WO2012133584A1 - Matériau actif d'électrode positive pour batterie secondaire, électrode positive pour batterie secondaire, et procédé de production de batterie secondaire - Google Patents

Matériau actif d'électrode positive pour batterie secondaire, électrode positive pour batterie secondaire, et procédé de production de batterie secondaire Download PDF

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WO2012133584A1
WO2012133584A1 PCT/JP2012/058241 JP2012058241W WO2012133584A1 WO 2012133584 A1 WO2012133584 A1 WO 2012133584A1 JP 2012058241 W JP2012058241 W JP 2012058241W WO 2012133584 A1 WO2012133584 A1 WO 2012133584A1
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positive electrode
secondary battery
active material
electrode active
group
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PCT/JP2012/058241
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English (en)
Japanese (ja)
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酒井　智弘
義久 別府
浩之 朝長
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旭硝子株式会社
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Priority to JP2013507695A priority Critical patent/JPWO2012133584A1/ja
Publication of WO2012133584A1 publication Critical patent/WO2012133584A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode active material for a secondary battery, a positive electrode for a secondary battery, and a method for manufacturing the secondary battery.
  • Patent Document 1 after synthesizing lithium iron phosphate by a hydrothermal method, a conductive carbon layer was formed on the surface of lithium iron phosphate by mixing and baking with sucrose and then pulverizing. A method for producing a positive electrode material is described. Furthermore, it is described that acetylene black is mixed in the obtained positive electrode material.
  • Patent Document 2 FePO 4 and Li 2 CO 3 are pulverized in the presence of isopropanol, calcined in a reducing gas to obtain an olivine-type phosphate compound, cellulose acetate dissolved in acetone, etc. A method of obtaining an olivine-type phosphate compound containing carbon by impregnating with a carbon source solution and calcining is described.
  • Patent Document 3 discloses a precursor obtained by melting a raw material comprising a compound that can be a phosphorus source, a lithium source, and an iron source to obtain a precursor glass of lithium iron phosphate, and then pulverizing the precursor glass.
  • a method of activating a carbon-based conductive active material derived from an organic compound in crystallized glass by mixing an organic compound as a carbon source in glass powder and firing in an inert or reducing atmosphere is described.
  • Patent Document 1 is a method of synthesizing a positive electrode material made of lithium iron phosphate by putting lithium phosphate, divalent iron chloride tetrahydrate and water into a pressure vessel. Therefore, productivity is inferior. Since pulverization is performed after the lithium iron phosphate and sucrose are fired, a surface of the pulverized particles that is not coated with carbon is generated. Therefore, the positive electrode material may not exhibit sufficient electrical conductivity. In the method described in Patent Document 2, since the pulverization step is omitted, the particle size of the olivine type compound is not controlled, and desired characteristics cannot be obtained.
  • the gist of the present invention is the following [1] to [16].
  • the raw material containing element A, element M, element X and element Z is adjusted so that the molar ratio of element A, element M, element X and element Z is the molar ratio represented by the following formula (2) Heating the raw material formulation to obtain a melt, A cooling step of cooling the melt to obtain a solidified product, A pulverization step for obtaining a pulverized product comprising the solidified product and an organic compound, and a surface of a compound having a composition represented by the following formula (2) by heating the pulverized product in an inert gas or a reducing gas A heating step of obtaining a positive electrode active material for a secondary battery in which at least a part of the electrode is coated with conductive carbon, A method for producing a positive electrode active material for a secondary battery, characterized in that For secondary batteries, wherein the organic compound is an organic compound having a residue ratio of 15% by mass or less when heated at 700 ° C.
  • a method for producing a positive electrode active material A a M b X c O d Ze (2) (In the formula (2), A is at least one element selected from the group consisting of Li, Na and K, M is at least one element selected from the group consisting of Fe, Mn, Co and Ni, and X is Si. , Z represents a halogen atom, a is 0.8 ⁇ a ⁇ 2.7, b is 0.6 ⁇ b ⁇ 1.4, c is 0.9 ⁇ c ⁇ 1.1, d is a, (The number depends on the numerical values of b, c and e, and the valence of M and the valence of X.
  • the surface of the compound having the composition represented by the formula (2) means the surface of the compound particle having the composition represented by the formula (2).
  • a method for producing a positive electrode active material for a battery A a M b X c O d1 Z e1 (1) (In the formula (1), A is at least one element selected from the group consisting of Li, Na and K, M is at least one element selected from the group consisting of Fe, Mn, Co and Ni, and X is Si.
  • Z represents a halogen atom
  • a is 0.8 ⁇ a ⁇ 2.7
  • b is 0.6 ⁇ b ⁇ 1.4
  • c is 0.9 ⁇ c ⁇ 1.1
  • d1 is a, b, c, and the number of e1, and the number that depends on the valence of M and the valence of X, and is a number that becomes d after the heating step
  • e1 is e1 ⁇ a, and 0 ⁇ e1 ⁇ 2.
  • a a M b X c O d Ze (2) (In the formula (2), A, M and X represent the same kind of element as described above, a, b and c represent the same numerical range as described above, but are values independent of the above, d is a, (The number depends on the numerical values of b, c and e, and the valence of M and the valence of X.
  • e is e ⁇ a and 0 ⁇ e ⁇ 2.2.
  • the pulverizing step is a step of pulverizing a mixture of the solidified product and the organic compound, or a step of pulverizing the solidified product and the organic compound.
  • the organic compound has at least one selected from the group consisting of a hydroxyl group or a hydroxyl group-derived group, a carboxyl group or a carboxyl group-derived group, a sulfonic acid group or a sulfonic acid group-derived group, and etheric oxygen.
  • the aforesaid At least one compound selected from the group consisting of aliphatic acyclic polymers, fatty acids, cellulose or cellulose derivatives, bicyclic monoterpenes or bicyclic monoterpene derivatives, and heterocyclic amines, [1]
  • a method for producing a substance At least one selected from the group consisting of polyvinyl alcohol, ethyl cellulose, melamine, and camphor.
  • the solvent is at least one selected from the group consisting of water, ethanol, isopropyl alcohol, acetone, hexane, and toluene.
  • the melting step includes A compound containing A is A carbonate, A bicarbonate, A hydroxide, A silicate, A phosphate, A borate, A fluoride, A chloride , At least one selected from the group consisting of A nitrate, A sulfate, and A organic acid salt (however, at least one of the at least one may form a hydrate salt).
  • a compound containing M is M oxide, M hydroxide, M oxyhydroxide, M silicate, M phosphate, M borate, metal M, M fluoride, Included as at least one selected from the group consisting of M chloride, M nitrate, M sulfate, M organic acid salt and M alkoxide,
  • a compound containing X is included as at least one selected from the group consisting of an oxide of X, an alkoxide of X, and an A or M silicate;
  • a compound containing Z is included as at least one selected from the group consisting of A or M fluoride and A or M chloride;
  • the positive electrode active material for a secondary battery is any one of the above [1] to [13], wherein the olivine type crystal structure particles are coated at least part of the surface with conductive carbon.
  • the manufacturing method of the positive electrode active material for secondary batteries [15] A positive electrode active material for a secondary battery is obtained by the manufacturing method according to any one of [1] to [14], and then the positive electrode active material for a secondary battery is used for the secondary battery. A method for producing a positive electrode for a secondary battery, comprising producing a positive electrode. [16] A method for producing a secondary battery, comprising: obtaining a positive electrode for a secondary battery by the production method according to [15], and then producing a secondary battery using the positive electrode for a secondary battery. .
  • the electrical conductivity of the positive electrode active material for a secondary battery can be enhanced and the composition and particle size can be controlled well. Therefore, by using the positive electrode active material for a secondary battery, a positive electrode for a secondary battery and a secondary battery that are excellent in characteristics and reliability can be manufactured inexpensively and easily.
  • FIG. 2 is a diagram showing an X-ray diffraction pattern of a silicate compound produced in Example 21.
  • FIG. 1 is a diagram showing an X-ray diffraction pattern of a silicate compound produced in Example 21.
  • a step of heating the raw material preparation prepared to obtain a melt (1) Cooling step (II): a step of cooling the melt (1) to obtain a solidified product
  • a step of obtaining a coated positive electrode active material for a secondary battery A a M b X c O d Ze (2) (In the formula (2), A is at least one element selected from the group consisting of Li, Na and K, M is at least one element selected from the group consisting of Fe, Mn, Co and Ni, and X is Si.
  • Z represents halogen
  • a is 0.8 ⁇ a ⁇ 2.7
  • b is 0.6 ⁇ b ⁇ 1.4
  • c is 0.9 ⁇ c ⁇ 1.1
  • d is a, b , C, e, and a number depending on the valence of M and the valence of X
  • e is e ⁇ a, and 0 ⁇ e ⁇ 2.2.
  • the melting step (I) is a step of obtaining a melt (1) having a composition represented by the following formula (1).
  • A is at least one element selected from the group consisting of Li, Na and K
  • M is at least one element selected from the group consisting of Fe, Mn, Co and Ni
  • X is Si.
  • d1 is a, b , C and e1, and a number depending on the valence of M and the valence of X, and is a number that becomes d after the first heating step, e1 is e1 ⁇ a, and 0 ⁇ e1 ⁇ 2.2, a number that becomes e after the first heating step, and 0 ⁇ e ⁇ e1.)
  • raw materials containing each element source (A, M, X, Z) are adjusted so as to have the composition represented by the above formula (1), and a raw material preparation is first prepared. Is preferred.
  • a 0.8 ⁇ a ⁇ 2.7
  • b 0.6 ⁇ b ⁇ 1.4
  • c is 0.9 ⁇ c ⁇ 1.1
  • e1 is e1 ⁇ a
  • the raw material preparation can be melted well, and a uniform melt can be obtained.
  • the compound (2) can be obtained in the subsequent heating step (IV), and further, the compound (2) containing an olivine type crystal structure, particularly the compound (2) consisting only of the olivine type crystal structure is obtained. preferable.
  • a and b are more preferably 1.2 ⁇ a ⁇ 2.6 and 0.7 ⁇ b ⁇ 1.3, and particularly preferably 1.8 ⁇ a ⁇ 2.2 and 0.7 ⁇ b ⁇ 1.3. .
  • a and b are within the above ranges, a compound (2) showing a multi-electron type reaction (a reaction of extracting A exceeding 1 mol per unit number of moles) is obtained, and this compound (2) is used as a positive electrode for a secondary battery.
  • the theoretical electric capacity can be increased.
  • the value of a is particularly preferably 1.8 ⁇ a ⁇ 2.2.
  • e1 is more preferably 0 ⁇ e1 ⁇ 1.2, particularly preferably 0 ⁇ e1 ⁇ 0.7. It is easy to manufacture a compound (2) as it is in the said range.
  • the value of d1 is a number that depends on the numerical values of a, b, c, e1, and the valence of M and the valence of X. It is a value that can change in the heating step (IV), and is a value that becomes d after the heating step (IV). For example, when the value of d1 increases or decreases due to oxidation / reduction or volatilization of the component in the heating step (IV), it is preferable to set the value taking into account the increase / decrease.
  • A is at least one element selected from the group consisting of Li, Na and K. Since A is suitable as a positive electrode active material for a secondary battery, it is preferable to make Li essential, and it is particularly preferable to use only Li.
  • the compound (2) containing Li increases the capacity per unit volume (mass) of the secondary battery.
  • M is at least one element selected from the group consisting of Fe, Mn, Co and Ni. M is preferably only one type or two types. In particular, when the compound (2) produced by the production method of the present invention is used as a positive electrode active material for a secondary battery, it is preferable from the viewpoint of cost that M is composed only of Fe, Mn alone, or Fe and Mn. .
  • the valence of M is a numerical value that can change in each step of the production method of the present invention, and is in the range of +2 to +4. The valence of M is +2, +8/3, +3 when M is Fe, +2, +3, +4 when Mn, +2, +8/3, +3 when Co, +2, +4 when Ni is M preferable.
  • X is Si.
  • the valence of X is basically +4 for Si.
  • Z is halogen.
  • the halogen include chlorine (Cl), fluorine (F), bromine (Br), and iodine (I). From the viewpoint of performance, chlorine or fluorine is preferable, and fluorine is particularly preferable.
  • the melt (1) may contain elements other than A, M, X, oxygen (O) and Z.
  • the element is preferably at least one element selected from the group consisting of La, Ca, Mg and Zn (hereinafter referred to as Y). By containing Y, the melt (1) can be easily melted.
  • the content of Y (the total amount in the case of a plurality of elements) is preferably 0.1 to 3% in terms of oxide equivalent (unit: mol%) of each element when it becomes a melt.
  • the raw material preparation is composed of a compound containing A, a compound containing M, a metal, a compound containing X, a compound containing Z, and the like, and preferably contains a compound containing Y as necessary.
  • Examples of the compound containing A include A carbonate (A 2 CO 3 ), A hydrogen carbonate (AHCO 3 ), A hydroxide (AOH), A silicate (A 2 O ⁇ 2SiO 2 , A 2 O ⁇ SiO 2 , 2A 2 O ⁇ SiO 2, etc.), A phosphate (A 3 PO 4 ), A borate (A 3 BO 3 ), A fluoride (AF), A From organic acid salts such as chloride (ACl), A nitrate (ANO 3 ), A sulfate (A 2 SO 4 ), A acetate (CH 3 COOA) and oxalate ((COOA) 2 ) At least one selected from the group consisting of these groups (provided that a part or all of the at least one may each form a hydrated salt) is preferred. Of these, A 2 CO 3 , AHCO 3 , and AF are more preferable because they are inexpensive and easy to handle.
  • Examples of the compound containing M include oxides of M (FeO, Fe 3 O 4 , Fe 2 O 3 , MnO, Mn 2 O 3 , MnO 2 , CoO, Co 3 O 4 , Co 2 O 3 , NiO, etc.), M oxyhydroxide (MO (OH)), M hydroxide (M (OH) 2 , M (OH) 3 etc.), M silicate (MO ⁇ SiO 2 , 2MO ⁇ SiO 2 etc.) , M phosphate (such as M 3 (PO 4 ) 2 ), M borate (such as M 3 (BO 3 ) 2 ), M fluoride (MF 2 ), M chloride (MCl 2 , MCl 3 etc.), M nitrate (M (NO 3 ) 2 , M (NO 3 ) 3 etc.), M sulfate (MSO 4 , M 2 (SO 4 ) 3 etc.), M acetate (M ( Selected from the group consisting of organic acid salts such as CH 3 COO
  • At least one compound selected from the group consisting of Fe 3 O 4 , Fe 2 O 3 , MnO, Mn 2 O 3 , MnO 2 , Co 3 O 4 and NiO is more preferable.
  • the compound when M is Fe is preferably Fe 3 O 4 and / or Fe 2 O 3
  • the compound when M is Mn is preferably MnO 2 .
  • the compound containing M may be one type or two or more types.
  • Examples of the compound containing X include X oxide (SiO 2 and the like), X alkoxide (Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 and the like), A or M silicate, SiO 2 is preferable because it is inexpensive.
  • At least one selected from the group consisting of A or M fluoride and A or M chloride is preferable, and A fluoride is particularly preferable.
  • a suitable combination of each raw material is that at least one compound selected from the group consisting of a carbonate of A, a hydrogencarbonate of A and AF; a compound containing M is an oxide of M; and a compound containing X A compound containing A, or a compound containing A is at least one selected from the group consisting of a carbonate of A, a bicarbonate of A and AF; an oxide of M being a compound containing M; A combination in which the compound containing X is an oxide of X; and the compound containing Z is a fluoride of A.
  • the composition of the raw material formulation corresponds theoretically to the composition of the melt obtained from the raw material formulation.
  • the composition of the resulting melt (1) is calculated from the charged amount of each raw material. It may be slightly different from the mol% based on oxide. In such a case, it is preferable to set the charging amount of each raw material in consideration of the amount lost due to volatilization or the like.
  • each raw material in the raw material formulation is not particularly limited. Considering reactivity and physical properties of the positive electrode positive electrode material, the purity excluding hydration water is preferably 99% by mass or more.
  • each raw material it is preferable to use a pulverized raw material.
  • Each raw material may be pulverized and mixed, or may be pulverized after mixing.
  • the pulverization is preferably performed by a dry method or a wet method using a mixer, a ball mill, a jet mill, a planetary mill or the like, and a dry method is preferable because a solvent removal step is unnecessary.
  • the particle size of each raw material in the raw material preparation is not limited as long as it does not adversely affect the mixing operation, the filling operation of the mixture into the melting container, the meltability of the mixture, and the like.
  • the raw material formulation obtained by the above method is then heated and melted.
  • the heating is preferably performed by putting the raw material preparation into a container or the like and heating and melting it using a heating furnace.
  • the container include alumina, carbon, silicon carbide, zirconium boride, titanium boride, boron nitride, carbon, platinum, platinum alloy containing rhodium, refractory bricks, and reduction.
  • a container made of a material such as a material (for example, graphite) can be used.
  • the container is preferably fitted with a lid in order to prevent volatilization and evaporation in the heating furnace.
  • the heating furnace is preferably a resistance heating furnace, a high frequency induction furnace, or a plasma arc furnace.
  • the resistance heating furnace is preferably an electric furnace provided with a heating element made of an alloy such as a nichrome alloy, silicon carbide, or molybdenum silicide.
  • the heating temperature is preferably 1,300 to 1,600 ° C, particularly preferably 1,400 to 1,550 ° C.
  • melting means that each raw material is melted and is in a transparent state visually.
  • the heating time is preferably 0.2 to 2 hours, particularly preferably 0.5 to 2 hours.
  • stirring may be performed to increase the uniformity of the melt.
  • the melt may be clarified at a temperature lower than the melting temperature until the next cooling step (II) is performed.
  • Heating is preferably carried out in air, in an inert gas, or in a reducing gas. Melting conditions can be changed as appropriate depending on conditions such as the type of container or heating furnace and the heating method such as a heat source.
  • the pressure may be any of normal pressure, pressurization, and reduced pressure (0.9 ⁇ 10 5 Pa or less).
  • the melting condition is preferably in a reducing gas. It may be in oxidizing gas. When melted in oxidizing gas, it is preferable to perform reduction (for example, change from M 3+ to M 2+ ) in the next heating step (IV).
  • the inert gas is 99% by volume or more of at least one inert gas selected from the group consisting of nitrogen gas (N 2 ) and rare gases such as helium gas (He) and argon gas (Ar).
  • the reducing gas refers to a gas that is substantially free of oxygen by adding a reducing gas to the above-described inert gas.
  • the reducing gas include hydrogen gas (H 2 ), carbon monoxide gas (CO), and ammonia gas (NH 3 ).
  • the amount of the reducing gas in the inert gas is preferably 0.1% by volume or more, and particularly preferably 1 to 10% by volume of the reducing gas contained in the total gas volume.
  • the oxygen content is preferably 1% by volume or less, and particularly preferably 0.1% by volume or less in the gas volume.
  • the cooling step (II) is a step of cooling the melt (1) obtained in the melting step (I) to near room temperature (20 to 25 ° C.) to obtain a solidified product.
  • the solidified product is preferably an amorphous material, but a part of the solidified product may be a crystallized product.
  • the next pulverization step (III) can be easily performed, and the composition and particle size of the compound (2) can be easily controlled.
  • the crystallized product becomes a crystal nucleus in the heating step (IV), which is a subsequent step, and it is easy to crystallize.
  • the amount of crystallized product in the solidified product is preferably 0 to 30% by mass with respect to the total mass of the solidified product.
  • the amount of crystallized product in the solidified product is preferably 0 to 30% by mass with respect to the total mass of the solidified product.
  • the cooling of the melt is preferably performed by a method of cooling in air, in an inert gas, or in a reducing gas because facilities and the like are simple.
  • the cooling rate is preferably not less than -1 ⁇ 10 3 °C / sec, -1 ⁇ 10 4 °C / sec or more is particularly preferable.
  • a temperature change per unit time (ie, cooling rate) in the case of cooling is indicated by a negative value
  • a temperature change per unit time in case of heating is indicated by a positive value.
  • the upper limit of the cooling rate is preferably about -1 ⁇ 10 10 ° C / second from the viewpoint of manufacturing equipment and mass productivity, and is particularly preferably -1 ⁇ 10 8 ° C / second from the viewpoint of practicality.
  • the cooling rate of the melt is particularly preferably from -10 3 ° C / second to -10 10 ° C / second from 1000 ° C to 50 ° C.
  • a cooling method a method of cooling by dropping a melt between twin rollers rotating at a high speed, a method of cooling by dropping a melt on a single rotating roller, or a carbon plate or a metal plate with cooled melt It is preferable to adopt a method of pressing and cooling. Among these, a cooling method using twin rollers is more preferable because the cooling rate is high and a large amount of processing can be performed. As the double roller, it is preferable to use one made of metal, carbon, or ceramic.
  • the solidified product is preferably flaky or fibrous.
  • the average thickness is preferably 200 ⁇ m or less, particularly preferably 100 ⁇ m or less.
  • the average diameter of the plane perpendicular to the flaky average thickness is not particularly limited.
  • the average diameter is preferably 50 ⁇ m or less, particularly preferably 30 ⁇ m or less.
  • the pulverization step (III) is a step of obtaining a pulverized product containing the solidified product and the organic compound obtained in the cooling step (II).
  • the pulverization step (III) is preferably a step of pulverizing the mixture of the solidified product and the organic compound, or a step of pulverizing the solidified product and the organic compound and mixing them.
  • the former is preferable from the viewpoint that an organic compound can be effectively used.
  • the organic compound may be mixed without being pulverized.
  • the compound (2) obtained in the subsequent heating step (IV) is an insulator, it is necessary to increase the electrical conductivity in order to use it as a positive electrode active material for a secondary battery. At least a part of the organic compound is carbonized in the heating step (IV) and coats at least a part of the surface of the compound (2) as conductive carbon. Since the conductive carbon functions as a conductive material for the compound (2), the electrical conductivity of the positive electrode active material for the secondary battery can be increased.
  • the organic compound used in the present invention is an organic compound having a residue ratio of 15% by mass or less when heated at 700 ° C. for 8 hours in an inert gas or a reducing gas.
  • the electrical conductivity of the positive electrode active material for secondary battery obtained from the compound (2) is improved.
  • the adhesiveness of the conductive carbon based on the compound (2) and the organic compound can be enhanced. Note that high adhesion means that the conductive carbon does not peel even when the positive electrode active material for secondary batteries is repeatedly used as the positive electrode.
  • An organic compound in which the ratio of the residue when heated at 700 ° C. for 8 hours in an inert gas or a reducing gas is more than 0% by mass and 10% by mass or less is particularly preferable.
  • the reason for improving adhesion is not necessarily clear, but is estimated as follows.
  • an organic compound When an organic compound is heated in an inert gas or a reducing gas, it undergoes a thermal decomposition reaction, and oxygen and hydrogen are released and carbonized.
  • the organic compound whose ratio of the residue when heated at 700 ° C. for 8 hours is within the above range remains preferentially and uniformly carbonized in the heating step (IV), and the excess portion remains. These parts are volatilized in the gas. Since the solidified product is crystallized in the heating step (IV) to become the compound (2), the surface of the compound (2) can be efficiently coated with conductive carbon.
  • the proportion of the residue determined by the method defined above may be 0% by mass.
  • the organic compound is heated while adsorbed on the surface of the solidified product. This is because it remains as a significant amount of conductive carbon and can cover at least a part of the surface of the compound (2).
  • An organic compound having a residue ratio of 15% by mass or less is a compound having a high thermal decomposition rate. Therefore, the organic compound is efficiently carbonized in the heating step (IV), and can cover at least a part of the surface of the compound (2) as conductive carbon.
  • the organic compound is an aliphatic non-hydroxy group having at least one selected from the group consisting of a hydroxyl group or a hydroxyl group-derived group, a carboxyl group or a carboxyl group-derived group, a sulfonic acid group or a sulfonic acid group-derived group, and an etheric oxygen atom.
  • Preference is given to at least one selected from the group consisting of cyclic polymers, fatty acids, cellulose or cellulose derivatives, bicyclic monoterpenes or bicyclic monoterpene derivatives, and heterocyclic amines. 1 type may be used for this organic compound, or 2 or more types may be used for it.
  • the aliphatic acyclic polymer has at least one selected from the group consisting of a hydroxyl group or a hydroxyl group-derived group, a carboxyl group or a carboxyl group-derived group, a sulfonic acid group or a sulfonic acid group-derived group, and etheric oxygen.
  • a polymer having an acyclic aliphatic monomer unit as a constituent unit is preferred. Examples of the monomer unit include structural units based on vinyl alcohol, acrylic acid, vinyl sulfonic acid, ethylene glycol, cyclic ether (ethylene oxide, propylene oxide, butylene oxide, etc.) and the like.
  • At least one selected from the group consisting of vinyl alcohol, acrylic acid and ethylene glycol is preferable.
  • the aliphatic acyclic polymer include polyethylene glycol, polyvinyl alcohol, polyacrylic acid and the like.
  • the hydroxyl group-derived group include an alkoxy group and a silyl group.
  • the carboxyl group-derived group include an ester group and an amide group.
  • the derivative group for the sulfonic acid group include a sulfonic acid ester, Examples thereof include sulfonic acid amides.
  • fatty acid a saturated fatty acid having 10 to 30 carbon atoms is preferable, and a saturated fatty acid having 10 to 20 carbon atoms is particularly preferable.
  • fatty acid a saturated fatty acid having 10 to 30 carbon atoms is preferable, and a saturated fatty acid having 10 to 20 carbon atoms is particularly preferable.
  • Preferable examples include stearic acid, oleic acid, linoleic acid and the like.
  • cellulose or cellulose derivatives include cellulose, ethyl cellulose, cellulose ester, and cellulose ether.
  • bicyclic monoterpene or the bicyclic monoterpene derivative include camphor.
  • heterocyclic amine a compound having 1 to 3 amino groups in the molecule is preferable.
  • Preferable examples include melamine.
  • the number average molecular weight of the organic compound is not particularly limited, but is preferably 100 to 50,000, particularly preferably 100 to 20,000.
  • the organic compound does not volatilize in the heating step (IV), and conductive carbon tends to remain.
  • it is below the upper limit of the above range, the organic compound is likely to adhere to the surface of the solidified product in the pulverization step (III).
  • More preferable organic compounds are at least one selected from the group consisting of polyethylene glycol, polyvinyl alcohol, stearic acid, ethyl cellulose, melamine, camphor and polyacrylic acid. Particularly preferred organic compounds are at least one selected from the group consisting of ethyl cellulose, melamine and camphor.
  • the ratio of the mass of the organic compound is such that the carbon equivalent amount (mass) in the organic compound is 0.1% of the total mass of the mass of the compound (2) and the carbon equivalent amount (mass) in the organic compound.
  • An amount of ⁇ 60% by mass is preferred, an amount of 0.1 ⁇ 40% by mass is more preferred, and an amount of 1 ⁇ 20% by mass is particularly preferred.
  • the amount of the organic compound used is selected so as to satisfy the above.
  • the total amount of the solidified product and the organic compound is preferably 1 to 50% by mass, more preferably 2 to 48% by mass, and particularly preferably 3 to 45% by mass.
  • the usage-amount of an organic compound is also called carbon source preparation amount (unit: mass%).
  • a carbon-based conductive material may be mixed in addition to the organic compound.
  • the carbon-based conductive substance also adheres as conductive carbon to the surface of the compound (2) after the heating step (IV) and functions as a conductive material.
  • carbon-based conductive substance carbon black, graphite, acetylene black, carbon fiber, amorphous carbon and the like are preferable.
  • amorphous carbon those in which the CO bond peak and CH bond peak causing the decrease in the conductivity of the positive electrode material are not substantially detected in the FTIR analysis are preferable.
  • the solidified product obtained in the cooling step (II) usually contains a large amount of amorphous material or consists of an amorphous material, there is an advantage that it is easy to grind. Further, there is an advantage that grinding can be performed without imposing a burden on an apparatus used for grinding and the particle size can be easily controlled.
  • pulverization is performed after the heating step.
  • the present inventor has noticed that residual stress is generated by pulverization and battery characteristics may be deteriorated. Therefore, in the manufacturing method of the present invention, a method is adopted in which the residual stress generated by pulverization before the heating step is reduced or removed in the heating step in the subsequent step.
  • the pulverization is preferably performed using a cutter mill, jaw crusher, hammer mill, ball mill, jet mill, planetary mill or the like. Moreover, pulverization can be efficiently advanced by using each method stepwise depending on the particle diameter. For example, it is preferable to perform preliminary pulverization with a cutter mill and then pulverization with a planetary mill or a ball mill because the time required for pulverization can be shortened. From the viewpoint of productivity, it is particularly preferable to use a ball mill. As the grinding media, it is preferable to use zirconia balls, alumina balls, glass balls or the like. In particular, zirconia balls are preferable because they have a low wear rate and can suppress the mixing of impurities.
  • the diameter of the grinding media is preferably 0.1 to 30 mm.
  • the pulverization medium and the pulverized product may be separated and pulverized using a smaller pulverization medium. With this method, the remaining of unground particles can be suppressed.
  • the pulverization container is not particularly limited, but the pulverization efficiency is good when the pulverization medium and the solidified material are placed in the container up to 30 to 80% of the container internal volume.
  • the pulverization time is preferably 6 to 360 hours, more preferably 6 to 120 hours, and particularly preferably 12 to 96 hours. If the pulverization time is not less than the lower limit of the above range, the pulverization can be sufficiently advanced, and if it is not more than the upper limit, excessive pulverization can be suppressed.
  • the pulverization may be performed either dry or wet. However, it is preferable to perform the pulverization in a wet manner because the pulverized product can be reduced in particle size and the pulverized product and the organic compound can be mixed uniformly. That is, the pulverization step (III) is preferably performed using a solvent (pulverization solvent). When the grinding solvent is filled up to 30 to 80% of the volume in the container with the grinding media, the grinding efficiency is improved. When the pulverization step (III) is performed in a wet manner, it is preferable to carry out the heating step (IV) after removing the pulverization solvent by sedimentation, filtration, drying under reduced pressure, heat drying, or the like. However, when the ratio of the solid content with respect to a grinding
  • the pulverizing solvent a solvent having an appropriate polarity that is difficult to dissolve the solidified product and is compatible with the organic compound, and does not significantly increase the viscosity when mixed with the solidified product and the organic compound is preferable.
  • Water is preferable from the viewpoint of cost and safety.
  • an organic solvent is preferable.
  • the organic solvent include ethanol, isopropyl alcohol, acetone, hexane, toluene and the like.
  • the grinding solvent is more preferably at least one selected from the group consisting of water, acetone and isopropyl alcohol, and acetone is particularly preferred.
  • the amount of the grinding solvent used is preferably such that the concentration, which is the ratio of the total amount (mass) of the solidified product and organic compound to the total amount (mass) of the solidified product, organic compound and solvent, is 1 to 80%.
  • An amount of 40% is particularly preferred.
  • Productivity can be improved by making the usage-amount of a grinding
  • the average particle size of the pulverized product is preferably 10 nm to 10 ⁇ m, particularly preferably 100 nm to 5 ⁇ m in terms of volume-based median diameter. It is preferable for the average particle size to be equal to or greater than the lower limit of the above range since the compounds (2) are not sintered together and the particle size becomes too large when the heating step (IV) is carried out. It is preferable for it to be below the upper limit of the above range because the heating temperature and time in the heating step (IV) can be reduced. However, if there are many very fine particles having a particle size of less than 10 nm, it may act as a sintering aid when carrying out the heating step (IV), and the average particle size after heating may increase. is there.
  • the average particle size can be measured by, for example, a sedimentation method, a laser diffraction / scattering particle size measuring device, or a flow particle image analyzer.
  • heating step (IV) In the heating step (IV), the pulverized product obtained in the pulverizing step (III) is heated in an inert gas or a reducing gas to synthesize the compound (2) from the pulverized product, and the surface of the compound (2) Is a step of obtaining a positive electrode active material for a secondary battery in which at least a part of is coated with conductive carbon.
  • it is preferable to obtain particles of the compound (2) more preferably to obtain crystal particles of the compound (2), and to obtain crystal particles of the compound (2) having an olivine type crystal structure. It is particularly preferred. It is preferable that the compound (2) does not contain an amorphous substance. When the compound (2) does not contain an amorphous substance, a halo pattern is not detected by X-ray diffraction.
  • the preferable ranges of the element A, the elements M, a, b, and c in the formula (2) are the same as those in the formula (1).
  • the value of e is more preferably 0 ⁇ e ⁇ 1.2, and particularly preferably 0 ⁇ e ⁇ 0.7.
  • the heating temperature is preferably 500 to 1,000 ° C, particularly preferably 600 to 900 ° C.
  • the heating is not limited to being held at a constant temperature, and may be performed by setting the holding temperature in multiple stages. As the heating temperature is increased, the particle diameter of the generated particles tends to increase. Therefore, it is preferable to set the heating temperature according to a desired particle diameter.
  • the heating time (holding time depending on the heating temperature) is preferably 1 to 72 hours in consideration of the desired particle size. Heating is preferably performed in a box furnace, tunnel kiln furnace, roller hearth furnace, roller kiln furnace, microwave heating furnace, or the like that uses electricity, oil, gas, or the like as a heat source.
  • Heating is performed in an inert gas or a reducing gas.
  • the pressure may be any of normal pressure, pressurization, and reduced pressure (0.9 ⁇ 10 5 Pa or less).
  • you may charge the container which put the reducing agent (for example, graphite) in the heating furnace.
  • reduction of M ions in the pulverized product for example, change from M 3+ to M 2+ ) can be promoted. Thereby, crystal grains of the compound (2), particularly the compound (2) are obtained.
  • the cooling rate in the cooling is preferably ⁇ 30 ° C./hour to ⁇ 300 ° C./hour. By setting the cooling rate within this range, distortion due to heating can be removed, and when the product is a crystal, the target product can be obtained while maintaining the crystal structure. Further, the cooling may be left to cool to room temperature.
  • the cooling is preferably allowed to cool to room temperature. Cooling is preferably performed in an inert gas or a reducing gas.
  • the compound (2) preferably contains a crystal part, and is particularly preferably a crystal. It can be approximated to a positive electrode active material for secondary batteries having a multi-electron type theoretical electric capacity.
  • a positive electrode active material for a secondary battery that usually includes particles having an olivine type crystal structure can be obtained.
  • the specific surface area of the positive electrode active material for secondary batteries in the present invention is preferably 10 to 70 m 2 / g. 15 to 60 m 2 / g is more preferable, and 20 to 50 m 2 / g is particularly preferable. By setting the specific surface area within this range, the conductivity is increased.
  • the specific surface area can be measured by, for example, a specific surface area measuring apparatus using a nitrogen adsorption method.
  • the crystal particles of the compound (2) constituting the positive electrode active material for a secondary battery include both primary particles and secondary particles.
  • the secondary particles may be crushed and pulverized within a range in which the primary particles are not destroyed.
  • the average particle size of the crystal particles is preferably 10 nm to 10 ⁇ m, particularly preferably 100 nm to 2 ⁇ m in terms of volume-based median diameter in order to increase conductivity.
  • the average particle size of the compound (2) is preferably 10 nm to 10 ⁇ m, particularly preferably 100 nm to 2 ⁇ m in terms of volume-based median diameter, even if it contains not only crystal particles but also amorphous particles.
  • the compound (2) constituting the positive electrode active material for a secondary battery is preferably a compound containing silicic acid from the viewpoint of theoretical capacity.
  • the compound (2) is preferably a compound represented by the formula (3).
  • m is preferably 0 ⁇ m ⁇ 1, more preferably 0.3 ⁇ m ⁇ 1, more preferably 0.5 ⁇ m ⁇ 1, since the capacity and voltage are improved.
  • Li 2 + f (Fe m Mn 1-m ) g SiO 4 + h (3) (F is ⁇ 0.1 ⁇ a ⁇ 0.4, g is 0.7 ⁇ b ⁇ 1.3, m is 0 ⁇ m ⁇ 1, h is f, g, and Fe m Mn (The number depends on the average valence of 1-m .)
  • the example of the compound (2) which comprises the positive electrode active material for secondary batteries is shown below.
  • the positive electrode active material for secondary batteries which is excellent in the characteristic including electrical conductivity and reliability can be manufactured cheaply and simply.
  • the manufacturability, characteristics, reliability, and the like of the positive electrode active material for a secondary battery including the compound (2) having an olivine type crystal structure can be improved.
  • the positive electrode active material for secondary batteries provided with the compound (2) having excellent chemical composition and uniformity of particle diameter and high crystallinity can be obtained.
  • a positive electrode for secondary battery and a secondary battery By using the positive electrode active material for secondary battery obtained by the manufacturing method of the present invention, a positive electrode for secondary battery and a secondary battery can be manufactured.
  • the secondary battery include a metal lithium secondary battery, a lithium ion secondary battery, and a lithium polymer secondary battery, and a lithium ion secondary battery is preferable.
  • the battery shape is not limited, and various shapes and sizes such as a cylindrical shape, a square shape, and a coin shape can be appropriately employed.
  • the positive electrode for a secondary battery can be manufactured according to a known electrode manufacturing method using the positive electrode active material for a secondary battery obtained by the manufacturing method of the present invention.
  • the positive electrode active material for a secondary battery of the present invention may be added to a known binder (polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, ethylene propylene diene polymer, styrene-butadiene rubber, acrylonitrile-butadiene rubber, if necessary.
  • the mixed powder is pressure-molded on a support made of stainless steel or filled into a metal container.
  • an organic solvent N-methylpyrrolidone, toluene, cyclohexane, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, methyl acrylate, diethyltriamine, NN-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran.
  • Etc. can also be employed such as applying the slurry obtained by mixing with a metal substrate such as aluminum or stainless steel.
  • the structure of the secondary battery a structure in a known secondary battery can be adopted except that the positive electrode for a secondary battery obtained by the production method of the present invention is used as an electrode.
  • the negative electrode a known negative electrode active material can be used as the active material, and at least one selected from the group consisting of carbon materials, alkali metal materials, and alkaline earth metal materials is preferably used.
  • the electrolytic solution a non-aqueous electrolytic solution is preferable. That is, as the secondary battery obtained by the production method of the present invention, a nonaqueous electrolyte lithium ion secondary battery is preferable.
  • the secondary battery obtained by the production method of the present invention is useful as a secondary battery mounted in a plug-in hybrid vehicle or an electric vehicle, or as a storage battery for storing power.
  • Examples 1 to 14 are reference examples
  • Examples 21 to 29 are examples
  • Examples 41 and 49 are comparative examples
  • Examples 30 to 33 and 42 to 48 are reference examples.
  • the ratio of the residue of an organic compound, the average particle diameter of the positive electrode active material for secondary batteries obtained, a specific surface area, the ratio of residual carbon, and the initial discharge capacity of a secondary battery were measured by the method shown below.
  • the proportion (mass%) of residual carbon in the positive electrode active material for secondary batteries was measured using a carbon analyzer (manufactured by Horiba, Ltd., apparatus name: EMIA-321V).
  • the charge / discharge characteristics of the secondary battery were measured using a charge / discharge evaluation apparatus (manufactured by Toyo System Co., Ltd., apparatus name: TOSCAT-3000).
  • the secondary battery was charged at a constant current up to 4.5 V at 25 ° C. and then at a constant voltage of 4.5 V until 1.5 mA / g, and the discharge capacity up to 1.5 V at 15 mA / g was evaluated.
  • Example 1 to 14 The proportion of organic compound residue was measured. The proportion of the organic compound residues in Examples 1 to 10 was 15% by mass or less. The proportion of the organic compound residues of Examples 11 to 14 exceeded 15% by mass. The results are shown in Table 1. In addition, the numerical value in the name of an organic compound means a number average molecular weight.
  • Example 21 Composition Li 2 O melt, FeO, MnO, SiO 2 in terms of the amount (unit: mol%) in 33.3 mol%, respectively, 16.7 mol%, 16.7 mol%, and 33.3 mol% Lithium carbonate (Li 2 CO 3 ), triiron tetroxide (Fe 3 O 4 ), manganese dioxide (MnO 2 ), silicon dioxide (SiO 2 ) are weighed, mixed and pulverized in a dry process A formulation was obtained.
  • Lithium carbonate Li 2 CO 3
  • triiron tetroxide Fe 3 O 4
  • MnO 2 manganese dioxide
  • SiO 2 silicon dioxide
  • the raw material formulation was filled in a platinum alloy crucible containing 20% by mass of rhodium.
  • the crucible was placed in an electric furnace (manufactured by Motoyama, apparatus name: NH-3035) equipped with a heating element made of molybdenum silicide. While flowing N 2 gas through the electric furnace at 2 L / min, the temperature was raised at a rate of + 300 ° C./hour and heated at 1,450 ° C. for 0.5 hour to obtain a melt.
  • the obtained solution was separated from zirconia balls, put into a PP bottle (250 mL) together with 400 g of zirconia balls having a diameter of 1 mm, and similarly pulverized at 280 rpm for 72 hours using a desktop pot mill frame.
  • the mass of melamine is 20% by mass with respect to the total amount of the mass of solidified product and the mass of melamine (also referred to as carbon source charge in this specification).
  • the average particle diameter of the obtained pulverized product was 0.19 ⁇ m in terms of volume-based median diameter.
  • Heating step (IV) The pulverized product obtained in the pulverization step (III) was dried and then placed in an alumina pot. Next, the alumina koji pot was placed in a reducing atmosphere firing furnace (manufactured by Motoyama, apparatus name: SKM-3035F-SP). While flowing 3 volume% H 2 —N 2 gas at 1.5 L / min in the firing furnace, heating was performed at 700 ° C. for 8 hours to obtain a positive electrode active material for a secondary battery. The specific surface area of the obtained positive electrode active material for secondary batteries was 29.8 m 2 / g.
  • the positive electrode active material for a secondary battery is obtained by coating at least a part of the surface of the crystal particles of the silicate compound deposited in the heating step (IV) with conductive carbon derived from melamine.
  • conductive carbon derived from melamine derived from melamine.
  • a positive electrode active material for a secondary battery obtained in the heating step (IV), acetylene black, and a polyvinylidene fluoride solution (solvent: N-methylpyrrolidone) containing 12.1% by mass of polyvinylidene fluoride are mixed, and N -Methylpyrrolidone was added to make a slurry.
  • the mass ratio of the positive electrode active material, acetylene black, and polyvinylidene fluoride was 80: 12: 8.
  • the slurry was coated on one side of a 20 ⁇ m thick aluminum foil using a doctor blade, then dried at 120 ° C., and further subjected to roll press rolling twice to produce a positive electrode sheet.
  • the positive electrode sheet punched out to a diameter of 18 mm is used as a positive electrode, a metal lithium foil having a thickness of 500 ⁇ m is used as a negative electrode, a stainless steel plate having a thickness of 1 mm as a negative electrode current collector, and a porous polypropylene having a thickness of 25 ⁇ m as a separator.
  • a stainless steel simple sealed cell battery was assembled in an argon glove box. Table 2 shows the initial discharge capacity of the obtained secondary battery.
  • Example 22 to 29 Production and evaluation of positive electrode active material for secondary battery
  • a positive electrode active material for a secondary battery was produced and evaluated in the same manner as in Example 21 with the formulation shown in Table 2. The results are shown in Table 2.
  • Example 30 Production and evaluation of positive electrode active material for secondary battery] (Melting step (I))
  • the composition of the melt is 33.0 mol% and 16.9 mol% in terms of Li 2 O, FeO, MnO, SiO 2 , P 2 O 5 , B 2 O 3 and Al 2 O 3 (mol%), respectively.
  • Li 2 CO 3 lithium carbonate
  • Fe 3 O 4 triiron tetraoxide
  • MnO 2 manganese dioxide
  • SiO 2 silicon dioxide
  • NH 4 H 2 PO 4 ammonium dihydrogen phosphate
  • B 2 O 3 aluminum oxide
  • Al 2 O 3 aluminum oxide
  • the raw material formulation was heated in the same manner as in Example 21 to obtain a melt, and a flaky solidified product was obtained.
  • the pulverization step (III) was performed in the same manner as in Example 21 except that the organic compound was changed to camphor to obtain a pulverized product having an average particle diameter of 0.16 ⁇ m in terms of volume-based median diameter.
  • the heating step (IV) was performed in the same manner as in Example 21 to obtain a positive electrode active material for a secondary battery.
  • the production of a positive electrode sheet, the production and evaluation of a secondary battery were carried out in the same manner as in Example 21. The results are shown in Table 2.
  • Example 31 Production and evaluation of positive electrode active material for secondary battery]
  • the composition of the melt is 32.8 mol%, 17.2 mol%, 17.2 mol%, 31.1 in terms of Li 2 O, FeO, MnO, SiO 2 and P 2 O 5 (mol%), respectively.
  • Ammonium hydrogen (NH 4 H 2 PO 4 ) was weighed, mixed and pulverized in a dry process to obtain a raw material formulation.
  • Example 32 Production and evaluation of positive electrode active material for secondary battery]
  • the composition of the melt is 32.8 mol%, 17.2 mol%, 17.2 mol%, 31.1 in terms of Li 2 O, FeO, MnO, SiO 2 and B 2 O 3 (mol%), respectively.
  • Lithium carbonate (Li 2 CO 3 ), triiron tetroxide (Fe 3 O 4 ), manganese dioxide (MnO 2 ), silicon dioxide (SiO 2 ), boron oxide ( B 2 O 3 ) was weighed, mixed and pulverized in a dry manner to obtain a raw material formulation.
  • Example 33 Production and evaluation of positive electrode active material for secondary battery] (Melting step (I)) Lithium carbonate (Li 2 CO 3 ), four so that the composition of the melt is 25 mol%, 50 mol%, and 25 mol% in terms of Li 2 O, FeO, and P 2 O 5 (mol%), respectively.
  • Triiron oxide (Fe 3 O 4 ) and ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) were weighed, mixed and pulverized in a dry manner to obtain a raw material formulation.
  • Example 41 Production and evaluation of positive electrode active material for secondary battery
  • the production of a positive electrode active material for a secondary battery, the production of a positive electrode sheet, the production and evaluation of a secondary battery were carried out in the same manner as in Example 21 except that no organic compound was added. The results are shown in Table 3.
  • Example 42 Production and evaluation of positive electrode active material for secondary battery
  • organic compounds 0.12 g (carbon source charge: 1.0% by mass) of D-glucose (manufactured by Kanto Chemical Co., Ltd., reagent) and 2.15 g (carbon source charge: sucrose manufactured by Kanto Chemical Co., Ltd.): 17.1% by mass) and 0.3 g (carbon source charge: 2.4% by mass) of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Black) as a carbon-based conductive substance
  • acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Black
  • Examples 43 to 45 Production and evaluation of positive electrode active material for secondary battery
  • Example 46 Production and evaluation of positive electrode active material for secondary battery
  • organic compounds 0.12 g (carbon source charge: 1.0% by mass) of D-glucose (manufactured by Kanto Chemical Co., Ltd., reagent) and 2.15 g (carbon source charge: sucrose manufactured by Kanto Chemical Co., Ltd.): 17.1% by mass) and 0.3 g (carbon source charge: 2.4% by mass) of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Black) as a carbon-based conductive substance
  • acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Black
  • Example 47 Production and evaluation of positive electrode active material for secondary battery
  • organic compounds 0.12 g (carbon source charge: 1.0% by mass) of D-glucose (manufactured by Kanto Chemical Co., Ltd., reagent) and 2.15 g (carbon source charge: sucrose manufactured by Kanto Chemical Co., Ltd.): 17.1% by mass) and 0.3 g (carbon source charge: 2.4% by mass) of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Black) as a carbon-based conductive substance
  • acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Black
  • Example 48 Production and evaluation of positive electrode active material for secondary battery
  • organic compounds 0.12 g (carbon source charge: 1.0% by mass) of D-glucose (manufactured by Kanto Chemical Co., Ltd., reagent) and 2.15 g (carbon source charge: sucrose manufactured by Kanto Chemical Co., Ltd.): 17.1% by mass) and 0.3 g (carbon source charge: 2.4% by mass) of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Black) as a carbon-based conductive substance
  • acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Black
  • Example 49 Production and evaluation of positive electrode active material for secondary battery
  • organic compounds 0.12 g (carbon source charge: 1.0% by mass) of D-glucose (manufactured by Kanto Chemical Co., Ltd., reagent) and 2.15 g (carbon source charge: sucrose manufactured by Kanto Chemical Co., Ltd.): 17.1% by mass) and 0.3 g (carbon source charge: 2.4% by mass) of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Black) as a carbon-based conductive substance
  • acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Black
  • the positive electrode active material for secondary battery obtained by the manufacturing method of the present invention By using the positive electrode active material for secondary battery obtained by the manufacturing method of the present invention, a positive electrode for secondary battery and a secondary battery can be manufactured.
  • the secondary battery obtained by the production method of the present invention is useful as a secondary battery mounted on a plug-in hybrid vehicle or an electric vehicle, or as a storage battery for storing power. It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2011-071049 filed on March 28, 2011 are cited herein as disclosure of the specification of the present invention. Incorporated.

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Abstract

La présente invention concerne un procédé de production d'un matériau actif d'électrode positive pour une batterie secondaire. L'état de la technique concernant les procédés de production de phosphure de fer et de lithium, qui est un matériau actif d'électrode positive pour batteries secondaires, est confronté à des problèmes tels qu'une faible productivité due à une synthèse réalisée dans une cuve résistant à la pression, une apparition de surfaces non recouvertes de carbone du fait d'une étape de pulvérisation, et une incapacité à recouvrir uniformément des composés organiques soumis à une pression uniaxiale se formant après avoir simplement mélangé les composés organiques. La présente invention concerne un procédé de production dans lequel une étape de fusion (I), une étape de refroidissement (II), une étape de pulvérisation (III), et une étape de chauffage (IV), sont réalisées selon cet ordre lors de la production de matériau actif d'électrode positive pour la batterie secondaire. Ceci permet d'augmenter la conductivité électrique du matériau actif d'électrode positive pour la batterie secondaire, et d'exercer un bon contrôle de la composition et de la taille des particules.
PCT/JP2012/058241 2011-03-28 2012-03-28 Matériau actif d'électrode positive pour batterie secondaire, électrode positive pour batterie secondaire, et procédé de production de batterie secondaire WO2012133584A1 (fr)

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JP2013008483A (ja) * 2011-06-23 2013-01-10 Taiheiyo Cement Corp リチウムイオン電池用正極活物質の製造法
JP2014524883A (ja) * 2011-07-21 2014-09-25 サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン 溶融製品の製造法
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US10535879B2 (en) 2013-01-31 2020-01-14 Sanyo Electric Co., Ltd. Positive electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery
CN104584290B (zh) * 2013-01-31 2018-09-28 三洋电机株式会社 非水电解质二次电池用正极和非水电解质二次电池
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CN108495819B (zh) * 2016-01-28 2020-11-20 住友金属矿山株式会社 带包覆膜的镍系锂-镍复合氧化物颗粒的制造方法
CN105576217B (zh) * 2016-03-17 2018-04-03 齐鲁工业大学 一种三维碳原位包覆的磷酸盐正极材料的制备方法
CN105576217A (zh) * 2016-03-17 2016-05-11 齐鲁工业大学 一种三维碳原位包覆的磷酸盐正极材料的制备方法
CN107994214A (zh) * 2017-11-14 2018-05-04 山东丰元化学股份有限公司 一种高性能磷酸铁锂复合材料及其制备方法

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