WO2011115211A1 - Procédé pour la production de poudre particulaire de phosphate de lithium-manganèse-fer, poudre particulaire de phosphate de lithium-manganèse-fer et batterie secondaire à électrolyte non aqueux utilisant cette poudre particulaire - Google Patents

Procédé pour la production de poudre particulaire de phosphate de lithium-manganèse-fer, poudre particulaire de phosphate de lithium-manganèse-fer et batterie secondaire à électrolyte non aqueux utilisant cette poudre particulaire Download PDF

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WO2011115211A1
WO2011115211A1 PCT/JP2011/056397 JP2011056397W WO2011115211A1 WO 2011115211 A1 WO2011115211 A1 WO 2011115211A1 JP 2011056397 W JP2011056397 W JP 2011056397W WO 2011115211 A1 WO2011115211 A1 WO 2011115211A1
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compound
olivine
lithium
powder
limn
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PCT/JP2011/056397
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English (en)
Japanese (ja)
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三島祐司
本田晋吾
西尾尊久
沖田朋子
山本博司
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戸田工業株式会社
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Priority to CN201180011603.6A priority Critical patent/CN102781827B/zh
Priority to KR1020127022574A priority patent/KR101810259B1/ko
Publication of WO2011115211A1 publication Critical patent/WO2011115211A1/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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention is a method for producing olivine-type lithium iron manganese phosphate particles that can be easily produced at low cost, and has a high energy density when used as a high-power secondary battery.
  • Provided are lithium iron manganese oxide particles and a secondary battery using the same.
  • LiFePO 4 3.5V class olivine type structure LiFePO 4 to 4.1V class LiMnPO 4 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 , improvement of charge / discharge characteristics is required.
  • 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.
  • grain surface there exists a tendency which coat
  • 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 it follows a two-phase reaction of the following formula due to the presence of a plateau region in charge / discharge characteristics indicated by capacity and voltage.
  • Non-Patent Documents 1 to 6 are methods in which Fe is dissolved in Mn sites.
  • LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) also has better charge / discharge characteristics at low current as the particle surface is coated with carbon.
  • the smaller the crystallite size satisfies the above condition the better the charge / discharge characteristics at a high current load.
  • each aggregate in order to obtain a high molding density, each aggregate is formed so as to form a network of secondary particles that are appropriately aggregated and a conductive auxiliary agent such as carbon having a high graphitization rate. The state needs to be controlled.
  • 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. Therefore, in order to secure charge / discharge capacity per unit volume, olivine-type lithium iron manganese phosphate coated with fine and moderate carbon was obtained and high density was obtained through a small amount of conductive auxiliary agent. There is a need to form aggregates.
  • lithium manganese iron phosphate particles having an olivine structure with a small change in particle size, low electrical resistance, and high filling property due to charge / discharge are used as the positive electrode active material powder for non-aqueous electrolyte secondary batteries. It is required to produce by an industrial method with a small load.
  • Patent Document 1 technology to reduce deterioration after charge / discharge cycle test
  • Patent Document 2 technology to add different metal elements to reduce electrical resistance
  • Patent Document 3 technology synthesized by hydrothermal method
  • Patent Document 1 is a technique for improving charge / discharge repetition characteristics when LiMn 1-x Fe x PO 4 particle powder having an olivine type structure is used as a positive electrode. There is no mention of collective control.
  • Patent Document 2 is not a technique related to the composite of LiMnPO 4 particle powder having an olivine structure and carbon.
  • 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.
  • the present invention establishes an industrial method of olivine-type lithium iron phosphate particles with a small olivine structure, which has a small change in particle size due to charge / discharge, low electrical resistance, and high packing properties, As a non-aqueous electrolyte secondary battery containing a high positive electrode active material, it is a technical subject to obtain a high capacity also in current load characteristics.
  • the present invention relates to a method for producing olivine-type lithium manganese iron phosphate LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) particle powder, wherein the raw material is Li compound, Mn compound , Fe compound, P compound and sugar or organic acid, and the raw material charge ratio is 0.95 ⁇ Li / (Mn + Fe) ⁇ 2.0, 0.95 ⁇ P / (Mn + Fe) ⁇ 1.3 in terms of mol ratio Obtained in the first step and the first step of obtaining an aqueous slurry having a pH of 5.5 to 12.5 by a neutralization reaction of a mixed solution containing 1 to 20 mol% of sugar or organic acid with respect to (Mn + Fe) The slurry is hydrothermally treated at a reaction temperature of 120 to 220 ° C., and the resulting compound has a production rate of LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) of 75 wt% or more, Size 10-250
  • the median diameter of the aggregated particles in the slurry is 0.1 to 10 ⁇ m
  • the crystal phase is (NH 4 ) Mn 1- ⁇ Fe ⁇ PO 4 (0 ⁇ ⁇ ⁇ 1) or a manufacturing method according to the first aspect of the present invention for obtaining an aqueous slurry containing aggregated particles satisfying HMn 1- ⁇ Fe ⁇ PO 4 (0 ⁇ ⁇ ⁇ 1) (Invention 2).
  • this invention is the manufacturing method of this invention 1 or 2 whose saccharide
  • the present invention is the production method according to any one of the present inventions 1 to 3, wherein in the second step, washing is performed so that the sulfur content in the compound is 0.1 wt% or less (Invention 4). .
  • the present invention is the production method according to any one of the present inventions 1 to 4, wherein in the third step, the organic substance to be added is at least one of carbon black, an oil and fat compound, a sugar compound, and a synthetic resin. (Invention 5).
  • the present invention also relates to olivine type lithium manganese iron phosphate LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) particle powder, wherein the content of lithium and phosphorus is in a molar ratio.
  • the crystallite size is 25 to 300 nm, the median diameter of the aggregated particles is 0.3 to 20 ⁇ m, and the electrical resistivity of the powder is 1 to 1.0 ⁇ 10 6 ⁇ ⁇ cm.
  • This is an olivine-type lithium iron manganese phosphate powder (this Invention 6).
  • the present invention also relates to lithium iron manganese phosphate particles having an olivine structure according to the present invention 6, wherein the lithium and phosphorus contents satisfy Li ⁇ P (the present invention 7).
  • the present invention also relates to lithium iron manganese phosphate particles having an olivine structure according to the present invention 6 or 7, wherein the unit cell volume V UC has the relationship represented by the following formula (1) (the present invention 8).
  • the present invention is a non-aqueous electrolyte secondary battery produced using the olivine-type lithium manganese iron phosphate particles according to any one of the present inventions 6 to 8 (Invention 9).
  • the method for producing olivine-type lithium iron manganese phosphate particles according to the present invention is low-cost and can be produced efficiently from almost equal amounts of raw materials. Is preferred.
  • lithium olivine manganese phosphate particles having an olivine structure according to the present invention have little change in particle size due to charge / discharge, low electrical resistance, and high filling properties, and are used for non-aqueous electrolyte secondary batteries. Suitable as a positive electrode active material.
  • the secondary battery using the olivine-type lithium manganese iron phosphate particles having the olivine structure as the positive electrode active material according to the present invention has a high capacity in the current load characteristics and can sufficiently withstand repeated charge and discharge.
  • Example 2 is a secondary electron image of the olivine-type lithium manganese iron phosphate particles obtained in Example 1 by a scanning electron microscope. It is the discharge characteristic which made the positive electrode the olivine type structure lithium iron iron phosphate particle powder obtained in Example 1, and evaluated it by the coin cell. It is a secondary electron image by the scanning electron microscope of the lithium iron manganese phosphate particle powder of the olivine type structure obtained in Comparative Example 4. It is a secondary electron image by the scanning electron microscope of the particle powder obtained by chemically oxidizing the lithium iron manganese phosphate particle powder of the olivine type structure obtained in Comparative Example 4. It is a Rietveld analysis result of the X-ray-diffraction pattern of the particle powder obtained by chemically oxidizing the lithium iron manganese phosphate particle powder of the olivine type structure obtained in Comparative Example 4.
  • the method for producing olivine-type lithium manganese iron phosphate LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) particle powder according to the present invention includes a Li compound, a Mn compound, an Fe compound, Using a P compound and a sugar or an organic acid, the raw material charge ratio is 0.95 ⁇ Li / (Mn + Fe) ⁇ 2.0, 0.95 ⁇ P / (Mn + Fe) ⁇ 1.3 in terms of mol ratio, and (Mn + Fe)
  • the raw materials used in the first step are preferably LiOH and Li 3 PO 4 as the Li compound, MnSO 4 and MnCO 3 as the Mn compound, FeSO 4 and FeCO 3 as the Fe compound, and P compound as the P compound.
  • H 3 PO 4 , (NH 4 ) H 2 PO 4 , (NH 4 ) 2 HPO 4 , NaH 2 PO 4 , Na 2 HPO 4 , and Na 3 PO 4 are preferred.
  • the Li compound, Mn compound, Fe compound, and P compound in the first step have a raw material charge ratio of 0.95 ⁇ Li / (Mn + Fe) ⁇ 2.0 and 0.95 ⁇ P / (Mn + Fe) ⁇ 1. 3 to be mixed.
  • the raw material charge ratio is outside the above range, the target lithium iron manganese phosphate cannot be obtained.
  • the molar ratio is 0.98 ⁇ Li / (Mn + Fe) ⁇ 1.8 and 0.98 ⁇ P / (Mn + Fe) ⁇ 1.2.
  • the sugar or organic acid used in the first step is preferably sucrose, ascorbic acid, or citric acid.
  • the addition amount of sugar or organic acid is 1 to 20 mol%, more preferably 1.5 to 18 mol%, based on (Mn + Fe).
  • the added sugar or organic acid works as a transition metal reducing agent, and after hydrothermal reaction.
  • the production rate of LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) is increased, and the primary particle diameter of the product is refined.
  • LiOH, NaOH, Na 2 CO 3 , NH 3 , urea, ethanolamine or the like is used as the alkali source used in the first step.
  • the aqueous slurry in the first step has a pH of 5.5 in order to increase the production rate of LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) of the compound obtained by the hydrothermal treatment in the second step.
  • the median diameter of the aggregated particles in the slurry in the first step is preferably 0.1 to 10 ⁇ m.
  • the crystal phase of the aggregated particles in the slurry is (NH 4 ) Mn 1- ⁇ Fe ⁇ PO 4 (0 ⁇ ⁇ ⁇ 1) or HMn 1- ⁇ Fe ⁇ PO 4 (0 ⁇ ⁇ ⁇ 1). It is preferable that the agglomerated particles are included. When one of the two phases is not included, the target lithium manganese iron phosphate cannot be obtained.
  • the agglomerated particles having the median diameter and the crystal phase can be obtained by mixing raw materials under conditions where crystal nuclei are generated and grown (generation of a large number of crystal nuclei) or by pulverization of the product.
  • Examples of the apparatus used for pulverization include a ball mill and a medium stirring mill.
  • the hydrothermal treatment in the second step is preferably performed at 120 to 220 ° C.
  • the hydrothermal treatment time is preferably 1 to 10 hours.
  • the production rate of LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) is 75 wt% or more.
  • the production rate of LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) remains low even after the subsequent steps.
  • a more preferable production rate is 80 wt% or more.
  • the crystallite size of the obtained compound based on LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) is 10 to 250 nm.
  • a compound having a crystallite size of less than 10 nm is industrially difficult to produce, and a compound having a crystallite size of more than 250 nm cannot obtain good battery characteristics.
  • a more preferable crystallite size is 30 to 150 nm.
  • the hydrothermal treatment in the second step needs to be performed by appropriately selecting the treatment temperature and the treatment time so as to satisfy the above generation rate and crystallite size. If the hydrothermal treatment temperature is low and the treatment time is short, the above-mentioned production rate may not be reached, or the crystallite size may not be reached, and if the hydrothermal treatment temperature is high and the treatment time is long, the above crystals May exceed child size.
  • the compound obtained by the hydrothermal treatment in the second step is subjected to filtration washing or decantation washing in order to remove impurity sulfate ions and control the composition ratio.
  • the apparatus used for cleaning include a press filter and a filter thickener.
  • the washing of the compound obtained by the hydrothermal treatment in the second step is preferably performed so that the sulfur content in the compound is 0.1 wt% or less. Washing is sufficient if sulfur in the compound can be sufficiently removed, and usually washing with water may be performed.
  • lithium compounds such as LiOH and Li 2 CO 3 are used for adjusting Li
  • manganese compounds such as MnCO 3 and MnC 2 O 4 are used for adjusting Mn
  • FeCO 3 and FeC are used for adjusting Fe.
  • an iron compound such as 2 O 4 and a PO 4 -containing compound such as H 3 PO 4 , (NH 4 ) H 2 PO 4 , (NH 4 ) 2 HPO 4 for adjusting P.
  • a fine lithium iron manganese phosphate solid solution coated with carbon 3 to 40 wt% of an organic substance is added in the third step to obtain a precursor powder. At that time, it is necessary to reduce the primary particle size of the precursor powder and to uniformly mix with the organic matter.
  • the apparatus used for mixing include a Henschel mixer, a raking machine, a high speed mixer, a medium stirring mill, and the like.
  • the organic substance to be added is preferably at least one of carbon black, an oil and fat compound, a sugar compound, and a synthetic resin.
  • the organic substance added is preferably at least one of an oil and fat compound, a sugar compound, and a synthetic resin.
  • the resulting compacted compact of olivine-type lithium manganese iron phosphate particles even at low temperatures such as 400 to 500 ° C. has an electrical resistivity of 1 to 1.0 ⁇ 10 6 ⁇ ⁇ cm. Satisfying and high performance secondary battery characteristics.
  • oil and fat compound examples include stearic acid and oleic acid
  • sugar compound examples include sucrose and dextrin
  • synthetic resin examples include polyethylene, polypropylene, and polyvinyl alcohol (PVA).
  • carbon black examples include acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) and ketjen black (manufactured by Lion Corporation).
  • Preferred binders include polyvinyl alcohol (PVA), polyvinyl butyral, starch, carboxymethyl cellulose and the like.
  • the precursor powder obtained in the third 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 inert gas N 2 , Ar, H 2 O, CO 2 or a mixed gas thereof is used.
  • the reducing gas H 2 , CO, or a mixed gas of these gases and the inert gas is used.
  • the apparatus used for firing include a gas flow type box muffle furnace, a gas flow type rotary furnace, and a fluidized heat treatment furnace.
  • the calcination temperature may be 250 ° C. or higher, but the reaction of unreacted substances is completed, and the added organic matter
  • it is preferably calcined at 350 to 850 ° C., more preferably at 400 to 750 ° C. for 1 to 10 hours.
  • the lithium iron manganese phosphate particles according to the present invention can produce LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) after hydrothermal treatment by adjusting an appropriate precursor slurry. The rate can be increased. Thereafter, the mixture is uniformly mixed with an organic substance and further baked, whereby the production rate of LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) is high, and fine manganese phosphate sufficiently covered with carbon Iron lithium particle powder can be obtained.
  • the lithium iron manganese phosphate particles according to the present invention are preferably produced by the production method according to the present invention 1 described above.
  • the content of lithium and phosphorus is 0.9 ⁇ Li / (Mn + Fe) ⁇ 1.2 and 0.9 ⁇ P / (Mn + Fe) ⁇ 1.2 in terms of mol ratio. It is.
  • the content of lithium and phosphorus is outside the above range, a heterogeneous phase is likely to be formed, and in some cases, grain growth is promoted and lithium manganese iron phosphate particles having high battery characteristics cannot be obtained.
  • Preferable lithium and phosphorus contents are 0.98 ⁇ Li / (Mn + Fe) ⁇ 1.05, 0.98 ⁇ P / (Mn + Fe) ⁇ 1.05, and more preferably 1 ⁇ Li / (Mn + Fe) in molar ratio. ) ⁇ 1.05, 1 ⁇ P / (Mn + Fe) ⁇ 1.05.
  • the lithium manganese iron particle powder according to the present invention preferably has a lithium and phosphorus content of Li ⁇ P.
  • the BET specific surface area of the lithium iron manganese phosphate particles according to the present invention is 6 to 70 m 2 / g.
  • the BET specific surface area is less than 6 m 2 / g, the movement of Li ions in the lithium iron manganese phosphate particle powder is slow, so that it is difficult to take out the current.
  • a preferred BET specific surface area is 10 to 65 m 2 / g, more preferably 15 to 60 m 2 / g.
  • the carbon content of the lithium iron manganese phosphate particles according to the present invention is 0.5 to 8.0 wt%.
  • the carbon content is less than 0.5 wt%, the particle growth during the heat treatment cannot be suppressed, and the electric resistance of the obtained powder is increased, which deteriorates the charge / discharge characteristics of the secondary battery.
  • the carbon content exceeds 8.0 wt%, the packing density of the positive electrode is lowered, and the energy density per volume of the secondary battery is reduced.
  • a more preferable carbon content is 1.0 to 6.0 wt%.
  • the lithium iron manganese phosphate particles according to the present invention have an impurity sulfur content of 0.08 wt% or less, and good storage characteristics can be obtained in a nonaqueous electrolyte secondary battery.
  • impurities such as lithium sulfate are formed, and these impurities undergo a decomposition reaction during charge and discharge, and the reaction with the electrolyte during high-temperature storage is promoted, and after storage Resistance rises intensely.
  • a more preferable sulfur content is 500 ppm or less.
  • the crystal phase of LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) having an olivine structure is 95 wt% or more.
  • LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) particles obtained after firing may be fine and the discharge capacity may be high.
  • Li 3 PO 4 itself does not contribute to charging and discharging, it is desirable that it be less than 5 wt%.
  • the crystallite size of the lithium iron manganese phosphate particles according to the present invention is 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 the current load characteristics of the secondary battery are deteriorated.
  • the preferred crystallite size is 30 nm to 200 nm, more preferably 40 nm to 150 nm.
  • the median diameter of the aggregated particles of the lithium iron manganese phosphate particles according to the present invention is 0.3 to 30 ⁇ m.
  • the median diameter is less than 0.3 ⁇ m, the positive electrode packing density is decreased and the reactivity with the electrolytic solution is increased.
  • the median diameter exceeds 30 ⁇ m, it is too large for the electrode film thickness and it is extremely difficult to form a sheet.
  • a preferable median diameter of the aggregated particles is 0.5 to 15 ⁇ m.
  • the density of the compression molded body of the lithium iron manganese phosphate particles according to the present invention is preferably 1.8 g / cc or more.
  • the true density of LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) is 3.6 g / cc, and the closer to the true density, the better the filling property. Therefore, a preferable compression molding density is 2.0 g / cc or more exceeding 50% of the true density.
  • the lithium manganese iron phosphate particle powder according to the present invention is considered to have a high compression-molded body density because the amount of remaining carbon is small and primary particles are appropriately aggregated.
  • the powder electrical resistivity of the lithium iron manganese phosphate particles according to the present invention is 1 to 1.0 ⁇ 10 6 ⁇ ⁇ cm.
  • the powder electrical resistivity is preferably 1 to 5.0 ⁇ 10 5 ⁇ ⁇ cm, more preferably 5 to 1.0 ⁇ 10 5 ⁇ ⁇ cm.
  • the unit cell volume V UC of the lithium iron manganese phosphate particles according to the present invention is preferably in the relationship of formula (1).
  • the lattice constant and the unit cell volume decrease linearly with the increase of the value of x in LiMn 1-x Fe x PO 4 having an olivine structure, and follow Vegard's law.
  • the unit cell volume of LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) having an olivine structure inferred from the linearity of the Vegard rule is 10.9 ⁇ (1-x) +291.36 Met. The closer to the unit cell volume, the transition metal substitution to the Li site and the loss of P and O are reduced. When the volume is smaller than the unit cell volume, Li is substituted to the transition metal site, and the theoretical capacity as an electrode is reduced. I think it will increase.
  • the present inventors According to the heat treatment of a precursor having a composition ratio deviated from the stoichiometric ratio of LiMn 1-x Fe x PO 4 having an olivine structure, the present inventors have made LiMn 1-x Fe x PO 4 ( It was confirmed that an impurity crystal phase that exists more stably than 0.05 ⁇ x ⁇ 0.5) tends to be generated.
  • the composition ratio of Li, Mn, Fe, and P is slight and a olivine-type LiMn 1-x Fe x PO 4 single crystal phase is formed, different lattice constants are obtained.
  • the unit cell volume is more than the above formula (1). In that case, it is assumed that the transition metal substitution to the Li site and the loss of P and O occur, and the battery characteristics deteriorate.
  • a conductive agent and a binder are added and mixed according to a conventional method.
  • the conductive agent acetylene black, 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 45 to 105 ⁇ 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 ⁇ m 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. in a non-oxidizing atmosphere of Fe 2+ .
  • 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.
  • 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 1 to 1.0 ⁇ 10 6 ⁇ . ⁇ Because it is as low as cm, the amount of carbon added during sheet preparation can be suppressed, 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 suppressed, resulting in density A high positive electrode 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 olivine-type lithium iron manganese phosphate LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5) particle powder according to the present invention is produced by hydrothermal reaction and firing, and is low in cost and in a small environment Can be manufactured with load.
  • the present invention is the manufacturing method of LiMn 1-x Fe x PO 4 of olivine (0.05 ⁇ x ⁇ 0.5), LiMn 1-x Fe x PO 4 by hydrothermal reaction (0.05 ⁇ x ⁇ 0.5) is produced at a high production rate, then uniformly mixed with an organic substance to control the aggregated particle size, and fired under conditions of an inert or reducing atmosphere, and is finely coated with carbon. In addition, it is possible to obtain a particle powder having a high filling property.
  • the nonaqueous electrolyte secondary battery using this as a positive electrode active material also has a current load characteristic.
  • the present inventor estimates that a high capacity can be obtained and that it can sufficiently withstand repeated charge and discharge.
  • the non-aqueous electrolyte secondary battery using the olivine-type lithium iron manganese phosphate particles according to the present invention as a positive electrode active material has a discharge capacity at 115 Ch / g at room temperature (25 ° C.) of 115 mAh / g or more.
  • the discharge capacity at 1 C at 95 ° C. is at least 95 mAh / g, and the discharge capacity at 5 C at room temperature is at least 80 mAh / g.
  • 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.
  • Particle size of the aggregated particles in the slurry in the first step were measured median diameter D 50 by a wet method.
  • the crystal phase of the aggregated particles in the slurry in the first step was obtained by filtering the aggregated particles in the slurry, and using Cu-K ⁇ , a wet cake using an X-ray diffractometer RINT-2500 [manufactured by Rigaku Corporation]. Measurement was performed under conditions of 40 kV and 300 mA, and the crystal phase was identified.
  • the TCH pseudo-void function is used as the profile function, the method such as Finger is used for asymmetry of the function, and the reliability factor S value is 2.0. Analyzed to cut.
  • the unit cell volume of the lithium iron manganese phosphate particles having the olivine structure (space group Pnma) according to the present invention was calculated from the product of the lattice constants a, b and c calculated by the Rietveld analysis.
  • the composition ratio of the compound powder after adjusting the composition ratio of the compound obtained by the hydrothermal treatment in the second step and the lithium manganese iron phosphate particle powder according to the present invention is determined by the emission plasma analyzer ICAP-6500 [Thermo [Fischer Scientific]. The sample was dissolved in an acid solution at 200 ° C. using an autoclave.
  • the specific surface area of the lithium iron manganese phosphate particles according to the present invention was measured using MONOSORB [manufactured by Yuasa Ionics Co., Ltd.] after drying and deaeration of the sample under nitrogen gas at 120 ° C. for 45 minutes.
  • Carbon and sulfur amounts 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 of the lithium iron manganese phosphate particles according to the present invention was calculated from the weight and volume of the compression molded body when compacted to 1.5 t / cm 2 with a 13 mm ⁇ jig. Moreover, the powder electrical resistivity was measured by the two-terminal method using the compression molded body.
  • NO 2 BF 4 having a molar number twice that of Li in the powder iron manganese phosphate is added to the powder of lithium manganese phosphate, left to stand for chemical oxidation, washed with acetonitrile and washed with Li. A particle powder with all removed was obtained.
  • the primary particle diameter was measured by SEM photographs obtained with a scanning electron microscope (SEM) of Hitachi S-4800 type, and the change rate of the primary particle diameter before and after chemical oxidation was calculated.
  • the secondary battery characteristics of the CR2032-type coin cell were evaluated using the lithium iron manganese phosphate particles having an olivine structure according to the present invention.
  • the positive electrode material slurry was adjusted to 8 wt%, applied onto an Al current collector with a doctor blade, dried in air at 120 ° C. for 10 minutes, and the dried sheet was pressurized to 3 t / cm 2 to form a positive electrode A sheet was produced.
  • the charge / discharge characteristics of the non-aqueous electrolyte secondary battery using the olivine type lithium iron manganese phosphate particles according to the present invention as the positive electrode active material were measured by measuring the discharge capacity at C / 10, 1C, and 5C at room temperature. And evaluated.
  • C / 10 is 10 hours
  • 1C is 1 hour
  • 5C is 1/5 hour
  • the theoretical capacity of LiMn 1-x Fe x PO 4 (0.05 ⁇ x ⁇ 0.5).
  • the current value is fixed so that a current of 170 mAh / g flows.
  • a higher C coefficient means higher current load characteristics.
  • the voltage range during charging and discharging is not particularly limited, but in the present invention, the voltage range was 2.0 to 4.5V.
  • Example 1 A solution of MnSO 4, H 3 PO 4 , and NH 4 OH was mixed, and NH 4 MnPO 4 was precipitated by a neutralization reaction at room temperature. After the precipitate was filtered off and washed with pure water, a solution of LiOH.H 2 O, FeSO 4 , H 3 PO 4 , and ascorbic acid was added, and the aqueous slurry adjusted to the raw material charge ratio shown in Table 1 Got.
  • the slurry was mixed with a ball mill, and the aggregated particles were pulverized to adjust the particle size.
  • the slurry was hydrothermally treated at 180 ° C. for 3 hours, and the resulting compound was filtered off, washed with pure water, and dried at 70 ° C. overnight. From the Rietveld analysis of the XRD pattern, the obtained dry powder has a production rate of LiMn 1-x Fe x PO 4 of 95% and 5 wt% of Li 3 PO 4 as an impurity crystal phase other than the olivine structure. confirmed.
  • the crystallite size was 70 nm according to Scherrer's equation. Further, the content of impurity sulfur in the dry powder was 0.1 wt% or less (second step).
  • the precursor powder obtained in the third step was put in an alumina crucible and baked in a nitrogen atmosphere at 650 ° C. for 5 hours.
  • the temperature increase rate was 200 ° C./hr, and the N 2 gas flow rate was 1 L / min (fourth step).
  • the obtained powder was lithium iron manganese phosphate particles having an olivine structure, and the composition ratio thereof was the same as the composition ratio of Li, Mn, Fe, and P adjusted in the third step.
  • FIG. 1 shows an SEM photograph (secondary electron image) of the olivine-type lithium iron manganese phosphate particles obtained.
  • Table 1 shows the manufacturing conditions of the first step and the properties of the obtained slurry
  • Table 2 shows the characteristics of the powder in the second step and the manufacturing conditions of the third step
  • Table 3 shows the obtained lithium iron manganese phosphate.
  • the powder characteristics of the particle powder are shown in Table 4 and FIG. 2 as the battery characteristics evaluated by a coin cell using the obtained lithium iron manganese phosphate particle powder as a positive electrode. Further, the change rate of the primary particle size before and after the removal of Li by chemical oxidation was about 10%.
  • Example 2 The same processing as in Example 1 was performed except that the raw material charging ratio was changed as shown in Table 1.
  • Example 3 A solution of Fe 3 (PO 4 ) 2 .8H 2 O, Li 3 PO 4 and LiOH.H 2 O was added to NH 4 MnPO 4 obtained in the same manner as in Example 1, and the raw material charging ratios are as shown in Table 1.
  • An aqueous slurry was obtained in the same manner as in Example 1 except that Thereafter, PVA was added as an organic substance in the third step to the slurry after the hydrothermal reaction, and the same treatment as in Example 1 was performed except that the slurry was evaporated to dryness.
  • Example 4 A solution of MnSO 4 , FeSO 4 , H 3 PO 4 , NH 4 OH was mixed, and NH 4 Mn 0.7 Fe 0.3 PO 4 was precipitated by a neutralization reaction at room temperature. The obtained precipitate was separated by filtration and washed with pure water, and then LiOH.H 2 O, H 3 PO 4 and sucrose were added to obtain an aqueous slurry adjusted to the raw material charging ratio shown in Table 1. Thereafter, the same treatment as in Example 1 was carried out except that 15 wt% of polyethylene and stearic acid were used as organic substances in the third step.
  • Example 5 A solution of MnSO 4 and Na 2 CO 3 was mixed, and MnCO 3 was precipitated by a neutralization reaction at room temperature. The obtained precipitate was separated by filtration and washed with pure water, and then H 3 PO 4 was added to precipitate HMnPO 4 . Thereafter, the same processing as in Example 1 was performed except that the raw material charging ratio was changed as shown in Table 1.
  • Example 6 A solution of MnSO 4 , FeSO 4 , and Na 2 CO 3 was mixed, and HMn 0.9 Fe 0.1 CO 3 was precipitated by a neutralization reaction at room temperature. The resulting precipitate was filtered and washed with pure water, and then a solution of H 3 PO 4 was added to precipitate HMn 0.9 Fe 0.1 PO 4 . Thereafter, the same processing as in Example 1 was performed except that the raw material charging ratio was changed as shown in Table 1.
  • Example 7 The raw material charging ratio was changed as shown in Table 1, and treatment was performed in the same manner as in Example 1 except that 20 wt% of sucrose and carbon black were used as organic substances in the third step.
  • the agglomerated particles of the slurry were not pulverized, so the median diameter D 50 of the agglomerated particles was as large as 16 ⁇ m, and the yield of LiMnPO 4 having a olivine structure of the compound obtained after hydrothermal treatment was as low as 71 wt%. It was. Even in the lithium manganese iron phosphate particles powder obtained by firing, 7 wt% of Li 3 PO 4 which is an impurity crystal phase was present, and the battery characteristics deteriorated.
  • Example 2 An aqueous system adjusted to the raw material charge ratio shown in Table 1, including a precipitate obtained by mixing a solution of MnSO 4, FeSO 4 , H 3 PO 4 , and LiOH ⁇ H 2 O and neutralizing reaction at room temperature A slurry was obtained. The slurry was mixed with a ball mill, the aggregated particles were pulverized to adjust the particle size, then hydrothermally treated at 180 ° C. for 3 hours, the resulting precipitate was filtered, washed with pure water, and dried at 70 ° C. overnight. . Thereafter, the same processing as in Example 1 was performed. The crystallite size of the obtained dry powder was as large as 260 nm, and impurity sulfur in the dry powder was 0.12 wt%. The lithium manganese iron phosphate particle powder obtained by firing had a large sulfur content and crystallite size, and the battery characteristics were poor.
  • Example 3 The same process as in Example 2 was performed except that the amount of sucrose, which is an organic substance, was changed to 1 wt% in the third step of Example 2.
  • the lithium manganese iron phosphate particles obtained by firing were coarse particles, had high electric resistance, and had poor battery characteristics.
  • Li 2 CO 3 , MnCO 3 , (NH 4 ) H 2 PO 4 are mixed so that the ratio of Li, Mn, and P is 1: 1: 1, and a mixed solvent composed of ethanol and water to which PVA is further added.
  • the obtained compound was separated by filtration and fired in air at 700 ° C. for 2 hours to obtain lithium iron manganese phosphate particles.
  • the obtained lithium iron manganese phosphate particles were coarse particles, had high electric resistance, and had poor battery characteristics.
  • FIG. 3 shows an SEM photograph of the obtained lithium iron manganese phosphate particle powder
  • FIG. 4 shows an SEM photograph when Li is eliminated by chemical oxidation
  • FIG. 5 shows a Rietveld analysis result of the XRD pattern. It was confirmed that LiMnPO 4 was changed to fine MnPO 4 by chemical oxidation.
  • Example 5 An aqueous slurry was obtained in the same manner as in Example 3. Without performing the hydrothermal reaction in the second step, the precipitate in the slurry was separated by filtration, washed with pure water, and dried at 70 ° C. overnight. Thereafter, the same processing as in Example 1 was performed.
  • the lithium manganese iron phosphate particle powder obtained by firing contained a large amount of impurity crystal phase Li 3 PO 4 , and the battery characteristics were poor.
  • the non-aqueous electrolyte secondary battery using the olivine type lithium iron manganese phosphate particles according to the present invention as a positive electrode active material has a discharge capacity of 115 mAh / g or more at C / 10 at room temperature and 1 C at room temperature.
  • the discharge capacity was 95 mAh / g or more, and the discharge capacity at 5 C at room temperature was 80 mAh / g or more.
  • Example 8 to 15 The precursor powder obtained in the second step was changed to Li 2 CO 3 , MnCO 3 , FeC 2 O 4 , (NH 4 ) in the same manner as in Example 1 except that the raw material charging ratio was changed as shown in Table 5. Fine powders of H 2 PO 4 and (NH 4 ) 2 HPO 4 were added as necessary and mixed by a ball mill, and the composition ratios of Li, Mn, Fe, and P were adjusted as shown in Table 5. Thereafter, the same processing as in Example 1 was performed.
  • the main component of the obtained powder was lithium iron manganese phosphate particles having an olivine structure, and the composition ratio was the same as the composition ratio of Li, Mn, Fe, and P adjusted in the third step.
  • Table 5 shows the manufacturing conditions of the first step and the properties of the obtained slurry
  • Table 6 shows the characteristics of the powder in the second step and the manufacturing conditions of the third step
  • Tables 7 and 8 show the phosphoric acid obtained.
  • the battery characteristics of the manganese iron lithium particle powder are shown in Table 9 and evaluated by a coin cell using the obtained lithium manganese iron phosphate particle powder as a positive electrode.
  • lithium iron manganese phosphate particles having an olivine structure when the lithium and phosphorus contents satisfy Li ⁇ P, the formation of an Mn 2 P 2 O 7 impurity crystal phase that deteriorates battery characteristics Tended to be suppressed.
  • the impurity crystal phase is not detected, but when Li and P are present out of the stoichiometric ratio, the excess Li It is believed that P and P do not adversely affect battery characteristics by forming an ion conductive amorphous phase.
  • a coin cell using an electrode in which the amount of the conductive material is doubled with respect to the evaluation method is 5C.
  • the discharge capacity was improved by 10 to 30%, and a further increase in capacity was confirmed.
  • the method for producing olivine-type lithium iron manganese phosphate particles according to the present invention can be achieved by using an approximately equal amount of raw material without using an excessive amount of raw material, and a low-cost and efficient production method. is there.
  • the olivine-type lithium manganese iron particle powder having the olivine structure according to the present invention makes it possible to produce a positive electrode sheet having a high filling property, and a secondary battery using the same has a high capacity in terms of current load characteristics. It was confirmed that it was obtained.
  • the present invention uses olivine-type lithium iron manganese phosphate particles produced by a low-cost and efficient production method as a positive electrode active material, so that the energy density per volume is high and the capacity is high even in high current load characteristics.
  • a non-aqueous electrolyte secondary battery can be obtained.

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Abstract

L'invention porte sur un procédé pour la production d'une poudre particulaire de phosphate de lithium-manganèse-fer à structure olivine, LiMn1-xFexPO4 (0,05 ≤ x ≤ 0,5). Le procédé est caractérisé par une première étape servant à obtenir une pâte liquide à base d'eau par la réaction de neutralisation d'une solution mélangée de matières de départ et une deuxième étape consistant à effectuer le traitement thermique de la pâte liquide obtenue dans la première étape, ayant un taux de production supérieur ou égal à 75 % en poids pour le composé LiMn1-xFexPO4 (0,05 ≤ x ≤ 0,5) obtenu et à laver ce composé après avoir amené la taille des cristallites à 10-250 nm. Le procédé est en outre caractérisé par une troisième étape servant à obtenir une poudre précurseur ayant une teneur en carbone de 3-40 % en poids par ajout d'une substance organique au composé obtenu dans la deuxième étape et un quatrième traitement pour la cuisson de la poudre de précurseur obtenue dans la troisième étape. La poudre particulaire peut être produite facilement à faible coût et la capacité de charge et de décharge est grande pour des batteries secondaires. L'invention porte également sur une batterie secondaire utilisant le procédé pour la production de la poudre particulaire de phosphate de lithium-manganèse-fer, qui a des propriétés de remplissage supérieures et des caractéristiques de charge et décharge répétées supérieures.
PCT/JP2011/056397 2010-03-19 2011-03-17 Procédé pour la production de poudre particulaire de phosphate de lithium-manganèse-fer, poudre particulaire de phosphate de lithium-manganèse-fer et batterie secondaire à électrolyte non aqueux utilisant cette poudre particulaire WO2011115211A1 (fr)

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KR1020127022574A KR101810259B1 (ko) 2010-03-19 2011-03-17 인산망간철리튬 입자 분말의 제조 방법, 인산망간철리튬 입자 분말, 및 상기 입자 분말을 이용한 비수전해질 이차 전지

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