WO2012026539A1 - 電極材料の連続製造方法 - Google Patents
電極材料の連続製造方法 Download PDFInfo
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- WO2012026539A1 WO2012026539A1 PCT/JP2011/069208 JP2011069208W WO2012026539A1 WO 2012026539 A1 WO2012026539 A1 WO 2012026539A1 JP 2011069208 W JP2011069208 W JP 2011069208W WO 2012026539 A1 WO2012026539 A1 WO 2012026539A1
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- 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
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- 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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- 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
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Definitions
- the present invention relates to a method for continuously producing an electrode material of a lithium transition metal composite oxide active material used for a positive electrode or a negative electrode in a lithium secondary battery using insertion and extraction of lithium.
- rechargeable secondary batteries such as Ni-MH alkaline storage batteries and lithium secondary batteries have been put into practical use and widely used with the downsizing, high performance, and portability of electronic devices.
- lightweight non-aqueous electrolyte lithium secondary batteries with high energy density are not only used in small-sized information communication devices such as mobile phones and notebook computers, but also in industrial applications such as automobiles that require high output characteristics. Expansion to large batteries is expected. Therefore, an efficient manufacturing process for these electrode materials is required.
- lithium cobaltate As a typical positive electrode material for a lithium secondary battery, lithium cobaltate (LiCoO 2 ), nickel lithium cobaltate (LiNi 0.85 Co 0.15 O 2 ), nickel cobalt lithium manganate (LiCo 1/3 Ni 1/3) Mn 1/3 O 2 ), lithium manganate (LiMn 2 O 4 ), and lithium titanate (Li 4 Ti 5 O 12 ) are known as negative electrode materials.
- the transition metal compound and the lithium compound, which are precursors are dry mixed and pulverized with powder, the mixture is filled in a mortar, and heated and fired while controlling the atmosphere or atmosphere. Manufactured.
- the contact between the precursor and the lithium compound is insufficient, the decomposition of the precursor decomposition gas (water, carbon dioxide), the supply of atmospheric gas into the mixture and the heat Since the transmission is not sufficiently performed, the filling amount is limited, and firing at a high temperature is required for a long time, which causes problems in quality and productivity.
- the precursor decomposition gas water, carbon dioxide
- Patent Document 1 a method of synthesizing a uniform and high-capacity positive electrode material (Patent Document 1) by performing firing while forcibly ventilating a supply gas to the mixed powder packed bed, and a transition metal compound and A method of pulverizing a lithium compound in an aqueous medium and obtaining a powder solid obtained by uniformly mixing the obtained solid-liquid mixture by spray drying, followed by firing (Patent Document 2), cobalt oxide fine particle powder added with water and lithium A mixture powder with a compound is compression-molded, and this molded body is fired in an oxygen-containing gas for a short time (2 to 10 hours) and then pulverized (Patent Document 3), and the mixed powder is mixed with a rotary kiln or a retort kiln.
- Patent Document 4 and Patent Document 5 A manufacturing method (Patent Document 4 and Patent Document 5) in which a uniform heating and firing is performed while rolling (fluidizing) the packed bed while charging in a rotary furnace. Further, as a continuous manufacturing method, a water-soluble lithium compound is used. When Mixed aqueous solution thinly sprayed deposited onto an endless belt with a precursor compound (1mm or less) is allowed to sequentially firing, a process for the continuous reaction synthesis (Patent Document 6) have been disclosed.
- Japanese Patent Laid-Open No. 5-62678 JP 2009-277667 A Japanese Patent No. 4058797 Japanese Patent Laid-Open No. 06-171947 Japanese Patent No. 3446390 Japanese Patent Publication No. 10-297925
- an object of the present invention is to provide a method capable of continuously producing a stable quality electrode material that is fired uniformly and in a short time.
- the present invention relates to the following matters.
- a step of dispersing a transition metal compound in an aqueous medium of a lithium compound to obtain a mixture Charging the mixture into a rotating cylinder, drying and firing, The method for continuously producing a lithium secondary battery electrode material, wherein the mixture is stirred by a stirring blade provided inside the rotating cylindrical body.
- the stirring blade provided in the inside of the rotating cylinder has a plurality of blade pieces provided so as to contact the inner surface of the rotating cylinder, and the stirring blade rotates by rotating the rotating cylinder, 2.
- the temperature for heating the mixture is 400 ° C. or higher and lower than 1100 ° C., and the heating time is 2 minutes or longer and less than 60 minutes, The manufacturing method as described in.
- transition metal compound is selected from the group consisting of one or more kinds of transition metal hydroxides, oxides, carbonates, and oxalates. .
- a mixture of a transition metal compound and a lithium compound charged in a rotating cylinder can be uniformly stirred and mixed by a stirring blade provided inside the rotating cylinder, and the cylinder Drying and firing can be performed while suppressing adhesion growth of the mixture on the inner surface of the body. Therefore, it is possible to efficiently and continuously produce an electrode material having a uniform and stable quality in a short time.
- the method for producing a lithium secondary battery electrode material of the present invention includes, as one aspect, (Step 1) A step of dispersing a transition metal compound in an aqueous solution medium of a lithium compound to obtain a mixture; (Step 2) charging the mixture into a rotating cylinder, and drying and baking the mixture with stirring blades provided inside the rotating cylinder.
- transition metal compound used in the above is not particularly limited, and examples thereof include transition metal hydroxides, oxides, carbonates, and oxalates having an average primary particle size of 0.1 ⁇ m to 15 ⁇ m. It is done.
- transition metal compounds include those in which two or more transition metal compounds are combined.
- the hydroxide include Co (OH) 2 , Ni (OH) 2 , Mn (OH) 2 , NiOOH, CoOOH, FeOOH, TiO (OH) 2 , Ti (OH) 4 , and complex hydroxides thereof. (Ni 1/3 Co 1/3 Mn 1/3 (OH) 2 , Ni 0.85 Co 0.15 (OH) 2, etc.).
- Examples of the oxide include Co 3 O 4 , NiO, Mn 2 O 3 , MnO 2 , Fe 3 O 4 , Fe 2 O 3 , TiO 2, and complex oxides thereof.
- Examples of the carbonate include NiCO 3 , CoCO 3 , MnCO 3 , basic carbonate and the like (Ni 0.85 Co 0.15 CO 3 and the like), and composite (basic) carbonates thereof.
- Examples of the oxalate include FeC 2 O 4 , CoC 2 O 4 , NiC 2 O 4 , MnC 2 O 4 , and composite oxalates thereof (Ni 0.85 Co 0.15 C 2 O 4 and the like). It is done.
- lithium compound used in the above examples include lithium hydroxide (LiOH, LiOH.H 2 O), lithium carbonate (Li 2 CO 3 ), lithium nitrate, lithium sulfate, lithium acetate, lithium phosphate, diphosphate phosphate.
- Water-soluble compound particles such as lithium hydrogen and lithium monohydrogen phosphate are exemplified.
- the amount ratio of the transition metal compound and the lithium compound used in the above (Step 1) is not particularly limited, and can be appropriately changed so that a target lithium transition metal composite oxide can be obtained.
- Step 1 when the transition metal compound is mixed and dispersed in the lithium compound aqueous solution, the aqueous solution is mixed with an organic solvent (for example, a polar solvent such as an alcohol or an aliphatic ketone compound) in order to wet the surface of the transition metal compound.
- an organic solvent for example, a polar solvent such as an alcohol or an aliphatic ketone compound
- Aromatic compounds such as xylene and toluene, nonpolar solvents such as N-methyl-2-pyrrolidone and dimethyl sulfoxide
- concentration of the organic solvent to be added is not particularly limited, but is preferably 0.5% by weight to 10% by weight with respect to the total weight of the mixture.
- a carbon material to form a composite, conductivity can be imparted to a spinel structure lithium titanium composite oxide or an olivine structure lithium iron phosphate composite having low conductivity.
- the carbon material include carbon fiber, carbon black, and an organic binder.
- the apparatus for efficiently obtaining the mixture is not particularly limited.
- a device that generates shearing force and impact force such as a vibration ball mill, an attritor type high-speed ball mill, a bead mill, and a roll mill can be used.
- the mixture obtained by (Step 1) preferably has a solid concentration of 10% by mass or more. If the solid concentration is too low, in the later-described (Step 2), the load at the time of drying becomes large, which hinders the production efficiency of the electrode material.
- the solid substance concentration represents the mass concentration of all additives present as a solid substance without dissolving in the lithium aqueous solution and the organic solvent for wetting described above.
- the measurement method is to weigh a certain amount of the mixture obtained in (Step 1) ⁇ A (g) ⁇ , then filter and dry the weight measurement mixture, and measure the weight of the remaining dry matter ⁇ B (g) ⁇ .
- Step 2 is performed using, for example, an apparatus having a rotating cylinder and drying and firing the mixture while stirring the mixture with at least one stirring blade provided inside the rotating cylinder. be able to.
- the stirring blade provided in the inside of the rotating cylinder has a plurality of blade pieces radially and equally spaced, and at least one tip of the blade pieces is in contact with the inner surface of the cylinder. It is preferable that the stirring blades are also rotated by the rotation. By rotating the stirring blade, the mixture in the cylindrical body is stirred and lifted by the blades of the stirring blade, and the mixture is prevented from growing on the inner surface of the cylindrical body, and contact with the gas in the rotating cylinder. And the heat transfer is kept good.
- the rotating cylindrical body is preferably inclined with respect to the horizontal plane, and the mixture in the cylindrical body is sequentially sent from the charging side to the taking-out side, and undergoes drying and baking during that time.
- the inclination angle with respect to the horizontal plane is preferably 1 degree or more and 10 degrees or less. If the inclination angle is too small, it is difficult to discharge the product, and regular recovery is impossible. If the inclination angle is too large, the residence time of the raw materials and the like in the rotating cylinder will be extremely short (less than 2 minutes), and drying and firing of the mixture described later will be insufficient.
- the rotational speed of the rotating cylindrical body is preferably 5 rpm or more and 40 rpm or less. If the rotation speed is too low, the residence time of the mixture is short, drying becomes insufficient, and at the same time, the mixture adheres to the inner surface of the cylindrical body. When the rotation speed is too high, the stirring effect of the mixture is not observed.
- the blade of the stirring blade and the rotating cylinder are not particularly limited, but preferably contain an alloy mainly composed of nickel or the like.
- nickel when nickel is the main component, it is preferable to contain 10 mass% or more and 95 mass% or less of nickel.
- the above apparatus can control the internal temperature to a predetermined temperature.
- the heating method may be a method using either an external or internal heating source, but external heating is preferable in consideration of firing atmosphere control described later.
- the mixture obtained in (Step 1) is charged into the rotating cylinder.
- the mixture is preferably directly charged in a slurry state, and raw material charging means for quantitatively charging the mixture into a rotating cylinder may be used. If the fluidity of the mixture is low, it may be charged with a screw.
- the heating temperature in the rotating cylinder is not particularly limited, but is preferably 400 ° C. or higher and lower than 1100 ° C.
- the temperature in the firing step is preferably 700 ° C. or more and less than 1100 ° C., and producing a lithium transition metal composite oxide having an olivine structure.
- the temperature is preferably 500 ° C. or higher and lower than 700 ° C.
- the heating time can be changed depending on the tilt angle and rotation speed of the rotating cylindrical body, and is not particularly limited, but is preferably 2 minutes or more and less than 60 minutes. If the heating time is too short, the crystallization of the electrode material will not proceed sufficiently, and the crystallinity will not change even if the heating time is too long.
- the atmospheric gas in the rotating cylinder can be prepared by the supplied atmospheric gas, and the apparatus having the rotating cylinder may further have means for controlling the atmospheric gas.
- the atmosphere gas can be appropriately changed so that the target lithium transition metal composite oxide can be obtained.
- oxygen gas is used as the layered structure lithium nickel.
- cobalt manganese composite oxide air is used.
- inert gas or reducing gas such as hydrogen gas or carbon monoxide gas is used.
- the lithium transition metal composite oxide that can be produced according to the present invention is not particularly limited.
- a layered structure of lithium cobaltate, lithium nickelate, lithium nickel cobalt manganese composite oxide, lithium nickel cobalt aluminum composite oxide examples thereof include lithium manganate having a spinel structure, lithium titanate, and the like, and lithium iron phosphate having an olivine structure.
- the electrolyte of the lithium secondary battery contains a lithium compound as a solute that exhibits ionic conductivity, It can be used as long as the solvent that dissolves and retains the solute does not decompose during charge / discharge or storage of the battery.
- solutes include LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3, etc.
- solvents include ethylene carbonate (EC), Cyclic carbonates such as propylene carbonate (PC) and vinylene carbonate (VC), chain carbonates such as dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), and diethyl carbonate (DEC), tetrahydrofuran (THF), 2 methyl tetrahydrofuran (2 MeTHF) ), Cyclic ethers such as dimethoxyethane (DME), ⁇ -butyrolactone (BL), acetonitrile (AN), sulfolane (SL), and sultone such as 1,3-propane sultone and 1,3-propene sultone
- the organic solvents can be used singly or in combination.
- electrolyte a gel polymer electrolyte in which a polymer electrolyte such as polyethylene oxide or polyacrylonitrile is impregnated with an electrolytic solution, or an inorganic solid electrolyte such as LiI can be used.
- the measurement methods in the following examples are as follows.
- the specific surface area was determined by a BET one-point continuous method using a Macsorb HM-model 1208 (MOUNTECH Co., Ltd.) after drying and degassing the calcined material sample at 100 ° C. for 30 minutes under a nitrogen gas flow.
- Example 1 Anatase-type titanium dioxide particles having an average primary particle diameter of 150 nm ⁇ TiO 2 (molecular weight 79.658) (Sakai Chemical Industry Co., Ltd. SA-1, average primary particle diameter 0.15 ⁇ m, specific surface area 9.7 m 2 / g) ⁇ 29 0.1% by mass and lithium carbonate particles ⁇ Li 2 CO 3 (molecular weight 73.8909) (60M manufactured by Kennametal, average primary particle size 5.3 ⁇ m, specific surface area 1.4 m 2 / g) ⁇ 11.0% by mass Then, 58.1% by mass of ion-exchanged water and 1.8% by mass of ethanol were mixed by stirring to prepare a mixture (solid content concentration 41% by mass, Li / Ti molar ratio 0.82).
- the obtained lithium titanium composite oxide had an average particle size of 0.35 ⁇ m and a specific surface area of 9 m 2 / g, and showed a single phase of Li 4 Ti 5 O 12 from crystal structure analysis (XRD) of X-ray diffraction.
- the mixture Li / Ti molar ratio 0.82 was filled in an alumina sagger, left in a muffle furnace, and fired at 850 ° C. in the atmosphere.
- the heating method was performed with a temperature rising time of 90 minutes, a 850 ° C. holding time of 90 minutes, and a cooling time of 120 minutes.
- the obtained lithium-titanium composite oxide has an average particle diameter of 0.5 ⁇ m and a specific surface area of 3 m 2 / g. From the crystal structure analysis (XRD) of X-ray diffraction, Li 4 Ti 5 O 12 and anatase TiO 2 Two phases were shown.
- XRD crystal structure analysis
- Example 2 Using the same rotating cylindrical body heating apparatus as in Example 1, a lithium-titanium composite oxide composited with fine carbon fibers using fine carbon fiber aggregates, titanium dioxide particles, and lithium hydroxide was subjected to the following procedure.
- Manufactured with. (1) Preparation of fine carbon fiber dispersion liquid of fine carbon fibers (AMC specific area surface area 230 m 2 / g, average outer diameter 11 nm, average inner diameter 6 nm, length 0.5 ⁇ m to 10 ⁇ m, manufactured by Ube Industries) 5 parts by weight of the aggregate was added to and mixed with an aqueous solution in which 1 part by weight of carboxymethyl cellulose (Daicel Finechem Co., Ltd.
- the inclination angle of the cylindrical rotating body was 2.5 degrees, the rotation speed was 20 rpm, and the mixture was charged, dried and fired while flowing 15 L / min of nitrogen gas from the collection side.
- the heating temperature of the cylindrical rotating body was 700 ° C. on the supply side, 900 ° C. in the center, and 900 ° C. on the recovery side, and the residence time of the heating part was 20 minutes.
- the lithium-titanium composite oxide obtained by the above, in which fine carbon fibers are complexed in a network shape, has an average particle size of 0.4 ⁇ m and a specific surface area of 14 m 2 / g. From the crystal structure analysis (XRD) of X-ray diffraction A single phase of Li 4 Ti 5 O 12 was shown. The lithium titanium composite oxide particles combined with the fine carbon fibers were pressurized to 100 kg / cm 2 G and measured with a DC resistance meter. The volume resistivity was 3 ⁇ 10 1 ⁇ ⁇ cm.
- Example 3 Using the same rotating cylindrical body heating apparatus as in Example 1, fine carbon fiber aggregates, magnetite particles, lithium carbonate, and lithium iron phosphate complexed with fine carbon fibers using phosphoric acid were obtained by the following procedure. Manufactured.
- Magnetite particles Fe 3 O 4 molecular weight 231.533 (Titanium Industry Co., Ltd., BL-100, specific surface area 5.5 m 2 / g) 14.3% by mass, and the fine particles prepared in Example 2 (1)
- Carbon fiber dispersion fine carbon fiber content 5 mass% was added and stirred and mixed to obtain a mixture (solid content 22.3 mass%, Li / Fe molar ratio 1.00, Li / Fe P molar ratio 1.00) was produced.
- the mixture was charged into a cylindrical rotating body (inclination angle of 3 °, rotation speed of 30 rpm) while hydrogen gas 7.5 L / min (about 1.5 times the theoretical amount) was allowed to flow from the recovery side, and dried. Firing was performed.
- the heating temperature of the cylindrical rotating body was 500 ° C. on the supply side, 600 ° C. in the center, and 600 ° C. on the recovery side, and the residence time of the heating part was 15 minutes.
- the resulting lithium iron phosphate composite oxide in which fine carbon fibers are complexed in a network, has an aggregate average particle size of 2.3 ⁇ m and a specific surface area of 13 m 2 / g, and crystal structure analysis of X-ray diffraction ( XRD) showed a single phase of lithium iron phosphate.
- XRD X-ray diffraction
- Example 4 Using the same rotating cylindrical body heating apparatus as in Example 1, nickel cobalt hydroxide, aluminum hydroxide, and lithium nickel cobalt aluminum composite oxide using the same lithium hydroxide as used in Example 2 were subjected to the following procedure. Manufactured with.
- Nickel cobalt hydroxide Ni 0.85 Co 0.15 (OH) 2 (molecular weight 92.744405)) (Honjo Chemical Co., Ltd. nickel hydroxide 10 ⁇ m type, specific surface area 6 m 2 / g, average particle diameter 10 ⁇ m) 47.3% by mass, aluminum hydroxide particles (Al (OH) 2 (molecular weight 78.003558)) 1.21% by mass, lithium hydroxide 23.1% by mass, ion-exchanged water 28.4% by mass, Were mixed by stirring to prepare a water-soluble mixture (solid content concentration 71.6% by mass, Li / (Ni + Co + Al) molar ratio 1.05).
- the mixture was charged into a rotating cylindrical body (inclination angle of 7 degrees, rotation speed of 30 rpm) while flowing 15 L / min of oxygen gas from the recovery side, and dried and fired.
- the heating temperature of the cylindrical rotating body was 600 ° C. on the supply side, 800 ° C. in the center, and 800 ° C. on the recovery side, and the residence time in the heating portion was 6 minutes.
- the lithium nickel cobalt aluminum composite oxide particles (LiNi 0.83 Co 0.14 Al 0.03 O 2 ) thus obtained have an average particle diameter of 10 ⁇ m, a specific surface area of 0.3 m 2 / g, and a bulk density of 1.8 g. / ML.
- Example 2 The mixture prepared in Example 4 was charged into the rotating cylinder under the same conditions as in Example 4 except that a rotating cylinder without stirring blades was used. One minute after the start of charging the mixture, it was discharged in a slurry state from the outlet of the cylindrical rotating body, and drying and firing did not proceed. Furthermore, dry matter adhered to the rotary cylinder inlet side, making it difficult to charge the mixture.
- Example 5 Using the same rotating cylindrical body heating apparatus as in Example 1, a lithium nickel cobalt manganese composite oxide was produced by the following procedure.
- Nickel cobalt manganese hydroxide Ni 1/3 Co 1/3 Mn 1/3 (OH) 2 (molecular weight 91.56323)) (Honjo Chemical Co., Ltd. nickel hydroxide cobalt manganese 10 ⁇ m type, specific surface area 7.5 m 2 / g, average particle diameter 11 ⁇ m) 49.2% by mass, lithium hydroxide (same as that used in Example 2) 23.7% by mass, and ion-exchanged water 27.1% by mass were mixed. , A mixture (solid concentration 72.9% by mass, Li / (Ni + Co + Mn) molar ratio 1.05) was prepared.
- the mixture was charged into a rotating cylindrical body (inclination angle of 5 degrees, rotation speed of 30 rpm) while flowing 15 L / min of air from the collection side, and dried and fired.
- the heating temperature of the rotating cylinder was 600 ° C. on the supply side, 950 ° C. in the center, and 900 ° C. on the recovery side, and the residence time of the heated portion was 11 minutes.
- the lithium nickel cobalt manganese composite oxide particles (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) had an average particle diameter of 11 ⁇ m, a specific surface area of 0.2 m 2 / g, and a bulk density of 1.7 g / mL. .
- the lithium nickel cobalt manganese composite oxide particles (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) had an average particle diameter of 11 ⁇ m, a specific surface area of 0.3 m 2 / g, and a bulk density of 1.6 g / mL. .
- the electrode materials obtained in the above examples and comparative examples were respectively used as positive electrode active materials, and the electrode materials, acetylene black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) and polyvinylidene fluoride (PVDF) (Kureha KF Polymer) ) was kneaded in a kneader using N-methylpyrrolidone as a solvent at a mass ratio of 90: 5: 5 to prepare an electrode slurry. After applying the electrode paste to the aluminum mesh substrate, vacuum drying was performed at 150 ° C. to prepare a positive electrode plate (15 mm ⁇ ).
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Abstract
Description
前記混合物を回転円筒体内に装入し、乾燥および焼成する工程とを有し、
前記回転円筒体の内部に備えられた撹拌羽により前記混合物が撹拌されることを特徴とするリチウム二次電池電極材料の連続製造方法。
本発明のリチウム二次電池電極材料の製造方法は、1つの態様として、
(工程1)リチウム化合物の水溶液媒体中、遷移金属化合物を分散させて混合物を得る工程と、
(工程2)前記混合物を、回転円筒体に装入し、該回転円筒体の内部に備えられた攪拌羽により前記混合物を乾燥、焼成する工程と
を含む。
上記(工程1)に用いる遷移金属化合物としては、特に限定されないが、たとえば、平均一次粒子径0.1μm以上、15μm以下の遷移金属の水酸化物、酸化物、炭酸塩、シュウ酸塩が挙げられる。本発明において、遷移金属化合物には、2種以上の遷移金属化合物が複合化されているものを含む。水酸化物としては、Co(OH)2、Ni(OH)2、Mn(OH)2、NiOOH、CoOOH、FeOOH、TiO(OH)2、Ti(OH)4等、およびこれらの複合水酸化物(Ni1/3Co1/3Mn1/3(OH)2、Ni0.85Co0.15(OH)2等)が挙げられる。酸化物としては、Co3O4、NiO、Mn2O3、MnO2、Fe3O4、Fe2O3、TiO2等およびこれらの複合酸化物が挙げられる。炭酸塩としては、NiCO3、CoCO3、MnCO3、塩基性炭酸塩等(Ni0.85Co0.15CO3等)、およびこれらの複合(塩基性)炭酸塩等が挙げられる。シュウ酸塩としては、FeC2O4、CoC2O4、NiC2O4、MnC2O4、およびこれらの複合シュウ酸塩(Ni0.85Co0.15C2O4等)が挙げられる。
上記(工程1)に用いるリチウム化合物としては、水酸化リチウム(LiOH、LiOH・H2O)、炭酸リチウム(Li2CO3)、硝酸リチウム、硫酸リチウム、酢酸リチウム、リン酸リチウム、リン酸二水素リチウム、リン酸一水素リチウムなどの水溶性化合物粒子等が挙げられる。
上記(工程1)において、リチウム化合物水溶液中に遷移金属化合物を混合して分散させる際に、遷移金属化合物表面を湿潤させるため、水溶液に有機溶媒(たとえば、アルコール、脂肪族ケトン化合物等の極性溶媒、キシレン、トルエン等の芳香族化合物、N-メチル-2-ピロリドン、ジメチルスルホキシド等非極性溶媒等)を添加してもよい。添加する有機溶媒の濃度は、特に限定はされないが、混合物全体の重量に対し、0.5重量%~10重量%であることが好ましい。
装入された混合物は、加熱された回転円筒体内の攪拌羽によって液滴状に掻き揚げられ、流動、浮遊しながら、円筒体表面及びガス中で急速に乾燥固化、脱水分解される。この乾燥固化された混合物がさらに加熱され、回転円筒体内で、撹拌、掻き揚げられながら、焼成される。本発明は、混合物を乾燥、焼成する工程において、上記撹拌羽を備えた回転円筒体を用いることにより、従来の方法に比べて、回転円筒体内面への付着物がない、混合物がより均一に複合化される、加熱時間が短縮化される等の利点がある。
回転円筒体内の雰囲気ガスは、供給される雰囲気ガスによって調製することができ、回転円筒体を有する上記装置が、さらに雰囲気ガスを制御する手段を有していてもよい。雰囲気ガスは、目的とするリチウム遷移金属複合酸化物が得られるように、適宜変更することができるが、たとえば、層状構造リチウムニッケルコバルト複合酸化物を製造するときは酸素ガスを、層状構造リチウムニッケルコバルトマンガン複合酸化物を製造するときは空気を、オリビン構造リチウム鉄リン酸複合酸化物を製造するときは不活性ガス、または水素ガス、一酸化炭素ガス等の還元性ガスを、スピネル構造リチウムチタン複合酸化物を製造するときは空気または不活性ガスを導入することが好ましい。
本発明により製造することができるリチウム遷移金属複合酸化物としては、特に限定はされないが、たとえば、層状構造のコバルト酸リチウム、ニッケル酸リチウム、リチウムニッケルコバルトマンガン複合酸化物、リチウムニッケルコバルトアルミ複合酸化物等、スピネル構造のマンガン酸リチウム、チタン酸リチウム等、オリビン構造のリン酸鉄リチウム等を挙げることができる。
本発明の製造方法により製造されたリチウム遷移金属複合酸化物を、リチウム二次電池の電極材料として用いる場合、リチウム二次電池の電解質は、イオン導電性を発現させる溶質としてのリチウム化合物を含み、溶質を溶解、保持する溶媒が電池の充放電時又は保存時において分解しない限り用いることができる。具体的な溶質としては、LiClO4、LiPF6、LiBF4、LiCF3SO3、LiN(CF3SO2)2、LiC(CF3SO2)3等、溶媒としては、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、ビニレンカーボネート(VC)等の環状カーボネート、ジメチルカーボネート(DMC)、メチルエチルカーボネート(MEC)、ジエチルカーボネート(DEC)等の鎖状カーボネート、テトラヒドロフラン(THF)、2メチルテトラヒドロフラン(2MeTHF)等の環状エーテル、ジメトキシエタン(DME)等の鎖状エーテル、γ―ブチロラクトン(BL)、アセトニトリル(AN)、スルホラン(SL)及び1,3-プロパンスルトン、1,3-プロペンスルトン等のスルトン類が挙げられ、これらの有機溶媒は、単独又は2種以上の混合物で用いることができる。更に電解質として、ポリエチレンオキシド、ポリアクリロニトリル等のポリマー電解質に電解液を含浸したゲル状ポリマー電解質や、LiI等の無機固体電解質を用いることができる。
<固形物濃度>
混合物の固形物濃度は、リチウム化合物の水溶液媒体中、遷移金属化合物を分散させた混合物100mLを採取し、重量測定後ろ過し、残存物をテフロン(登録商標)ビーカーに移し、110℃、5時間乾燥した後、乾燥物の重量を測定し、個々の重量から質量濃度を算出した。
<平均粒子径>
焼成物の平均粒子径は、レーザー回折・散乱型粒度分布計Microtrac MT3300EXII(日機装株式会社製)を用いて定量化した。
<比表面積>
比表面積は、焼成物試料を窒素ガス流通下、100℃、30分間乾燥脱気した後、Macsorb HM-model1208(株式会社 MOUNTECH)を用いてBET1点連続法により求めた。
平均一次粒子径150nmのアナターゼ型二酸化チタン粒子{TiO2(分子量79.8658)(堺化学工業(株)SA-1、平均一次粒子径0.15μm、比表面積9.7m2/g)}29.1質量%と、炭酸リチウム粒子{Li2CO3(分子量73.8909)(ケナメタル社製60M、平均一次粒子径5.3μm、比表面積1.4m2/g)}11.0質量%と、イオン交換水58.1質量%と、エタノール1.8質量%とを攪拌混合して混合物(固形分濃度41質量%、Li/Tiモル比0.82)を作製した。該混合物について、傾斜角度5度、回転速度30rpmの円筒回転体(炉体長さ:5m、炉芯管直径:20cm、攪拌羽:中心から羽先端長さ9cm、10枚)を用いて、空気15L/分を回収側から流しながら、乾燥、焼成処理を行った。円筒回転体の加熱温度は、供給側700℃、中央部850℃、回収側850℃であり、加熱部分の滞留時間は7分であった。得られたリチウムチタン複合酸化物は、平均粒子径0.35μm、比表面積9m2/gであり、X線回折の結晶構造解析(XRD)からLi4Ti5O12の単相を示した。
実施例1で使用したものと同じアナターゼ型二酸化チタン粒子72.6質量%と、炭酸リチウム粒子27.4質量%とを、混合機(日本コークス工業(株)FMミキサー)で30分間攪拌混合した。混合物(Li/Tiモル比0.82)をアルミナ製匣鉢に充填し、マッフル炉に静置して大気中850℃にて焼成した。加熱方法は、昇温時間90分、850℃保持時間90分、冷却時間120分で行った。得られたリチウムチタン複合酸化物は、平均粒子径0.5μm、比表面積3m2/gであり、X線回折の結晶構造解析(XRD)からLi4Ti5O12とアナターゼ型TiO2との2相を示した。
実施例1と同一の回転円筒体加熱装置を用い、微細な炭素繊維凝集体、二酸化チタン粒子、および水酸化リチウムを用いて微細な炭素繊維で複合化されたリチウムチタン複合酸化物を以下の手順で製造した。
(1)微細な炭素繊維分散液の調製
微細な炭素繊維(宇部興産(株)製AMC 比面積表面積230m2/g、平均外径11nm、平均内径6nm、長さ0.5μmから10μm)の凝集体5重量部を、カルボキシメチルセルロース(ダイセルファインケム(株)CMCダイセル1110)1重量部をイオン交換水94重量部に溶解した水溶液に添加、混合した後、超音波発生装置((株)日本精機製作所Ultrasonic Homogenizer MODEL US-600T)にて40分開繊、分散処理をおこない、微細な炭素繊維を5質量%含有する微細な炭素繊維分散液を調製した。
(2)焼成用混合物の調製と、微細な炭素繊維と複合化されたリチウムチタン複合酸化物粒子の製造
水酸化リチウム粒子(LiOH・H2O(分子量41.96362))(本荘ケミカル(株)製ザラメ状)12.6質量%と、ルチル型二酸化チタン粒子(TiO2(分子量79.8658))(デユポン社製R-101、平均一次粒子径0.29μm)29.1質量%と、上記(1)で製造した微細な炭素繊維分散液(微細な炭素繊維含有量5質量%)23.3質量%と、イオン交換水35.0質量%とを攪拌混合し、混合物(固形分濃度42.9質量%、Li/Tiモル比0.82)を作製した。円筒回転体の傾斜角度を2.5度、回転速度を20rpmとし、窒素ガス15L/分を回収側から流しながら、該混合物を装入し、乾燥、焼成を行った。円筒回転体の加熱温度は、供給側700℃、中央部900℃、回収側900℃であり、加熱部分の滞留時間は20分であった。
実施例1と同一の回転円筒体加熱装置を用い、微細な炭素繊維凝集体、マグネタイト粒子、炭酸リチウム、およびリン酸を用いて微細な炭素繊維と複合化したリン酸鉄リチウムを以下の手順で製造した。
実施例1と同一の回転円筒体加熱装置を用い、ニッケルコバルト水酸化物、水酸化アルミニウム、実施例2で用いたものと同じ水酸化リチウムを用いてリチウムニッケルコバルトアルミ複合酸化物を以下の手順で製造した。
実施例4で調製した混合物を、攪拌羽が無い回転円筒体を用いた以外は実施例4と同一条件で、回転円筒体に装入した。該混合物を装入開始した1分後に、円筒回転体出口よりスラリー状態で排出され、乾燥、焼成は進まなかった。更に回転円筒体入口側で、乾燥物が付着し、該混合物の装入が困難となった。
実施例1と同一の回転円筒体加熱装置を用い、リチウムニッケルコバルトマンガン複合酸化物を以下の手順で製造した。
実施例5で用いたものと同じニッケルコバルトマンガン水酸化物67.5質量%と、水酸化リチウム32.5質量%とを混合機(日本コークス工業(株)FMミキサー)で30分間攪拌混合した。混合物(Li/(Ni+Co+Mn)モル比1.05)をアルミナ製匣鉢に充填し、マッフル炉に静置して大気中で昇温時間120分、950℃保持時間120分、冷却時間150分で行った。
Claims (10)
- リチウム化合物の水溶液媒体中、遷移金属化合物を分散させて混合物を得る工程と、
前記混合物を回転円筒体内に装入し、乾燥および焼成する工程とを有し、
前記回転円筒体の内部に備えられた撹拌羽により前記混合物が撹拌されることを特徴とするリチウム二次電池電極材料の連続製造方法。 - 前記回転円筒体の内部に備えられた撹拌羽が、回転円筒体内面に接触するように備えられた複数個の翼片を有し、回転円筒体が回転することにより撹拌羽が回転し、前記混合物を、掻き揚げ、流動、浮遊させることを特徴とする、請求項1に記載の製造方法。
- 前記乾燥および焼成する工程において、前記混合物を加熱する温度が、400℃以上、1100℃未満であり、かつ、加熱する時間が、2分以上60分未満であることを特徴とする請求項1または2に記載の製造方法。
- 前記回転円筒体が、水平面に対して1度以上、10度以下で傾斜していることを特徴とする請求項1~3のいずれか1項に記載の製造方法。
- 前記回転円筒体の回転速度が、5rpm以上40rpm以下であることを特徴とする請求項1~4のいずれか1項に記載の製造方法。
- 前記回転円筒体及び撹拌羽が、10質量%以上のニッケルを主成分とする合金からなることを特徴とする請求項1~5のいずれか1項に記載の製造方法。
- 前記遷移金属化合物が、1種類以上の遷移金属の水酸化物、酸化物、炭酸塩、シュウ酸塩からなる群から選択されることを特徴とする請求項1~6のいずれか1項に記載の製造方法。
- 前記混合物に含まれる固形物濃度が10質量%以上である請求項1~7のいずれか1項に記載の製造方法。
- 前記混合物が低級アルコール化合物または脂肪族ケトン化合物を含有することを特徴とする請求項1~8のいずれか1項に記載の製造方法。
- 請求項1~9のいずれか1項に記載の製造方法により製造され、層状構造、スピネル構造、またはオリビン構造を有するリチウム二次電池電極材料。
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JP5569258B2 (ja) | 2014-08-13 |
CN103098269B (zh) | 2016-01-20 |
US20130146809A1 (en) | 2013-06-13 |
TW201222951A (en) | 2012-06-01 |
CN103098269A (zh) | 2013-05-08 |
KR20130106380A (ko) | 2013-09-27 |
JP2012048968A (ja) | 2012-03-08 |
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