250 ° C. ( Invention 4).
  • the present invention is a carbon composite lithium manganese iron phosphate particle powder obtained by the production method described in any of the present inventions 1 to 4 (Invention 5).
  • the present invention is a non-aqueous electrolyte secondary battery produced using the carbon composite lithium manganese iron phosphate particle powder described in the present invention 5 (Invention 6).
  • the method for producing carbon composite lithium manganese phosphate particles according to the present invention is low in cost and can be produced with a small environmental load, and the powder obtained by the method has low electrical resistance and high filling properties.
  • a secondary battery using it as a positive electrode active material has a high capacity in current load characteristics at low temperatures, and sufficiently withstands repeated charge and discharge even at high temperatures. Therefore, the carbon composite lithium manganese iron phosphate particles according to the present invention are suitable as a positive electrode active material for a non-aqueous electrolyte secondary battery.
  • Example 2 is a high-magnification secondary electron image of the carbon composite lithium iron manganese phosphate particles obtained in Example 1 with a scanning electron microscope.
  • 2 is a low-magnification secondary electron image of the carbon composite lithium iron manganese phosphate particles obtained in Example 1 with a scanning electron microscope.
  • the carbon composite lithium manganese iron phosphate particle powder obtained in Example 1 is made positive, and the discharge capacity evaluated at 25 ° C. and 0 ° C. using a coin cell is dependent on the current load. It is the electric current load dependence of the discharge curve which made the carbon composite lithium manganese iron phosphate particle powder obtained in Example 1 positive electrode and evaluated at 0 ° C. using a coin cell.
  • the carbon composite lithium iron manganese phosphate particles according to the present invention are produced based on lithium iron manganese phosphate obtained by hydrothermal treatment.
  • Hydrothermal treatment is a method of synthesizing a compound under high temperature and high pressure by mixing aqueous solutions of raw material compounds.
  • the method for obtaining lithium iron manganese phosphate by hydrothermal treatment is not limited, but the following method is preferably used in order to obtain fine lithium iron manganese phosphate with a high production rate.
  • the product obtained by the hydrothermal treatment is a fine Li 1- ⁇ Mn 1-x Fe x P 1- ⁇ O 4- ⁇ (0.02 ⁇ x ⁇ 0.5, 0 ⁇ ⁇ ) with a crystallite size of 200 nm or less. , ⁇ ⁇ 0.2).
  • ⁇ , ⁇ , and ⁇ are crystallographic parameters, and ⁇ and ⁇ did not exceed 0.2.
  • ⁇ is a parameter added to satisfy the electrical neutral condition.
  • Li source LiOH.H 2 O, Li 2 CO 3 , Mn raw material, MnSO 4 .H 2 O, MnCO 3 , Fe raw material, FeSO 4 .nH 2 O, FeCO 3 , P raw materials include H 3 PO 4 , (NH 4 ) H 2 PO 4 , (NH 4 ) 2 HPO 4 , (NH 4 ) 3 PO 4 and the like.
  • the raw material fine particles it is preferable to make the raw material fine particles so that the raw material mixing and dissolution / precipitation reaction can be performed quickly under the condition that many crystal nuclei of lithium iron manganese phosphate are generated.
  • a medium such as a ZrO 2 ball
  • the apparatus used for pulverization include a ball mill and a medium stirring mill
  • the high concentration raw material mixing apparatus include a roller and a kneader.
  • an organic acid such as ascorbic acid or citric acid or a reducing sugar such as glucose may be used.
  • the amount is preferably 1 to 20 mol% with respect to (Mn + Fe), and Li 1 ⁇ Mn 1 ⁇ x Fe x P 1 ⁇ O 4 ⁇ (0.02 ⁇ x ⁇ 0.5) after hydrothermal treatment. , 0 ⁇ ⁇ , ⁇ ⁇ 0.2), and the primary particle size of the product tends to be refined.
  • LiOH, NH 3 , NaOH, Na 2 CO 3 , NH 3 , urea, ethanolamine, or the like can be used as an alkali source during hydrothermal treatment.
  • the pH needs to be 5.5 to 12.5.
  • reaction rate and particle size of lithium iron manganese phosphate tend to increase, but it is preferable to react at 90 to 300 ° C. for 2 to 3 hours.
  • the reaction rate of lithium iron manganese phosphate after the hydrothermal treatment obtained by this method exceeds 80 wt%.
  • the product may be subjected to filtration washing or decantation washing for removal of impurity sulfate ions or ammonium ions and adjustment of the Li, Mn, Fe, and P composition ratios.
  • the apparatus include a press filter and a filter thickener.
  • the first step of the present invention is to obtain an aqueous suspension or hydrate containing an olivine-type lithium iron manganese phosphate, a lithium compound and / or a phosphorus compound, and an organic substance produced by hydrothermal treatment.
  • An aqueous slurry of lithium manganese iron phosphate obtained by hydrothermal treatment as a method of obtaining an aqueous suspension or hydrate containing lithium manganese iron phosphate and lithium compound and / or phosphorus compound and organic matter produced by hydrothermal treatment
  • Lithium manganese iron phosphate produced by hydrothermal treatment has many defects in the crystal. Therefore, in order to form a desired lithium manganese iron phosphate solid solution with few defects, it is necessary to adjust the main component composition ratio before firing. That is, the main component composition ratio is 0.98 ⁇ Li / (Mn + Fe) ⁇ 1.15, 0.98 ⁇ P / (Mn + Fe) ⁇ 1 with respect to lithium iron manganese phosphate obtained by hydrothermal treatment. .15, P ⁇ Li needs to be adjusted by adding a lithium compound and / or a phosphorus compound. Except for a predetermined composition ratio, an impurity phase is excessively generated, which causes deterioration of battery characteristics.
  • LiOH Li 2 CO 3 or the like
  • LiOH LiOH, Li 2 CO 3 or the like
  • H 3 PO 4 As the phosphorus compound used for adjusting the main component composition ratio in the present invention, H 3 PO 4 , (NH 4 ) H 2 PO 4 , (NH 4 ) 2 HPO 4 , (NH 4 ) 3 PO 4, or the like is used. Can do.
  • a compound containing lithium and phosphorus it can be used LiH 2 PO 4, Li 3 PO 4, LiPO 3 , and the like.
  • a lithium compound, a phosphorus compound, a compound containing lithium and phosphorus may be used in combination.
  • 60 wt% or more of the lithium compound and / or phosphorus compound added to adjust the composition ratio is Li 1-y H 2 + y PO 4 (0 ⁇ y ⁇ 1).
  • the carbon composite lithium manganese phosphate obtained after firing has a lattice of sites unique to each element. Defects are almost reduced, and a high-performance positive electrode active material can be obtained by increasing crystallinity.
  • 75 wt% or more is used with respect to the lithium compound and / or the phosphorus compound to which Li 1-y H 2 + y PO 4 is added.
  • LiH 2 PO 4 is preferably used at 60 wt% or more, more preferably 75 wt% or more.
  • the amount of LiH 2 PO 4 used is less than 60 wt%, the adjustment of the main component composition ratio is not uniform at the individual particle level, and coarse Li 3 PO 4 and Li 4 P 2 O 4 are produced excessively, It becomes a factor which deteriorates battery characteristics.
  • Li 3 PO 4 is preferably used because it easily forms water-insoluble fine particles of 50 nm or less and can be easily and uniformly mixed with lithium iron manganese phosphate before firing.
  • the aqueous suspension or hydrated product obtained in the first step needs to contain 1 to 20 wt% of organic matter relative to lithium iron manganese phosphate obtained by hydrothermal treatment.
  • the amount of the organic substance is preferably 5 to 15 wt%.
  • the amount of the organic substance added is too small, the amount of residual carbon after firing is small, and the composite of lithium iron manganese phosphate and carbon by firing is insufficient.
  • alpha-Fe impurity phase when the addition amount of the organic material is too large, (Mn + Fe) 2 P , (Mn + Fe) 3 P product is promoted, and is a cause of deteriorating the battery characteristics.
  • a water-soluble or water-dispersible organic substance can be used, and it is particularly preferable to use a water-soluble organic substance for uniform improvement of the lithium manganese iron phosphate particle surface. Both water-soluble organic substances and water-dispersible organic substances may be used.
  • the water-soluble organic substance is preferably a water-soluble organic substance belonging to a polyhydric alcohol, sugar, or organic acid containing a hydroxy group (—OH) or a carboxyl group (—COOH), specifically, polyvinyl alcohol (PVA). Sucrose, citric acid, ethylene glycol and the like.
  • water-dispersible organic substances include hydrophilized synthetic fibers and carbon black, such as polyethylene particles, acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) and ketjen black (manufactured by Lion Co., Ltd.).
  • hydrophilized synthetic fibers and carbon black such as polyethylene particles, acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) and ketjen black (manufactured by Lion Co., Ltd.).
  • an alkaline solution such as PVA having a hydrophilic group and a hydrophobic group, a nonionic surfactant (for example, polyoxyethylene ether), or LiOH.
  • lithium iron phosphate with an olivine structure produced by hydrothermal treatment and a lithium compound for adjusting the main component composition ratio and / or a phosphorus compound and an organic substance are mixed in the presence of water. Uniform mixing is achieved. As a result, the particle surface of lithium iron manganese phosphate is improved, and an olivine-type lithium iron manganese phosphate particle powder having high battery characteristics can be obtained by an industrial manufacturing method with a low environmental load. is there.
  • the lithium compound and / or phosphorus compound for adjusting the main component composition ratio is Li 1-y H 2 + y PO 4 (0 ⁇ y ⁇ 1), and water is added as an organic substance to be added.
  • soluble organic matter in order to cause a phosphate ester reaction and a polymerization reaction by dehydration by heating when drying and obtaining a precursor powder for firing in the second step, together with carbon obtained by firing, It is believed that the Li-P amorphous phase improves the surface of lithium manganese iron phosphate particles.
  • the present invention dries the aqueous suspension or hydrate of lithium manganese iron phosphate obtained in the first step to obtain a precursor mixed powder for firing.
  • the drying temperature is preferably 40 to 250 ° C.
  • a method for drying an aqueous suspension or a hydrated product an aqueous slurry is mixed with a disper or the like and dried with a normal dryer, a method with a spray dryer or a slurry dryer, an aqueous cake or a dry powder with water. Examples include a method of kneading the hydrated product added with a roller and a kneader and drying with a normal dryer.
  • Li 1-y H 2 + y PO 4 used for adjusting the main component composition ratio is acidic, so that drying in a short time is desirable so as not to damage lithium iron manganese phosphate particles after hydrothermal treatment. (E.g., within 1 hour for a 500 g slurry).
  • the aggregate particle size of the carbon composite lithium manganese iron phosphate particles according to the present invention there is almost no change in the aggregate particle size before and after firing. Therefore, it is necessary to adjust the aggregate particle diameter between the first step and the second step or after the third step.
  • the adjustment of the aggregate particle diameter can be controlled by the mixing / drying method, classification / pulverization in each step. Examples of the pulverizing apparatus include a high-speed impact pulverizer and an agate mortar.
  • the precursor powder mixture for firing obtained in the second step is fired at a temperature of 250 to 850 ° C. in an inert gas or reducing gas atmosphere having an oxygen concentration of 0.1% or less.
  • an apparatus for performing firing there are a gas flow type box muffle furnace, a gas flow type rotary furnace, a fluidized heat treatment furnace, and the like.
  • the inert gas N 2 , Ar, H 2 O, CO 2 or a mixed gas thereof is used.
  • As the reducing gas, H 2 , CO, or a mixed gas of these gases and the inert gas is used.
  • a trace amount of Fe 3+ contained in the Fe raw material is changed to Fe 2+ by an organic substance or a reducing gas to generate lithium iron manganese phosphate, and therefore a precursor for firing in an atmosphere having an oxygen concentration of 0.1% or less. It is necessary to fire the mixed powder.
  • the carbon composite lithium manganese iron phosphate particles according to the present invention each have a lithium and phosphorus content of 0.98 to 1.15 in terms of a molar ratio to the transition metal, and the lithium content is not less than phosphorus. .
  • the lithium and phosphorus contents are 1.01 to 1.10, respectively, in molar ratio to the transition metal, and the lithium content is not less than phosphorus.
  • the BET specific surface area of the carbon composite lithium iron manganese phosphate particles according to the present invention is preferably 6 to 70 m 2 / g.
  • the BET specific surface area value is less than 6 m 2 / g, the lithium iron manganese phosphate particles are large particles, and the movement of Li ions in the crystal is slow, so that it is difficult to extract current.
  • the BET specific surface area value is less than 6 m 2 / g, the lithium iron manganese phosphate particles are large particles, and the movement of Li ions in the crystal is slow, so that it is difficult to extract current.
  • 70 m ⁇ 2 > / g since the fall with the packing density of a positive electrode and the reactivity with electrolyte solution increase, it is unpreferable. More preferably, it is 8 to 28 m 2 / g, and even more preferably 9 to 20 m 2 / g.
  • the carbon content of the carbon composite lithium manganese phosphate particles according to the present invention is preferably 0.7 to 8.0 wt%.
  • the carbon content is less than 0.7 wt%, the electric resistance of the obtained powder becomes high, and the charge / discharge characteristics of the secondary battery are deteriorated.
  • the content exceeds 8.0 wt%, the positive electrode filling density decreases, and the energy density per volume of the secondary battery decreases. More preferably, it is 1.0 to 4.0 wt%.
  • the carbon composite lithium manganese iron phosphate particle powder according to the present invention has an impurity sulfur content of 0.08 wt% or less, and good storage characteristics can be obtained in a non-aqueous electrolyte secondary battery.
  • impurities such as lithium sulfate are formed, and these impurities cause a decomposition reaction during charge and discharge, and the resistance increase during high temperature cycle characteristics becomes severe. More preferably, it is 0.05 wt% or less.
  • the crystallite size of the carbon composite lithium manganese phosphate particles according to the present invention is preferably 25 to 300 nm. It is extremely difficult to mass-produce a powder having a crystallite size of less than 25 nm while satisfying other powder characteristics by the production method of the present invention, and Li moves inside the particle at a crystallite size exceeding 300 nm. Time is required, and as a result, the current load characteristic of the secondary battery is deteriorated. More preferably, it is 30 to 200 nm, and still more preferably 40 to 150 nm.
  • the agglomerated particle size of the carbon composite lithium manganese phosphate particles according to the present invention is preferably 0.3 to 30 ⁇ m.
  • the aggregated particle diameter is less than 0.3 ⁇ m, it is not preferable because the positive electrode packing density decreases and the reactivity with the electrolyte increases.
  • the aggregated particle diameter exceeds 30 ⁇ m, the electrode film thickness becomes closer, and there are cases where only a few particles are placed in the film thickness direction of the electrode, making sheeting extremely difficult. More preferably, it is 0.5 to 25 ⁇ m, and even more preferably 1.0 to 20 ⁇ m.
  • the compression-molded body density of the carbon composite lithium manganese phosphate particles according to the present invention is preferably 1.8 g / cc or more.
  • the closer to the true density, the better the packing property, and the true density of the layered compound LiCoO 2 often used as the positive electrode active material of the secondary battery is 5.1 g / cc, whereas the true density of lithium iron manganese phosphate is The density is as low as 3.5 g / cc. Therefore, a preferable compression molding density is 2.0 g / cc or more exceeding 50% of the true density.
  • the electric resistivity of the compression-molded body of carbon composite lithium iron manganese phosphate particles according to the present invention is preferably 1.0 ⁇ 10 3 ⁇ ⁇ cm or less. If the electrical resistivity is low, the amount of the conductive material added when producing the positive electrode sheet can be reduced, and a positive electrode sheet having a high density can be obtained.
  • a conductive agent and a binder are added and mixed according to a conventional method.
  • the conductive agent carbon black, graphite and the like are preferable, and as the binder, polytetrafluoroethylene, polyvinylidene fluoride and the like are preferable.
  • the solvent for example, N-methyl-pyrrolidone is used, and the positive electrode active material sieved to 75 ⁇ m or less and the slurry containing the additive are kneaded until they become honey. The obtained slurry is applied onto the current collector with a doctor blade having a groove of 25 to 500 ⁇ m.
  • the coating speed is about 60 cm / sec, and an Al foil of about 20 ⁇ m is usually used as a current collector. Drying is performed at 80 to 180 ° C. to remove the solvent and soften the binder.
  • the sheet is subjected to a calender roll treatment so as to have a pressure of 1 to 3 t / cm 2 . In the step of forming the sheet, an oxidation reaction of Fe 2+ to Fe 3+ occurs even at room temperature. Therefore, it is desirable to carry out in a non-oxidizing atmosphere as much as possible.
  • the density of the compression molded body of the positive electrode active material is as high as 1.8 g / cc or more, and the electrical resistivity of the compression molded body of the positive electrode active material is 0.1 to 10 4 ⁇ ⁇ cm. Therefore, the amount of carbon added during sheet preparation can be reduced, and since the BET specific surface area of the positive electrode active material is as low as 6 to 70 m 2 / g, the amount of binder added can be reduced, resulting in a high-density positive electrode. A sheet is obtained.
  • lithium metal lithium metal, lithium / aluminum alloy, lithium / tin alloy, graphite or the like can be used, and the negative electrode sheet is produced by the same doctor blade method or metal rolling as the positive electrode.
  • an organic solvent containing at least one of carbonates such as propylene carbonate and dimethyl carbonate and ethers such as dimethoxyethane can be used as the solvent for the electrolytic solution.
  • At least one lithium salt such as lithium perchlorate and lithium tetrafluoroborate can be dissolved in the above solvent and used.
  • the secondary battery manufactured using the positive electrode sheet of the present invention has a discharge capacity of 150 mAh / g or more at 0.1 C at 25 ° C., a discharge capacity at 1 C of room temperature of 140 mAh / g or more, and a discharge capacity of 5 C at room temperature. It is a characteristic of 120 mAh / g or more.
  • 0.1 C is a current value fixed so that a current of 170 mAh / g in theoretical capacity of LiMn 1-x Fe x PO 4 (0.02 ⁇ x ⁇ 0.5) flows in 20 hours.
  • I is a current value fixed so that a current having a theoretical capacity of 170 mAh / g flows in 1 hour
  • 5C is a current value fixed so that a current having a theoretical capacity of 170 mAh / g flows in 1/5 hour.
  • a higher C coefficient means higher current load characteristics.
  • the secondary battery manufactured using the positive electrode sheet according to the present invention showed excellent characteristics in terms of current load characteristics at low temperatures and cycle characteristics at high temperatures, as shown in FIGS.
  • the carbon composite lithium manganese iron phosphate particles according to the present invention are produced by hydrothermal treatment and heat treatment, and can be produced at low cost and with low environmental load. According to the production method of the present invention, the obtained carbon composite lithium iron manganese phosphate particle powder is controlled in crystallinity, particle surface, and aggregated particle size, and therefore when used as a positive electrode active material for a secondary battery.
  • the present inventor presumes that a high capacity can be obtained even in current load characteristics at room temperature and low temperature, and that charging and discharging can be sufficiently repeated at high temperature.
  • a typical embodiment of the present invention is as follows.
  • the Li and P concentrations of the lithium and phosphorus-containing main raw materials were measured by neutralization titration using a pH meter and hydrochloric acid or NaOH reagent.
  • the Fe concentration of the iron raw material was quantified by titration (JIS K5109), and the Mn concentration of the manganese raw material was also quantified by titration (Analytical Chemistry Handbook, edited by the Japan Analytical Chemical Society). Based on these analysis results, the reaction concentration and the raw material charge ratio were determined. The weight ratio of the additive was calculated by the amount charged.
  • the reaction rate of the hydrothermal treatment was evaluated by thermal analysis using an atmospheric tubular furnace (HS10S-2050TF, manufactured by Heat System Co., Ltd.).
  • the dry powder of lithium iron manganese phosphate obtained by hydrothermal treatment was calculated from the ratio of weight loss before and after heat treatment at 700 ° C. for 2 hours in an inert gas atmosphere.
  • the X-ray diffractometer SmartLab [manufactured by Rigaku Corporation] was used to measure under the conditions of Cu-K ⁇ , 45 kV, 200 mA, and the Rietveld method was used. .
  • the X-ray diffraction pattern was measured in steps of 0.02 ° with a counting time of 3.0 seconds and 2 ⁇ in the range of 15-90 ° so that the count number of the maximum peak intensity was 8000-15000.
  • SRM674b of NIST National Institute of Standards and Technology
  • RIETA 2000 was used as a Rietveld analysis program.
  • the TCH pseudo-void function is used as the profile function
  • the method such as Finger is used for asymmetry of the function
  • the reliability factor S value is 2.0. Analyzed to cut. The same method was used to evaluate the lattice constant (unit cell volume) and crystallite size of the electrode active material.
  • the Li, Mn, Fe, and P main elements of lithium manganese iron phosphate in each step were measured by ICP measurement using an emission plasma analyzer ICAP-6500 [manufactured by Thermo Fisher Scientific Co., Ltd.].
  • the sample was dissolved in an acid solution at 200 ° C. using an autoclave.
  • the powder evaluation of the carbon composite lithium manganese iron phosphate particles obtained by the present invention was performed as follows.
  • MONOSORB [manufactured by Yuasa Ionics Co., Ltd.] was used for the BET specific surface area after the sample was dried and deaerated under nitrogen gas at 120 ° C. for 45 minutes.
  • Residual carbon and residual sulfur were quantified by burning them in an oxygen stream in a combustion furnace using EMIA-820 [manufactured by Horiba Ltd.].
  • the density of the compression-molded body was compacted to 1.5 t / cm 2 with a 13 mm ⁇ jig and calculated from the weight and volume.
  • the electrical resistivity of the compression molded body was measured by the two-terminal method.
  • Hitachi S-4300 scanning electron microscope (SEM) was used for shape observation of the carbon composite lithium manganese phosphate obtained by the present invention.
  • the carbon of the conductive auxiliary agent used is acetylene black.
  • the binder used was polyvinylidene fluoride (KF polymer manufactured by Kureha Co., Ltd.) having a polymerization degree of 630,000, and was dissolved in N-methylpyrrolidone (manufactured by Kanto Chemical Co., Inc.).
  • the dried sheet was pressurized to 3 t / cm 2 to prepare a positive electrode sheet having a thickness of about 30 to 40 ⁇ m.
  • a positive electrode sheet punched to 2 cm 2 , a 0.15 mm Li negative electrode punched to 17 mm ⁇ , a separator (Celguard # 2400) in 19 mm ⁇ , EC and DMC (ethylene carbonate: dimethyl carbonate 3: 7) in which 1 mol / l LiPF 6 was dissolved
  • a CR2032-type coin cell manufactured by Hosen Co., Ltd. was prepared using an electrolytic solution (manufactured by Kishida Chemical Co., Ltd.) mixed in a volume ratio.
  • the discharge capacity at constant current values of 0.1 C, 1 C, and 5 C at 25 ° C. was evaluated in a coin cell using a positive electrode sheet having an electrode composition ratio A.
  • the current load characteristics at 0 ° C. and 25 ° C. were evaluated in a coin cell using a positive electrode sheet having an electrode composition ratio B.
  • the current value during charging was a constant current value of 0.1 C, and discharging was performed at a constant current value corresponding to 0.1 to 5 C.
  • the charge / discharge curve / discharge capacity at 60 ° C. was evaluated in a coin cell using a positive electrode sheet having an electrode composition ratio B.
  • Charge with a constant current value corresponding to 0.2 C, 1, 2, 12,..., 10 ⁇ i + 2 (i 1 to 6) discharge at a constant current value corresponding to 0.2 C, others 1 C
  • the discharge capacity of each cycle when discharged at a constant current value corresponding to is measured.
  • the voltage range during charging and discharging was performed with a lower limit of 2.0 V, an upper limit of 4.5 V, a lower limit of 2.0 V, and an upper limit of 4.3 V.
  • An aqueous slurry adjusted to a raw material charge ratio of 8: 0.2: 1.05 was obtained.
  • the main crystal phase in the slurry was NH 4 MnPO 4 .
  • the slurry was mixed with a ball mill, and the aggregated particles were pulverized to adjust the particle size.
  • the cake obtained is peptized and a slurry is prepared. From the results of the reaction rate and the main component composition ratio, the lithium compound and / or phosphorus compound and organic matter are added and mixed so that the main component composition ratio shown in Table 1 is obtained. did. The main component composition ratio was confirmed by ICP measurement.
  • the addition amount of the organic substance in% by weight shown in Table 1 is a value with respect to the solid content obtained when the cake of lithium manganese iron phosphate obtained after the hydrothermal treatment is dried. (First step).
  • the obtained precursor mixed powder for firing was placed in an alumina crucible and subjected to heat treatment at 700 ° C. for 5 hours in a nitrogen atmosphere.
  • the temperature rising rate was 200 ° C./hr, and the N 2 gas flow rate was 1 L / min.
  • the obtained powder was fine, and was carbon composite lithium manganese iron phosphate particle powder. Further, as a result of ICP measurement, the composition ratio of Li, Mn, Fe, and P adjusted in the first step was not different. 1 and 2 show high and low magnification SEM photographs (secondary electron images) of the carbon composite lithium manganese iron phosphate particles obtained. It was found that the obtained powder was composed of primary particles of 100 nm or less and agglomerated particles of several tens ⁇ m in which the primary particles were aggregated.
  • Table 2 shows the powder characteristics obtained by making a positive electrode at the electrode composition ratio A and evaluated by the coin cell
  • FIGS. 3 to 6 show the battery characteristics at the electrode composition ratio B.
  • good results were obtained not only in the battery characteristics at 25 ° C. but also in the current load characteristics at 0 ° C. and the cycle characteristics at 60 ° C.
  • Table 1 shows the experimental conditions of the following examples and comparative examples
  • Table 2 shows the powder characteristics
  • Table 3 shows the battery characteristics.
  • Examples 2 and 3 The lithium compound and / or phosphorus compound described in Table 1 and the carbon source were changed in the subsequent steps for the hydrothermal treatment and the lithium iron manganese phosphate particle-containing cake obtained after washing with the same specifications as in Example 1. In the same manner as in Example 1, drying, pulverization / classification, baking, and pulverization / classification were performed to obtain lithium iron manganese phosphate particles. Tables 2 and 3 show the evaluation results.
  • Example 4 After drying the cake containing lithium manganese iron phosphate particles after hydrothermal treatment and washing with the same specifications as in Example 1, using the lithium compound and / or phosphorus compound and carbon source listed in Table 1, 7 .5 wt% water was added and mixed in a coffee mill. Subsequent treatment was performed by the method described in Example 1 to obtain lithium iron manganese phosphate particles. Tables 2 and 3 show the evaluation results.
  • a part of the sample after washing with water was taken out and dried at 105 ° C. overnight, and Li 1 - ⁇ Mn 0.85 Fe 0.15 P 1- ⁇ O 4- ⁇ was obtained by Rietveld analysis of the XRD diffraction pattern. It was found to contain (0 ⁇ ⁇ , ⁇ ⁇ 0.2) and 4.3 wt% of the impurity phase Li 3 PO 4 .
  • the lithium manganese phosphate particle-containing slurry obtained by peptizing the obtained cake was dried, pulverized and classified in the same manner as in Example 1 except that the lithium compound and / or phosphorus compound described in Table 1 and the carbon source were changed. Firing, pulverization and classification were performed to obtain lithium iron manganese phosphate particles. Tables 2 and 3 show the evaluation results.
  • the result was 3.0 wt% impurity phase Li 3 PO 4 and Li 1- ⁇ MnP 1- ⁇ in the Rietveld analysis of the XRD diffraction pattern. It was found that O 4- ⁇ (0 ⁇ ⁇ , ⁇ ⁇ 0.2).
  • the lithium manganese phosphate particle-containing slurry obtained by peptizing the obtained cake was dried, pulverized and classified in the same manner as in Example 1 except that the lithium compound and / or phosphorus compound described in Table 1 and the carbon source were changed. Firing, pulverization and classification were performed to obtain lithium iron manganese phosphate particles. Tables 2 and 3 show the evaluation results. In the coin cell using the electrode composition ratio B, a discharge capacity of 128 mAh / g (1C) was obtained at 0 ° C., and the capacity retention rate after 62 cycles at 60 ° C. was 98%.
  • the obtained powder was fine, the unit cell volume close to the formula (1) was obtained because LiMnPO 4 itself hardly forms a defect structure. On the other hand, the battery characteristics are very poor and the carbon coating seems to be insufficient. At the same time, since the amount of carbon was large and the aggregated particle size was small, the density of the compression molded product was lowered.
  • Example 4 except that the lithium compound and / or phosphorus compound and carbon source described in Table 1 were changed with respect to the cake containing lithium manganese iron phosphate particles after hydrothermal reaction and water washing obtained in the same specifications as in Example 1. Similarly, after drying the cake, the lithium compound and / or phosphorus compound, carbon source and water were mixed, re-dried, pulverized / classified, fired, and pulverized / classified to obtain lithium iron manganese phosphate particles. . Tables 2 and 3 show the evaluation results.
  • Example 1 except that the lithium compound and / or phosphorus compound and carbon source described in Table 1 were changed with respect to the cake containing lithium manganese iron phosphate particles after the hydrothermal reaction and water washing obtained in the same specifications as Example 1.
  • mixing, drying, pulverization / classification, firing, and pulverization / classification were performed to obtain lithium iron manganese phosphate particles.
  • Tables 2 and 3 show the evaluation results.
  • Comparative Examples 3 and 4 did not use Li 1-y H 2 + y PO 4 for adjusting the composition ratio, an undesirable impurity crystal phase was generated. As a result, it is surmised that the surface modification of the particles became insufficient and sufficient battery characteristics could not be obtained.
  • Example 5 The firing precursor mixed powder obtained in the second step in the same manner as in Example 1 is fired at 800 ° C., which is 100 ° C. higher than the other examples, pulverized and classified, and lithium manganese iron phosphate particles A powder was obtained. Tables 2 and 3 show the evaluation results.
  • the impurity phase Fe 2 P was detected from the lithium iron manganese phosphate obtained in Comparative Example 5, and the unit cell volume was large, probably because Fe was reduced from the olivine structure. In addition, it was difficult to say that the battery characteristics shown in Table 3 were good because the impurity phase suppressed the modification of the particle surface.
  • the method for producing carbon composite lithium iron manganate particles according to the present invention is a low cost and low environmental load production method.
  • the carbon composite lithium iron manganese phosphate particles according to the present invention can produce a highly filled positive electrode sheet, and a secondary battery using the positive electrode sheet has a current load at 25 ° C. and 0 ° C. It was confirmed that a high capacity was obtained in terms of characteristics. At the same time, as a result of the high-temperature charge / discharge cycle test at 60 ° C., a capacity retention rate of 98% or more was confirmed.
  • the present invention uses an olivine-type carbon composite lithium iron manganate particle powder produced by a low-cost, low environmental load manufacturing method as a secondary battery positive electrode active material, thereby increasing the energy density per volume.
  • a high capacity can be obtained even in a low temperature, high current load characteristic, and a nonaqueous solvent secondary battery having a high capacity retention rate in a high temperature cycle characteristic can be obtained.

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PCT/JP2013/073132 2012-08-31 2013-08-29 Procédé de production de poudre de particules de phosphate de fer et manganèse lithié et de fibres de carbone, poudre de particules de phosphate de fer et manganèse lithié et de fibres de carbone, et batterie secondaire à électrolyte non aqueux utilisant la poudre de particules de phosphate de fer et manganèse lithié et de fibres de carbone Ceased WO2014034775A1 (fr)

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