WO2010032449A1 - マンガン酸リチウム粒子粉末の製造方法及び非水電解質二次電池 - Google Patents
マンガン酸リチウム粒子粉末の製造方法及び非水電解質二次電池 Download PDFInfo
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- WO2010032449A1 WO2010032449A1 PCT/JP2009/004636 JP2009004636W WO2010032449A1 WO 2010032449 A1 WO2010032449 A1 WO 2010032449A1 JP 2009004636 W JP2009004636 W JP 2009004636W WO 2010032449 A1 WO2010032449 A1 WO 2010032449A1
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
- C04B2235/81—Materials characterised by the absence of phases other than the main phase, i.e. single phase materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention provides a method for producing lithium manganate particles having high output and excellent high-temperature stability.
- spinel type structure LiMn 2 O 4 As a positive electrode active material useful for a high energy type lithium ion secondary battery having a voltage of 4V class, spinel type structure LiMn 2 O 4 , rock salt type structure LiMnO 2 , LiCoO 2 , LiCo 1-X Ni X O 2 , LiNiO 2, etc. are generally known. Among them, LiCoO 2 is excellent in that it has a high voltage and a high capacity, but there is a problem of high manufacturing cost due to a small supply amount of cobalt raw material. It includes environmental safety issues of waste batteries. Accordingly, active research has been conducted on spinel structure type lithium manganate particles (basic composition: LiMn 2 O 4 -hereafter the same-) made from manganese, which is supplied at a low cost and has good environmental friendliness. Yes.
- spinel structure type lithium manganate particles basic composition: LiMn 2 O 4 -hereafter the same-
- the lithium manganate particle powder can be obtained by mixing a manganese compound and a lithium compound at a predetermined ratio and firing at a temperature range of 700 to 1000 ° C.
- lithium manganate particle powder is used as a positive electrode active material of a lithium ion secondary battery
- charge / discharge cycle characteristics are inferior although it has high voltage and high energy density. This is due to the fact that the crystal lattice expands and contracts due to the lithium ion desorption / insertion behavior in the crystal structure with repeated charge and discharge, and that the lattice breaks due to the volume change of the crystal and that manganese dissolves in the electrolyte. It is said that.
- the positive electrode active material made of lithium manganate particle powder is excellent in filling property, has an appropriate size, and further suppresses elution of manganese.
- a method of controlling the particle size and particle size distribution of lithium manganate particles a method of obtaining a highly crystalline lithium manganate particle powder by controlling the firing temperature, and strengthening the bonding power of crystals by adding different elements
- a method of suppressing the elution of manganese by mixing an additive and a surface treatment is a method of controlling the particle size and particle size distribution of lithium manganate particles, a method of obtaining a highly crystalline lithium manganate particle powder by controlling the firing temperature, and strengthening the bonding power of crystals by adding different elements.
- Patent Documents 1 to 6 it has been known that lithium manganate particles contain aluminum as one of different elements. Further, it is known that a boron auxiliary effect can be obtained by adding boron oxide, boric acid, lithium borate, or ammonium borate as the boron source during firing (Patent Documents 7 to 11). ).
- Lithium manganate particle powder contains Ca compound and / or Ni compound and Al compound (Patent Document 1), Lithium manganate particle powder contains Al, and the peak position of each diffraction surface of X-ray diffraction Limiting (Patent Document 2), Lithium manganate particle powder contains different elements such as Al, and firing is performed in multiple stages (Patent Document 3), Lithium manganate particle powder contains Al In addition, lithium manganate having a specific surface area of 0.5 to 0.8 m 2 / g and a sodium content of 1000 ppm or less (Patent Document 4), and lithium manganate particle powder contains a different element such as Al.
- lithium manganate having a (400) plane half-width of 0.22 ° or less and an average diameter of crystal grains of 2 ⁇ m or less Lithium manganate particles containing different elements such as Al, lithium manganate having a crystallite size of 600 mm or more and a lattice strain of 0.1% or less (Patent Document 6), lithium compound and manganese dioxide Lithium manganate represented by the chemical formula in which the boron compound is heat-treated at a temperature of 600 ° C. to 800 ° C. and the boron is taken into the lattice (Patent Document 7), the melting point of the oxide Is added with elements and fluorine compounds of 800 ° C.
- Patent Document 8 Lithium manganate particle powder (Patent Document 9) containing, as a boric acid species, the use of lithium tetraborate is specified and contained Um particles (Patent Document 10) have been described, respectively.
- lithium manganate As the positive electrode active material for nonaqueous electrolyte secondary batteries, lithium manganate, which improves output characteristics and high-temperature characteristics, is currently the most demanded, but materials and manufacturing methods that satisfy the necessary and sufficient requirements have not yet been obtained. Absent.
- Patent Documents 1 to 10 describe lithium manganate obtained by substituting a part of manganese for a metal element with a different element, and lithium manganate added with a small amount of a boron compound. The storage characteristics were not satisfactory and practically still insufficient.
- the present inventors have arrived at the present invention as a result of various investigations on the shape and firing temperature of the additive element.
- the present invention provides a method for producing lithium manganate particles by mixing a lithium compound, a manganese compound and a boron compound and then firing the mixture in a temperature range of 800 ° C. to 1050 ° C.
- D 50 is a method for producing lithium manganate particle powder, wherein the average particle size (D 50 ) of the manganese compound is 15 times or less (Invention 1).
- the present invention also relates to the method for producing lithium manganate particles according to the present invention 1 wherein the average particle diameter (D 50 ) of the boron compound is 1 ⁇ m to 100 ⁇ m (the present invention 2).
- the present invention also relates to the method for producing lithium manganate particles according to the present invention 1 or 2, wherein the manganese compound has an average particle size (D 50 ) of 1 ⁇ m to 20 ⁇ m (the present invention 3).
- the obtained lithium manganate particle powder is formed of secondary particles obtained by agglomerating or sintering primary particles having a particle diameter of 1 ⁇ m or more.
- the average particle size (D 50 ) of secondary particles of lithium particles is 1 ⁇ m to 20 ⁇ m, and the particle size distribution (D 90 -D 10 ) is 2 to 40 ⁇ m, according to any one of the present inventions 1 to 3. This is a method for producing lithium manganate particles (Invention 4).
- the present invention also provides a non-aqueous electrolyte secondary using a lithium manganate particle powder obtained by the method for producing a lithium manganate particle powder according to any one of the present inventions 1 to 4 as a positive electrode active material or a part thereof. It is a battery (Invention 5).
- the lithium manganate particles produced according to the present invention are suitable as a positive electrode active material for a non-aqueous electrolyte secondary battery because of high output and particularly excellent high-temperature stability.
- lithium manganate particles having excellent characteristics by mixing a manganese compound, a lithium compound, and if necessary, a compound of a different element and a refined boron compound in a predetermined ratio and firing at a predetermined temperature A powder can be obtained.
- the particle size (D 50 ) is not more than 15 times the average particle size (D 50 ) of the secondary particles of the manganese compound.
- lithium manganate fine powder is generated. Decreases.
- segregation of boron melted at the time of firing becomes large, and the degree of aggregation of lithium manganate varies, resulting in a portion that is prone to cohesive failure.
- they are 2 times or more and 14 times or less, More preferably, they are 3 times or more and 13 times or less.
- the average particle diameter (D 50 ) of the secondary particles of the boron compound used in the present invention is preferably 1 to 100 ⁇ m, more preferably 1 to 70 ⁇ m.
- the average particle diameter (D 50 ) of the secondary particles of the manganese compound used in the present invention is preferably 1.0 to 20 ⁇ m, more preferably 2.0 to 19 ⁇ m.
- Examples of the manganese compound in the present invention include trimanganese tetraoxide (Mn 3 O 4 ) and manganese dioxide (MnO 2 ). In particular, it is preferable to use trimanganese tetraoxide.
- Examples of the boron compound used in the present invention include boric acid, lithium tetraborate, boron oxide, and ammonium borate. It is particularly preferable to use boric acid.
- lithium compound in the present invention examples include lithium carbonate and lithium hydroxide. It is particularly preferable to use lithium carbonate.
- a lithium compound, a manganese compound, a different metal element A method of mixing and firing a compound of the above and a boron compound, a composite of a manganese compound and a different metal element (a method of coating a surface of a compound of a different metal element by a dry method or a wet method, a compound of a different metal element on the surface of a manganese compound Any method of mixing and baking with a lithium compound and a boron compound may be used.
- Boron compounds promote crystal growth of lithium manganate particles as a sintering aid during firing.
- the boron compound is preferably added in an amount such that boron in the boron compound is 0.1 to 2.5 mol% with respect to manganese. When it is less than 0.1 mol%, the sintering promoting effect cannot be sufficiently obtained. When it exceeds 2.5 mol%, the sintering promoting effect is saturated, so that it is not added more than necessary. Further, the degree of aggregation and sintering of lithium manganate particles becomes too strong, and fine powder is generated. More preferably, it is 0.3 to 2.0 mol%.
- the firing temperature is preferably 800 ° C. or higher. If it is less than 800 degreeC, the sufficient sintering promotion effect of the particle
- the firing atmosphere may be in an oxygen-containing gas, such as air.
- the firing time may be selected so that the reaction proceeds uniformly, but it is preferably 1 to 48 hours, more preferably 10 to 24 hours.
- the boron compound has the effect of dulling the edges of the lithium manganate particles (angular portions: the bonding sites between the crystal planes and the crystal planes) during firing to form rounded particles.
- the edge (angular portion) of the lithium manganate particle is blunted to form a rounded particle, so that the elution site of manganese can be reduced. As a result, the stability of the secondary battery can be reduced. It is thought that the property can be improved.
- the boron compound reacts with lithium in the lithium compound to form a B—Li compound during firing. Since this B-Li compound is considered to be melted at 800 ° C. or higher, it is considered that the B-Li compound is present in a state of covering lithium manganate particles. Further, even if the lithium manganate particles are measured with a powder X-ray diffractometer (XRD), no crystalline phase containing boron can be detected, so that the B—Li compound exists in an amorphous state. it is conceivable that.
- This B—Li-based compound serves as a kind of protective film, and is considered to be able to prevent elution of manganese particularly at high temperatures.
- the average particle diameter of the boron compound is larger than the range of the present invention, it is considered that the B—Li compound produced excessively during firing strengthens the bond with oxygen.
- this B—Li-based compound film is too thick (when the amount of boron added is excessive), it is considered that the diffusion of oxygen into the lithium manganate lattice, which should have been taken in by firing, is inhibited. Therefore, it is considered that oxygen necessary for the lattice is not completely taken in, the lithium manganate particle powder is in an oxygen deficient state, and the spinel structure is easily distorted. It is considered that the distorted lattice is in a state in which manganese is easily eluted because there is little oxygen that is a binding factor of manganese.
- the boron compound can be unevenly distributed on the surface of the lithium manganate particles by reducing the particle size according to the present invention, the B-Li compound film can be made thin, oxygen deficiency is small, manganese It is considered that lithium manganate particles in which elution of selenium is suppressed are obtained. In the present invention, it is more preferable that the boron compound is uniformly distributed on the surface of the lithium manganate particles.
- lithium manganate particles obtained by the method for producing lithium manganate particles according to the present invention will be described.
- the chemical formula of the lithium manganate particles in the present invention is Li 1 + x Mn 2-xy Y1 y O 4 + B, and Y1 is at least one selected from Ni, Co, Mg, Fe, Al, Cr, and Ti. Preferably there is.
- x is preferably 0.03 to 0.15
- y is preferably 0 to 0.20.
- x When x is less than 0.03, the capacity is increased but the high temperature characteristics are remarkably deteriorated. If it exceeds 0.15, the high temperature characteristics are improved, but the capacity is remarkably lowered or a Li-rich phase is generated, which causes an increase in resistance. More preferably, it is 0.05 to 0.15.
- the capacity drop is large, which is not practical. More preferably, it is 0.01 to 0.20, and still more preferably 0.05 to 0.15.
- Boron is considered to form B-Li compounds and coat lithium manganate particles. Boron is not contained in the lattice of the lithium manganate, and the B—Li compound is present in the vicinity of the particle surface and is considered to exist in an amorphous state.
- This B—Li-based compound serves as a kind of protective film, and is considered to be able to prevent elution of manganese particularly at high temperatures.
- the boron element is also present inside the lithium manganate particles, the stability is lowered when the secondary battery is manufactured.
- the boron content is 0.1 to 2.5 mol% with respect to manganese.
- the B—Li compound does not sufficiently cover the lithium manganate particles, and the effect of suppressing elution of manganese cannot be obtained.
- it exceeds 2.5 mol% fine powder of lithium manganate is generated, and the battery characteristics are deteriorated.
- the boron content is more preferably 0.3 to 2.0 mol% with respect to manganese.
- the average particle diameter (D 50 ) of the secondary particles of the lithium manganate particles in the present invention is preferably 1 to 20 ⁇ m. When the average particle size is less than 1 ⁇ m, the stability decreases. When the average particle diameter exceeds 20 ⁇ m, the output decreases. More preferably, it is 2 to 15 ⁇ m, and still more preferably 3 to 10 ⁇ m.
- the width of the particle size distribution of the secondary particles of the lithium manganate particles in the present invention is preferably (D 90 -D 10 ) of 2 to 30 ⁇ m.
- the particle size distribution exceeds the width (D 90 -D 10 )
- the particle size distribution is wide, which is not preferable.
- a more preferable width of the particle size distribution is 3 to 20 ⁇ m.
- the size of the boron compound added in the present invention is large, the manganese compound is not uniformly applied during firing, and the bonding between the lithium manganate secondary particles is locally increased. Further, since fine powder is generated, the width of (D 90 -D 10 ) is increased.
- the generation of fine powder is suppressed, the binding between secondary particles is reduced, and as a result, the width of (D 90 -D 10 ) can be reduced.
- the average particle diameter of the primary particles constituting the lithium manganate particles in the present invention is 1 ⁇ m or more.
- the primary particle diameter is less than 1 ⁇ m, the stability is lowered. If it exceeds 15 ⁇ m, the output of the secondary battery may decrease. More preferably, it is 1.2 to 13.0 ⁇ m.
- 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
- the binder polytetrafluoroethylene, polyvinylidene fluoride and the like are preferable.
- the secondary battery manufactured using the positive electrode active material in the present invention is composed of the positive electrode, the negative electrode, and the electrolyte.
- lithium metal lithium metal, lithium / aluminum alloy, lithium / tin alloy, graphite, graphite or the like can be used.
- 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.
- An important point in the present invention is to average particle diameter of the boron compound (D 50) in the following 15 times the average particle size of the manganese compound (D 50).
- the sintering aid effect is uniformly distributed throughout the manganese compound particles,
- the B—Li-based compound produced in the firing process is thinly coated on the lithium manganate particles, it is possible to promote strong sintering of the particles even by adding a small amount of a boron compound.
- boron compound if a large amount of boron compound is added, a large amount of fine powder may be generated during pulverization after firing.
- the sintering promoting effect can be sufficiently obtained even by adding a small amount of the boron compound, so that the generation of fine powder during pulverization can be suppressed.
- the lithium compound, the manganese compound, and the boron compound are easily mixed uniformly, and manganese
- a thin film of B-Li compound is produced uniformly, and the thin film makes it easy to absorb oxygen, and as a result, produces a lithium manganate particle powder that is less prone to oxygen deficiency. be able to.
- a typical embodiment of the present invention is as follows.
- the average particle diameter (D 50 ) is a volume-based average particle diameter measured by a wet laser method using a laser type particle size distribution measuring device Microtrac HRA [manufactured by Nikkiso Co., Ltd.] for manganese compounds and lithium manganate. is there.
- the boron compound it is a volume-based average particle diameter measured by a dry laser method using a HELOS particle size distribution measuring apparatus (manufactured by Sympatec).
- the average particle diameter (D 50 ) is a particle diameter at which the cumulative ratio is 50% when the cumulative ratio with respect to the particle diameter is determined with the total volume of the lithium manganate particle powder being 100%. Further, the particle size of which cumulative percentage becomes 10% when the determined cumulative percentage of particle diameter on the total volume of the lithium manganate particles as 100% and D 10, as 100% the total volume of the lithium manganate particles cumulative percentage of time of obtaining the particle diameter expressed in cumulative volume particle diameter at 90% was D 90.
- the width of the particle size distribution (D 90 -D 10 ) is a value obtained by subtracting D 10 from the D 90 .
- the average particle diameter of the primary particles of the lithium manganate particles was read from the SEM image.
- the negative electrode was metallic lithium blanked into diameter of 16 mm, the electrolytic solution 3 EC and DEC in which LiPF 6 was dissolved in 1 mol / l at a volume ratio of: was prepared a coin cell of a CR2032 type using a mixed solution of 7.
- the initial charge / discharge characteristics are as follows: at room temperature, charging is performed at a current density of 0.1 C up to 4.3 V, and after performing constant voltage charging for 90 minutes, discharging is performed at a current density of 0.1 C up to 3.0 V; The initial charge capacity, initial discharge capacity, and initial efficiency at that time were measured.
- a high-temperature cycle test was conducted as a characteristic at high temperatures.
- charge and discharge were performed at a C rate of 0.1 C in the first cycle, the 11th cycle, the 21st cycle, and the 31st cycle at a voltage range of 3.0 to 4.3 V in a 60 ° C constant temperature bath, and other cycles was repeatedly charged and discharged at a rate of 1C.
- the “high temperature cycle capacity retention rate” was the ratio of the discharge capacity at the 31st cycle to the initial discharge capacity.
- the “rate characteristic” is the ratio between the 30th cycle and the 31st cycle (30th cycle / 31st cycle ⁇ 100).
- Oxygen deficiency can be determined by measuring a specific capacity (3.3V Foot) from 3.3 V to 3.0 V at 0.1 C discharge. When oxygen vacancies are generated, a plateau region is generated in the 3.3 V to 3.0 V region during discharge, and the oxygen vacancy state is large when the specific capacity is 1.0 mAh / g or more. It can be said that a large amount of manganese is easily eluted.
- a specific capacity 3.3V Foot
- Example 1 Under nitrogen aeration, 0.5 mol of manganese sulfate was added to 3.5 mol of sodium hydroxide to make the total amount 1 L, and the obtained manganese hydroxide was aged at 90 ° C. for 1 hour. After aging, air was passed through, oxidized at 90 ° C., washed with water and dried to obtain manganese oxide particles.
- the obtained manganese oxide particle powder was Mn 3 O 4 , the particle shape was granular, and the average particle size was 4.8 ⁇ m.
- the aqueous suspension containing the manganese oxide particles was washed with 5 times the amount of water using a filter press, and then poured so that the concentration of the manganese oxide particles became 10 wt%.
- the obtained lithium manganate particle powder In the X-ray diffraction of the obtained lithium manganate particles, no peaks related to the added boron and boron compound were detected, and it was confirmed to be a lithium manganate single phase.
- the SEM image of the obtained lithium manganate particle powder is shown in FIG. 1, and the SEM image of the used boric acid is shown in FIG. As shown in FIG. 1, it can be confirmed that the obtained lithium manganate particle powder is a rounded particle without an angular portion of the particle.
- the obtained lithium manganate particles had a composition of Li 1 + x Mn 2-xy Y1 y O 4 , x was 0.072, y was 0.10, and the average primary particle size was 4 ⁇ m. Yes, the average particle size (D 50 ) of the secondary particles was 8.8 ⁇ m.
- the coin-type battery produced using the positive electrode active material made of the lithium manganate particles obtained here has an initial discharge capacity of 108 mAh / g and a specific capacity (3.3 VFoot) related to oxygen deficiency is 0.223 mAh / g. Met. Further, the capacity retention rate after 31 cycles at 60 ° C. was 97%, and the rate characteristic was 99.6%.
- Examples 2-3 and 5 A lithium manganate particle powder was obtained in the same manner as in Example 1 except that the particle size and firing temperature of the boron compound used were variously changed. The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.
- Example 4 A lithium manganate particle powder was obtained in the same manner as in Example 1 except that the element Y1 covering the manganese oxide compound particles was not used. The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.
- Comparative Example 1 Manganese in the same manner as in Example 1 except that Mn 3 O 4 particle powder having an average secondary particle diameter of 4.8 ⁇ m coated with aluminum hydroxide and boric acid having an average particle diameter (D 50 ) of 193 ⁇ m were used. Lithium acid particle powder was obtained.
- FIG. 3 shows an SEM image of the obtained lithium manganate particles
- FIG. 4 shows an SEM image of boric acid used. The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.
- Comparative Example 2 Lithium manganate particles were obtained in the same manner as in Example 1 except that the average particle sizes of the manganese compound and boron compound used were variously changed. The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.
- Comparative Example 3 Lithium manganate particles powder in the same manner as in Comparative Example 2 except that the particle size of the manganese compound and boron compound to be used and the mixing amount of Li were variously changed, and the Y1 element covering the manganese oxide compound particles was not used. Got. The production conditions at this time are shown in Table 1, and the characteristics of the obtained lithium manganate particles are shown in Table 2.
- the lithium manganate particle powder obtained in Comparative Example 1 generates more fine powder. Moreover, the lithium manganate particle powder obtained in the comparative example has a high specific capacity regarding oxygen deficiency, and is considered to have caused oxygen deficiency. As a result, it is considered that manganese elution is not suppressed, the high-temperature cycle characteristics in the battery are lowered, and at the same time, the rate characteristics are deteriorated.
- the method for producing lithium manganate particles according to the present invention provides lithium manganate suitable as a positive electrode active material for a secondary battery having high crystallinity, high output characteristics, and excellent high-temperature storage characteristics. It is suitable as a method for producing lithium acid particle powder.
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Abstract
Description
本発明において重要な点は、ホウ素化合物の平均粒径(D50)をマンガン化合物の平均粒径(D50)の15倍以下にすることにある。
窒素通気のもと、3.5モルの水酸化ナトリウムに0.5モルの硫酸マンガンを加え全量を1Lとし、得られた水酸化マンガンを90℃で1時間熟成させた。熟成後、空気を通気させ90℃で酸化させ、水洗、乾燥後、酸化マンガン粒子粉末を得た。
用いるホウ素化合物の粒径、焼成温度を種々変化させた以外は、前記実施例1と同様にしてマンガン酸リチウム粒子粉末を得た。このときの製造条件を表1に、得られたマンガン酸リチウム粒子粉末の諸特性を表2に示す。
酸化マンガン化合物粒子を被覆するY1の元素を用いなかったこと以外は、前記実施例1と同様にしてマンガン酸リチウム粒子粉末を得た。このときの製造条件を表1に、得られたマンガン酸リチウム粒子粉末の諸特性を表2に示す。
水酸化アルミニウムで被覆した平均二次粒子径が4.8μmのMn3O4粒子粉末と平均粒径(D50)が193μmのホウ酸とを用いた以外は前記実施例1と同様にしてマンガン酸リチウム粒子粉末を得た。得られたマンガン酸リチウム粒子粉末のSEM像を図3に、使用したホウ酸のSEM像を図4に示す。また、このときの製造条件を表1に、得られたマンガン酸リチウム粒子粉末の諸特性を表2に示す。
用いるマンガン化合物及びホウ素化合物の平均粒径を種々変化させた以外は、前記実施例1と同様にしてマンガン酸リチウム粒子粉末を得た。このときの製造条件を表1に、得られたマンガン酸リチウム粒子粉末の諸特性を表2に示す。
用いるマンガン化合物及びホウ素化合物の粒径、Liの混合量を種々変化させ、酸化マンガン化合物粒子を被覆するY1の元素を用いなかったこと以外は、前記比較例2と同様にしてマンガン酸リチウム粒子粉末を得た。このときの製造条件を表1に、得られたマンガン酸リチウム粒子粉末の諸特性を表2に示す。
Claims (5)
- リチウム化合物、マンガン化合物及びホウ素化合物を混合した後、800℃~1050℃の温度範囲で焼成してマンガン酸リチウム粒子粉末を得る製造方法において、前記ホウ素化合物の平均粒径(D50)がマンガン化合物の平均粒径(D50)の15倍以下であることを特徴とするマンガン酸リチウム粒子粉末の製造方法。
- ホウ素化合物の平均粒径(D50)が1μm~100μmである請求項1に記載のマンガン酸リチウム粒子粉末の製造方法。
- マンガン化合物の平均粒径(D50)が1μm~20μmである請求項1又は2に記載のマンガン酸リチウム粒子粉末の製造方法。
- 得られるマンガン酸リチウム粒子粉末は、粒子径が1μm以上である一次粒子が凝集あるいは焼結した二次粒子で形成されており、化学式:Li1+xMn2-x-yY1yO4+B(Y1=Ni、Co、Mg、Fe、Al、Cr、Tiの中の少なくとも一種、0.03≦x≦0.15、0≦y≦0.20)で表され、マンガン酸リチウム粒子の二次粒子の平均粒径(D50)が1μm~20μmであって、且つ、粒度分布の幅(D90-D10)が2~30μmである請求項1~3のいずれかに記載のマンガン酸リチウム粒子粉末の製造方法。
- 請求項1~4のいずれかに記載のマンガン酸リチウム粒子粉末の製造方法によって得られたマンガン酸リチウム粒子粉末を正極活物質またはその一部として用いた非水電解質二次電池。
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US8852811B2 (en) | 2014-10-07 |
JP2010095439A (ja) | 2010-04-30 |
KR20110061565A (ko) | 2011-06-09 |
CN102149641B (zh) | 2014-12-10 |
US20110210287A1 (en) | 2011-09-01 |
CA2736985A1 (en) | 2010-03-25 |
KR101593725B1 (ko) | 2016-02-12 |
CN102149641A (zh) | 2011-08-10 |
EP2330079A1 (en) | 2011-06-08 |
TW201026607A (en) | 2010-07-16 |
TWI515168B (zh) | 2016-01-01 |
EP2330079A4 (en) | 2013-07-31 |
JP5472602B2 (ja) | 2014-04-16 |
EP2330079B1 (en) | 2018-12-12 |
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