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WO2011138965A1 - Composé (acide silicique)-(acide borique), composé (acide silicique)-(acide borique)-(acide phosphorique), électrode positive pour batterie secondaire, et procédé pour la production de batterie secondaire - Google Patents

Composé (acide silicique)-(acide borique), composé (acide silicique)-(acide borique)-(acide phosphorique), électrode positive pour batterie secondaire, et procédé pour la production de batterie secondaire Download PDF

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WO2011138965A1
WO2011138965A1 PCT/JP2011/060603 JP2011060603W WO2011138965A1 WO 2011138965 A1 WO2011138965 A1 WO 2011138965A1 JP 2011060603 W JP2011060603 W JP 2011060603W WO 2011138965 A1 WO2011138965 A1 WO 2011138965A1
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atom
boric acid
compound
group
silicic acid
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English (en)
Japanese (ja)
Inventor
義久 別府
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AGC Inc
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Asahi Glass Co Ltd
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Priority to CN2011800228192A priority Critical patent/CN102884000A/zh
Priority to JP2012513833A priority patent/JPWO2011138965A1/ja
Publication of WO2011138965A1 publication Critical patent/WO2011138965A1/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
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/12—Borates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/122—Lepidoic silicic acid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a silicic acid-boric acid compound and a silicic acid-boric acid-phosphoric acid compound, a positive electrode for a secondary battery, and a method for producing a secondary battery.
  • lithium ion secondary batteries have been widely used as power sources for portable electronic devices such as mobile phones and laptop computers, and portable power tools.
  • Application of a lithium ion secondary battery as a power source for an electric vehicle is desired, and attempts have been made to increase the capacity of the positive electrode material of the lithium ion secondary battery in order to realize application to a power source for an electric vehicle.
  • an olivine-type boric acid compound and a manufacturing method thereof have been proposed from the viewpoints of resources, safety, cost, stability, and the like.
  • LiMBO 3 Fe, Mn, Co
  • Patent Document 1 includes x Li in the unit formula, and [SiO 4 ], [SO 4 ], [PO 4 ], [GeO 4 ], [VO 4 ], [AlO 4 ], [BO]. 4 ] and the like, and compounds having an orthosilicate structure have been proposed as electrode materials.
  • Non-Patent Document 1 uses expensive oxalate as an M source, and there is a problem that the manufacturing cost increases. Moreover, in order to inhibit the generation and grain growth of LiMBO 3 due to the large amount of gas generated due to decomposition of the raw material, two-stage heating, that is, pulverizing and heating the raw material formulation to generate gas, then crushing, pulverizing, After passing through processes such as molding, it is necessary to synthesize LiMBO 3 particles by heating again at a high temperature. For this reason, there was a problem in manufacturability. It is Li 1.7 Mn 0.7 Fe 0.3 Si 0.7 P 0.3 O 4 that is actually disclosed as an electrode material in Patent Document 1 as a compound containing Si.
  • Li 2 MnSiO 4 and LiFePO 4 are mixed and pulverized, sealed in a tube, and heated to produce the solid phase reaction.
  • the solid-phase reaction has a complicated manufacturing process, is expensive to manufacture, is difficult to mass-produce, and composition control is not easy.
  • An object of the present invention is to provide a method in which the composition of the silicic acid-boric acid compound and the silicic acid-boric acid-phosphoric acid compound can be easily controlled and manufactured. According to the method of the present invention, it is possible to provide a method for producing a silicic acid-boric acid compound and a silicic acid-boric acid-phosphoric acid compound which are excellent in battery characteristics and reliability at low cost and efficiently. Furthermore, this invention provides the manufacturing method of the positive electrode for secondary batteries which is excellent in a battery characteristic and reliability, and a secondary battery.
  • the present invention is the following [1] to [19].
  • the oxide equivalent amount of each atom when it becomes a melt (unit: Mol%) 15% ⁇ A 2 O ⁇ 30%, 35% ⁇ MO ⁇ 55%, 3% ⁇ SiO 2 ⁇ 50%, 1% ⁇ B 2 O 3 ⁇ 20%, 0.8 ⁇ A 2 O / (0.5SiO 2 + B 2 O 3 ) ⁇ 1.2, 0.8 ⁇ A 2 O / 0.5MO ⁇ 1.2, Heating the raw material formulation to obtain a melt, Cooling the melt to obtain a solidified product, Pulverizing the solidified product to obtain a pulverized product; and Heating the pulverized product to obtain a silicic acid-boric acid compound having a
  • a x M y Si 1-a B a O z (1) (Wherein, A and M are the same kind of atoms as described above, and x, y and a are 0.8 ⁇ x ⁇ 1.2, 0.8 ⁇ y ⁇ 1.2, 0.05 ⁇ a ⁇ 0.7, and z is a number depending on the valence N of x, y, a and M.)
  • a x M y Si 1-a B a O z (1) (Wherein, A and M are the same kind of atoms as described above, and x, y and a are 0.8 ⁇ x ⁇ 1.2, 0.8 ⁇ y ⁇ 1.2, 0.05 ⁇ a ⁇ 0.7, and z is a number depending on the valence N of x, y, a and M.)
  • the atom A contained in the raw material preparation is A carbonate, A bicarbonate, A hydroxide, A borate, A nitrate, A chloride, A sulfuric acid.
  • Atom M is selected from the group consisting of M oxide, M oxyhydroxide, M metal, M borate, M chloride, M nitrate, M sulfate, and M organic salt
  • At least one Si is a silicate of A selected from the group consisting of silicon oxide, A 2 SiO 3 and A 4 SiO 4 (where A is the same kind of atom as described above), and MSiO 3 and M 2 SiO 4 M silicate selected from the group consisting of (wherein M is the same kind of atom as described above), and included as at least one selected from the group consisting of: B is boron oxide, boric acid, A borate (where A is the same kind of atom as described above), and M borate (where M is the same kind of atom as described above).
  • a and M are the same kind of atoms as described above, and x, y, a and b are 0.8 ⁇ x ⁇ 1.2, 0.8 ⁇ y ⁇ 1.2, 0.
  • a and M are the same kind of atoms as described above, and x, y, a and b are 0.8 ⁇ x ⁇ 1.2, 0.8 ⁇ y ⁇ 1.2, 0.
  • Atom A contained in the raw material preparation is A carbonate, A bicarbonate, A hydroxide, A borate, A phosphate and hydrogen phosphate, A At least one selected from the group consisting of nitrate, A chloride, A sulfate, A acetate, and A oxalate (however, these compounds each form a hydrate salt)
  • Atom M is selected from the group consisting of M oxide, M oxyhydroxide, M metal, M borate, M chloride, M nitrate, M sulfate, and M organic salt
  • At least one Si is a silicate of A selected from the group consisting of silicon oxide, A 2 SiO 3 and A 4 SiO 4 (where A is the same kind of atom as
  • the silicic acid-boric acid compound having the composition represented by the formula (1) is a compound having a composition represented by the following formula (3) and is a crystal particle: 3] The method for producing a silicic acid-boric acid compound.
  • the silicic acid-boric acid-phosphoric acid compound having the composition represented by the formula (2) is a compound having a composition represented by the following formula (5), and is a crystal particle: [4] ] To [6] a process for producing a silicic acid-boric acid-phosphoric acid compound.
  • the solidified product includes at least one carbon source selected from an organic compound and a carbon-based conductive active material, and the amount of the carbon source is determined based on the amount of the solidified product and the carbon source.
  • the step of heating the pulverized product to obtain a silicic acid-boric acid compound and a silicic acid-boric acid-phosphoric acid compound is performed at 500 ° C. to 1,000 ° C. in an inert gas or a reducing gas.
  • a process for producing a silicic acid-boric acid compound and a silicic acid-boric acid-phosphoric acid compound is performed at 500 ° C. to 1,000 ° C. in an inert gas or a reducing gas.
  • the conductivity of the silicic acid-boric acid-phosphoric acid compound particles is 0.1 to 20% by mass with respect to the total mass of the silicic acid-boric acid-phosphoric acid compound and the conductive carbonaceous layer.
  • the silicic acid-boric acid-phosphoric acid compound according to [15] which contains a carbonaceous layer on the surface of the particles or at the interface between the particles.
  • a composite oxide selected from the group consisting of silicic acid-boric acid compounds and silicic acid-boric acid-phosphoric acid compounds is obtained by the production method of [1] to [13].
  • a method for producing a positive electrode for a secondary battery wherein a positive electrode for a secondary battery is produced using a positive electrode material for a secondary battery.
  • a method for producing a secondary battery comprising obtaining a positive electrode for a secondary battery by the production method according to [18], and then producing a secondary battery using the positive electrode for a secondary battery. .
  • a method for efficiently producing a silicic acid-boric acid compound and a silicic acid-boric acid-phosphoric acid compound using an inexpensive raw material and a simple technique is provided.
  • the composition of the silicic acid-boric acid compound and the silicic acid-boric acid-phosphoric acid compound can be easily controlled, so that the silicic acid-boric acid compound and the silicic acid-boric acid- A phosphoric acid compound can be produced efficiently. Therefore, by using the silicic acid-boric acid compound and the silicic acid-boric acid-phosphoric acid compound obtained by the present invention, a positive electrode for secondary batteries and a secondary battery excellent in battery characteristics and reliability can be produced.
  • the present invention also provides a silicic acid-boric acid compound and a silicic acid-boric acid-phosphoric acid compound that are excellent in battery characteristics and reliability.
  • FIG. 6 is a diagram showing an X-ray diffraction pattern of silicic acid-boric acid compound particles produced in Examples 3, 5 and 7.
  • FIG. 3 is a diagram showing an X-ray diffraction pattern of silicic acid-boric acid compound particles produced in Examples 9 and 11.
  • FIG. 4 is a diagram showing an X-ray diffraction pattern of silicic acid-boric acid-phosphoric acid compound particles produced in Examples 19 and 21.
  • A represents at least one atom selected from the group consisting of Li, Na and K.
  • A represents an atom of the above three alkali metal elements.
  • A may consist of a combination of two or more atoms.
  • M represents at least one atom selected from the group consisting of Fe, Mn, Co and Ni.
  • M represents an atom of the above four transition metal elements. M may consist of a combination of two or more atoms.
  • chemical formulas, such as Formula (1), Formula (2), Formula (3) represent an average composition.
  • a crystal having an olivine structure is hereinafter referred to as an olivine crystal, and a particle containing the olivine crystal is also referred to as an olivine crystal particle.
  • the olivine-type crystal particle may partially include a crystal structure other than the olivine-type crystal structure, or may partially include an amorphous structure. It is preferable that substantially all of the olivine type crystal particles are made of olivine type crystals.
  • step (11), step (12), step (13), and step (14) are performed in this order. Other steps may be performed before, between, and after the steps (11) to (14) as long as each step is not affected.
  • Step (11) at least one atom A selected from the group consisting of Li, Na and K, at least one atom M selected from the group consisting of Fe, Mn, Co and Ni, Si and B, and melting
  • the oxide equivalent amount (unit: mol%) of the content of each atom when it becomes a product is 15% ⁇ A 2 O ⁇ 30%, 35% ⁇ MO ⁇ 55%, 3% ⁇ SiO 2 ⁇ 50% 1% ⁇ B 2 O 3 ⁇ 20%, 0.8 ⁇ A 2 O / (0.5SiO 2 + B 2 O 3 ) ⁇ 1.2, 0.8 ⁇ A 2 O / 0.5MO ⁇ 1.2, heating the raw material formulation to obtain a melt
  • Step (12) a step of cooling the melt to obtain a solidified product
  • Step (13) pulverizing the solidified product to obtain a pulverized product
  • step (21), step (22), step (23), and step (24) are performed in this order. Do. Other steps may be performed before, between, and after the steps (21) to (24) as long as each step is not affected.
  • the oxide equivalent amount (unit: mol%) of the content of each element when it becomes a melt is 15% ⁇ A 2 O ⁇ 30%, 35% ⁇ MO ⁇ 55%, 3% ⁇ SiO 2 ⁇ 50%, 1% ⁇ B 2 O 3 ⁇ 20%, 1% ⁇ P 2 O 5 ⁇ 18%, 1% ⁇ (B 2 O 3 + P 2 O 5 ) ⁇ 25%, 0.8 ⁇ A 2 O / (0.5SiO 2 + B 2 O 3 + P 2 O 5 ) ⁇ 1.2, 0.8 ⁇ A 2 O / 0.5MO ⁇ 1.2 is heated to obtain a melt.
  • Step (22) a step of cooling the melt to obtain a solidified product
  • Step (23) a step of pulverizing the solidified product to obtain a pulverized product
  • Step (24) A step of heating the pulverized product to obtain a silicic acid-boric acid-phosphoric acid compound having a composition represented by the formula (2).
  • the composition has a relatively high molar ratio of B 2 O 3 in terms of oxide, the material cost can be reduced. Moreover, since the upper limit of the heating temperature at the time of melting a raw material formulation rises, a melting temperature range can be expanded and it becomes easy to manufacture. Furthermore, in the case of the second embodiment containing P, since it can be melted in a wide composition range in step (21), a silicic acid-boric acid-phosphoric acid compound in a wide composition range can be obtained and produced. Cost can be reduced.
  • each step will be specifically described.
  • Step (11) in the production method of the first embodiment of the present invention is first selected from the group consisting of at least one atom A selected from the group consisting of Li, Na and K and Fe, Mn, Co and Ni. At least one kind of atom M, and Si and B (however, at least one selected from the group consisting of atom A, atom M, Si and B is contained as an oxide) and becomes a melt.
  • the oxide conversion amount (unit: mol%) of the content of each atom is 15% ⁇ A 2 O ⁇ 30%, 35% ⁇ MO ⁇ 55%, 3% ⁇ SiO 2 ⁇ 50%, 1% ⁇ B 2 O 3 ⁇ 20%, 0.8 ⁇ A 2 O / (0.5SiO 2 + B 2 O 3 ) ⁇ 1.2, 0.8 ⁇ A 2 O / 0.5MO ⁇ 1.2
  • a raw material formulation is obtained. Subsequently, the raw material formulation is heated to obtain a melt. Before the raw material preparation is heated, it may be mixed, pulverized and heated to obtain a melt. Alternatively, the raw material preparation may be manufactured after each raw material has been pulverized in advance. The raw material mixture is mixed and pulverized using a ball mill, a jet mill, a planetary mill or the like in a dry or wet manner. A dry method is preferable in that it is not necessary to remove the dispersion medium.
  • the melt has the above composition range because the composition of the finally obtained silicic acid-boric acid compound can be easily controlled to satisfy the formula (1).
  • the raw material composition is such that the melt satisfies 15% ⁇ A 2 O ⁇ 30%, 35% ⁇ MO ⁇ 55%, 3% ⁇ SiO 2 ⁇ 50%, and 1% ⁇ B 2 O 3 ⁇ 20%. This is preferable because the product can be easily melted.
  • MO is 55% or more
  • SiO 2 is 3% or less
  • B 2 O 3 is 1% or less
  • a 2 O is 30% or more
  • MO is 35% or less, SiO 2 is 50% or more, or B 2 O 3 is 20% or more, it is difficult to obtain a target silicic acid-boric acid compound. It becomes.
  • dissolves means that a raw material formulation melt
  • the melt further has a composition satisfying 18% ⁇ A 2 O ⁇ 25%, 3% ⁇ MO ⁇ 50%, 3% ⁇ SiO 2 ⁇ 40%, and 2% ⁇ B 2 O 3 ⁇ 18%. Since the desired silicic acid-boric acid compound can be obtained, it is particularly preferable.
  • the melt is not limited to those consisting only of atoms A, M, silicon (Si), boron (B), and oxygen (O), but Ti, V, B, Al, Ca, Cu, Mg, and Zn. It may contain at least one atom X selected from the group consisting of By containing the atom X, the raw material preparation can be easily melted.
  • the content of atoms X (the total amount in the case of a plurality of atoms) is 0.1 to 5% in terms of oxide equivalent (unit: mol%) of the content of each atom when it becomes a melt. preferable.
  • atoms A, atoms M, Si and B are converted into oxides (unit: mol%) of the content of each atom when it becomes a melt, 15% ⁇ A 2 O ⁇ 30% 35% ⁇ MO ⁇ 55%, 3% ⁇ SiO 2 ⁇ 50%, 1% ⁇ B 2 O 3 ⁇ 20%, 0.8 ⁇ A 2 O / (0.5SiO 2 + B 2 O 3 ) ⁇
  • the raw materials are selected and mixed so that a melt satisfying 1.2, 0.8 ⁇ A 2 O / 0.5MO ⁇ 1.2 is obtained.
  • the raw material is a compound containing atom A, a compound containing atom M, a compound containing Si, a compound containing B, or a compound containing atom X as necessary.
  • Step (21) in the production method of the second embodiment of the present invention includes at least one atom A selected from the group consisting of Li, Na and K, and at least selected from the group consisting of Fe, Mn, Co and Ni. 1 type of atom M and Si, B, and P (however, at least one selected from the group consisting of atom A, atom M, Si, B, and P is included as an oxide) and melted.
  • the oxide equivalent amount (unit: mol%) of the content of each atom when it becomes a product is 15% ⁇ A 2 O ⁇ 30%, 35% ⁇ MO ⁇ 55%, 3% ⁇ SiO 2 ⁇ 50% 1% ⁇ B 2 O 3 ⁇ 20%, 1% ⁇ P 2 O 5 ⁇ 18%, 1% ⁇ (B 2 O 3 + P 2 O 5 ) ⁇ 25%, 0.8 ⁇ A 2 O /(0.5SiO 2 + B 2 O 3 + P 2 O 5 ) ⁇ 1.2, 0.8 ⁇ A 2 O / 0.
  • a raw material formulation with 5MO ⁇ 1.2 is obtained.
  • a silicic acid-boric acid compound containing phosphoric acid is preferable because a silicic acid-boric acid compound having a wide composition range can be obtained.
  • the raw material formulation Is preferable because it can be melted.
  • composition range of the melt in the production method of the second embodiment is preferable because the composition of the resulting silicic acid-boric acid compound can be easily controlled to be represented by the formula (2).
  • the melt in the manufacturing method of the second embodiment is not limited to the one consisting only of atom A, atom M, silicon (Si), boron (B), phosphorus (P), and oxygen (O), Ti, It may contain at least one atom X selected from the group consisting of V, B, Al, Ca, Cu, Mg and Zn.
  • atom X selected from the group consisting of V, B, Al, Ca, Cu, Mg and Zn.
  • the content of atoms X (the total amount in the case of a plurality of atoms) is 0.1 to 5% in terms of oxides (unit: mol%) of the content of each element when it becomes a melt. Is preferred.
  • atoms A, atoms M, Si, B, and P are converted into oxides (unit: mol%) of the content of each atom when it becomes a melt, and 15% ⁇ A 2 O ⁇ 30%, 35% ⁇ MO ⁇ 55%, 3% ⁇ SiO 2 ⁇ 50%, 1% ⁇ B 2 O 3 ⁇ 20%, 1% ⁇ P 2 O 5 ⁇ 18%, and 1% ⁇ (B 2 O 3 + P 2 O 5 ) ⁇ 25%, 0.8 ⁇ A 2 O / (0.5SiO 2 + B 2 O 3 + P 2 O 5 ) ⁇ 1.2, 0.8 ⁇ A 2 O / 0.5MO ⁇
  • the raw materials are selected and mixed so as to obtain a melt that is 1.2.
  • the raw material is a compound containing atom A, a compound containing atom M, a compound containing Si, a compound containing B, a compound containing P, or a compound containing atom X as necessary.
  • A may be at least one atom selected from the group consisting of Li, Na and K. However, since it is suitable as a positive electrode material for a secondary battery, it is preferable to make Li essential. It is particularly preferred.
  • the silicic acid-boric acid compound containing Li can increase the capacity per unit volume (mass) of the secondary battery.
  • Examples of the compound containing the atom A include A carbonate (A 2 CO 3 ), A bicarbonate (AHCO 3 ), A hydroxide (AOH), A borate (A 2 O ⁇ B 2 O 3 , A 2 O ⁇ 2B 2 O 3 ), A phosphate and hydrogen phosphate (A t H 3 -t PO 4 , 0 ⁇ t ⁇ 3), A nitrate (ANO 3 ), A At least one selected from the group consisting of chloride (ACl), A sulfate (A 2 SO 4 ), A acetate (CH 3 COOA), and A oxalate ((COOA) 2 ) These compounds may each form a hydrated salt).
  • a 2 CO 3 or AHCO 3 is particularly preferable because it is inexpensive and easy to handle.
  • ⁇ Compound containing atom M> M may be at least one atom selected from the group consisting of Fe, Mn, Co and Ni.
  • a silicic acid-boric acid compound When applying a silicic acid-boric acid compound to a positive electrode material for a secondary battery, it is preferable to use at least one atom selected from the group consisting of Fe and Mn as M from the viewpoint of cost. Fe is particularly preferable because the theoretical capacity of the positive electrode material for a secondary battery is easily developed. From the viewpoint of increasing the operating voltage, at least one atom selected from the group consisting of Co and Ni is preferable.
  • 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
  • M oxyhydroxide (MO (OH)) metal M
  • M borate M phosphate (M 3 (PO 4 ) 2 , MPO 4 )
  • M chloride M nitrate
  • M at least one selected from the group consisting of sulfates of M, organic salts of M, and the like.
  • Fe 3 O 4 , Fe 2 O 3 , MnO 2 , Co 3 O 4 or NiO is more preferable because it is inexpensive and easy to handle.
  • Fe 3 O 4 , Fe 2 O 3 or MnO 2 is particularly preferred.
  • silicate of A selected from the group consisting of silicon oxide (SiO 2 ), A 2 SiO 3 and A 4 SiO 4 (where A is the same kind of atom as described above), And at least one selected from the group consisting of M silicates selected from the group consisting of MSiO 3 and M 2 SiO 4 (wherein M is the same type of atom as described above).
  • SiO 2 is particularly preferable from the viewpoint of inexpensiveness.
  • the compound containing Si may be crystalline or amorphous.
  • the compound containing B is preferably at least one selected from the group consisting of boron oxide (B 2 O 3 ), boric acid (H 3 BO 3 ), A borate, M borate, and the like.
  • B 2 O 3 or H 3 BO 3 is particularly preferable because it is inexpensive and easy to handle.
  • NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , A phosphate or P 2 O 5 is particularly preferable because it is inexpensive and easy to handle.
  • a compound containing an atom A includes A carbonate (A 2 CO 3 ), A bicarbonate (AHCO 3 ), A hydroxide (AOH), A borate (A 2 O ⁇ B 2 O 3 , A 2 O.2B 2 O 3 ), A nitrate (ANO 3 ), A chloride (ACl), A sulfate (A 2 SO 4 ) and A acetate (CH 3 COOA), and And at least one selected from the group consisting of the oxalate salt of element A ((COOA) 2 ) (however, these compounds may each form a hydrate salt),
  • a compound containing an atom M is an oxide of M (FeO, Fe 3 O 4 , Fe 2 O 3 , MnO, Mn 2 O 3 , MnO 2 , CoO, Co 3 O 4
  • a more preferable combination of the compound containing atom A, the compound containing atom M, the compound containing Si and the compound containing B as a raw material formulation is:
  • the compound containing the atom A is A carbonate (A 2 CO 3 ) or A bicarbonate (AHCO 3 );
  • the compound containing the atom M is an oxide 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) or M Oxyhydroxide (MO (OH)) of
  • the compound containing Si is silicon oxide (SiO 2 )
  • the compound containing B is boron oxide (B 2 O 3 ) or boric acid (H 3 BO 3 ). It is a combination.
  • a compound containing an atom A includes A carbonate (A 2 CO 3 ), A bicarbonate (AHCO 3 ), A hydroxide (AOH), A borate (A 2 O ⁇ B 2 O 3 , A 2 O.2B 2 O 3 ), A phosphate and hydrogen phosphate (A t H 3 -t PO 4 , 0 ⁇ t ⁇ 3), A nitrate (ANO 3 ), A chloride (ACl), A sulfate (A 2 SO 4 ) and A acetate (CH 3 COOA), and A oxalate ((COOA) 2 ) (wherein these compounds are hydrated salts, respectively) And at least one selected from the group consisting of:
  • the compound containing atom M is M oxide, M oxyhydroxide (MO (OH)
  • the compound containing Si is a silicate of A selected from silicon oxide (SiO 2 ), A 2 SiO 3 and A 4 SiO 4 (wherein A is the same kind of atom as described above), and MSiO 3 and At least one selected from M silicates selected from M 2 SiO 4 (wherein M is the same type of atom as described above);
  • the compound containing B is at least one selected from the group consisting of boron oxide (B 2 O 3 ), boric acid (H 3 BO 3 ), A borate, and M borate, and P A compound containing phosphorus oxide (P 2 O 5 ), ammonium phosphate ((NH 4 ) 3 PO 4 ), ammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 , NH 4 H 2 PO 4 ), phosphoric acid (H 3 PO 4 ), polyphosphoric acid (H (n + 2) P n O (3n
  • a more preferable combination of the compound containing atom A as the raw material formulation, the compound containing atom M, the compound containing Si, the compound containing B, and the compound containing P is:
  • the compound containing the atom A is A carbonate (A 2 CO 3 ) or A bicarbonate (AHCO 3 );
  • the compound containing the atom M is an oxide 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) or M Oxyhydroxide (MO (OH)) of
  • the compound containing Si is silicon oxide (SiO 2 )
  • the compound containing B is boron oxide (B 2 O 3 ) or boric acid (H 3 BO 3 );
  • the combination in which the compound containing P is ammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 , NH 4 H 2 PO 4 ).
  • the composition of the raw material formulation corresponds theoretically to the composition of the melt obtained from the raw material formulation.
  • this raw material formulation there are components that are easily lost due to volatilization etc. during melting, such as Li, B, P, etc., so the composition of the resulting melt is calculated from the charge of each raw material It may be slightly different from the oxide equivalent amount (unit: mol%) of the content of each element.
  • the purity of the raw material in a raw material formulation is not specifically limited, The range which does not reduce a desired characteristic is preferable.
  • the purity excluding the water of hydration is preferably 99% or more, particularly preferably 99.9% or more.
  • the particle size of the raw material is not particularly limited as long as it is within a range in which a uniform melt can be obtained by melting.
  • the container used for heating is preferably made of alumina, carbon, silicon carbide, zirconium boride, titanium boride, boron nitride, platinum or platinum containing rhodium, but refractory bricks should be used. You can also. Furthermore, it is preferable to attach a lid to the container in order to prevent volatilization and evaporation.
  • Heating is preferably performed using a resistance heating furnace, a high frequency induction furnace or a plasma arc furnace.
  • the electric resistance furnace is particularly preferably an electric furnace provided with a heating element made of a metal such as a nichrome alloy, silicon carbide, or molybdenum silicide.
  • the temperature at which the raw material mixture is heated and melted is preferably 1,200 ° C. to 1,500 ° C., particularly preferably 1,300 ° C. to 1,450 ° C.
  • the raw material formulation of the second embodiment can be melted at a lower temperature than the raw material formulation of the first embodiment, and a particularly preferred temperature range is 1,250 ° C. to 1,400 ° C.
  • the time for heating and melting the raw material preparation is preferably 0.2 to 2 hours, particularly preferably 0.5 to 2 hours. If the melting time is not less than the lower limit of the above range, the uniformity of the melt will be sufficient, and if it is not more than the upper limit, the raw material components will not easily evaporate.
  • Step (12) or Step (22) the melt obtained in step (11) or step (21) is rapidly cooled to around room temperature (20 to 25 ° C.) to obtain a solidified product.
  • the solidified product preferably contains an amorphous part. By including the amorphous part, it is softer than the crystalline part and thus easily pulverized, and the material diffusion in the amorphous part is fast, so that the reactivity can be increased. It becomes easy to control the composition of the silicic acid-phosphoric acid compound. Furthermore, in the post-process (4), the product can be prevented from being agglomerated, and the particle size of the product can be easily controlled.
  • the amorphous part is preferably 80 to 100% by mass of the solidified product.
  • the amorphous part prefferably be in this range because the solidified product is easily pulverized and the reactivity is increased.
  • the wear of the cooling device is remarkably accelerated, and the burden on the subsequent step (13) or step (23) is increased.
  • the cooling of the melt is preferably performed in an inert gas or a reducing gas because the equipment is simple. According to this cooling method, an amorphous substance can be obtained more easily.
  • 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 ie, the heating rate
  • 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 ⁇ 1 ⁇ 10 8 ° C./second is particularly preferable from the viewpoint of practicality.
  • a method for cooling the melt a method in which the melt is dropped between twin rollers rotating at high speed, a method in which the melt is dropped on a single rotating roller, and cooling is performed, or a carbon plate on which the melt is cooled.
  • a method of cooling by pressing on a metal plate is preferable.
  • a cooling method using twin rollers is particularly preferable because the cooling rate is high and a large amount of processing can be performed.
  • the double roller it is preferable to use one made of metal, carbon or ceramic.
  • a fiber-like solidified product is obtained by continuously winding a fiber-like solidified product (long fiber) from a melt with a drum that rotates at a high speed, or by using a spinner that rotates at a high speed and has pores on the side walls. You may use the method of obtaining (short fiber). If these apparatuses are used, the melt is effectively cooled, and a solidified product having a high purity and a uniform chemical composition can be obtained.
  • a cooling method there is also a method in which the melt is directly poured into water, but this method is difficult to control, it is difficult to obtain an amorphous material, the solidified product becomes a lump, and the disadvantage of requiring a lot of labor for grinding There is.
  • a cooling method there is also a method in which a melt is directly added to liquid nitrogen, and the cooling rate can be made faster than in the case of water, but there are problems similar to the method using water, and the cost is high.
  • 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 surface perpendicular to the average thickness in the case of flakes is not particularly limited.
  • the average diameter is preferably 50 ⁇ m or less, particularly preferably 30 ⁇ m or less.
  • Step (13) or step (23) is a step of pulverizing the solidified product obtained in step (12) or step (22) to obtain a pulverized product.
  • the solidified product may be pulverized after containing at least one carbon source selected from the group consisting of an organic compound and a carbon-based conductive active material. Alternatively, the solidified product may be preliminarily pulverized before the carbon source is included.
  • the solidified product and the carbon source may be pulverized in advance and mixed.
  • the carbon source has an action of preventing oxidation and promoting reduction in step (13) or step (23), step (14) or step (24).
  • silicic acid-boric acid compound or silicic acid-boric acid-phosphoric acid compound can be used as a conductive material for the positive electrode material.
  • the mixing / pulverization is preferably performed by a dry or wet method using a ball mill, a jaw crusher, a jet mill, a planetary mill or the like.
  • a carbon source when included, it is preferable to pulverize in a wet manner in order to uniformly disperse the carbon source on the surface of the pulverized product.
  • the carbon source is an organic compound
  • wet pulverization using a dispersion medium capable of dissolving the organic compound is preferable.
  • the subsequent step (14) or step (24) is preferably performed after removing the dispersion medium by sedimentation, filtration, drying under reduced pressure, drying by heating, or the like.
  • the average particle diameter of the pulverized product is preferably 1 nm to 100 ⁇ m, more preferably 10 nm to 10 ⁇ m, and particularly preferably 10 nm to 1 ⁇ m in terms of volume median diameter in order to increase conductivity when applied to a positive electrode material for a secondary battery.
  • the average particle size is not less than the lower limit of the above range, because the pulverized products are not sintered together in the subsequent step (14) or step (24) and the particle size becomes too large.
  • the heating temperature and time of a following process (14) or process (24) can be reduced, it is preferable.
  • Organic compound at least one selected from the group consisting of saccharides, amino acids, peptides, aldehydes and ketones is preferable, and saccharides, amino acids and peptides are particularly preferable.
  • sugars include monosaccharides such as glucose, fructose, and galactose; oligosaccharides such as sucrose, maltose, cellobiose, and trehalose; polysaccharides such as invert sugar, dextrin, amylose, amylopectin, and cellulose; Can be mentioned.
  • amino acids include amino acids such as alanine and glycine.
  • Peptides include low molecular weight peptides having a molecular weight of 1,000 or less. Furthermore, organic compounds having a reducing functional group such as an aldehyde group or a ketone group are also included. As the organic compound, specifically, glucose, sucrose, glucose-fructose invert sugar, caramel, starch, pregelatinized starch, carboxymethylcellulose and the like are preferable.
  • Carbon-based conductive active material As the carbon-based conductive active material, carbon black, graphite, acetylene black, carbon fiber, amorphous carbon and the like are preferable.
  • carbon-based conductive active material By including a carbon-based conductive active material at the time of mixing and pulverizing the solidified product, after producing the silicic acid-boric acid compound or silicic acid-boric acid-phosphoric acid compound in step (14) or step (24), carbon There is no need to provide a separate step of mixing the conductive conductive material.
  • the distribution of the carbon-based conductive active material in the powder of the silicic acid-boric acid compound and the silicic acid-boric acid-phosphoric acid compound can be reduced. It becomes uniform, and the contact area with the organic compound or a thermal decomposition product (carbide) thereof increases. This makes it possible to increase the bonding strength of the carbon-based conductive active material to the silicic acid-boric acid compound and the silicic acid-boric acid-phosphoric acid compound.
  • the amount of the carbon source is preferably such that the ratio of the carbon equivalent (mass) to the total mass of the solidified product and the carbon equivalent (mass) in the carbon source is 0.1 to 20% by mass. An amount of mass% is particularly preferred.
  • the carbon source at least the lower limit of the above range, the conductivity when the silicic acid-boric acid compound and silicic acid-boric acid-phosphoric acid compound are used as a positive electrode material for a secondary battery can be sufficiently enhanced. .
  • the amount not more than the upper limit of the above range when the silicic acid-boric acid compound and the silicic acid-boric acid-phosphoric acid compound are used as the positive electrode material for the secondary battery, the characteristics as the positive electrode material for the secondary battery are high. Can be retained.
  • Step (14) is a step of obtaining a silicic acid-boric acid compound having a composition represented by formula (1), preferably crystal grains thereof.
  • A +1 valence
  • M +2 valence
  • Si +4 valence
  • Step (24) is a step of obtaining a silicic acid-boric acid-phosphoric acid compound having a composition represented by formula (2), preferably crystal grains thereof.
  • A is +1 valence
  • M is +2 valence
  • Si is +4 valence
  • B is +3 valence
  • P is +5 valence. It is preferable to have a relationship of x + 2y + 4 (1-ab) + 3a + 5b ⁇ / 2.
  • Step (14) or step (24) preferably includes crystal nucleation and grain growth of the pulverized product. Further, when at least one selected from the group consisting of an organic compound and a carbon-based conductive active material is included in the previous pulverization step, the resulting silicic acid-boric acid compound, preferably on the surface of the crystal particles It is preferably a step of bonding at least one selected from an organic compound, a carbon-based conductive active material, and a reactant thereof. When the step (13) or the step (23) is performed by a wet method, the dispersion medium may be removed at the same time as the heating and firing.
  • a silicic acid-boric acid compound when applied to a positive electrode material for a secondary battery, good characteristics are exhibited, which is preferable.
  • 0.3 to 15 mol% of a part of atom M may be substituted with an atom having a valence of +2 or +3 in order to improve performance. .
  • Ti, V, B, Al, Ca, Cu, Mg, and Zn are mentioned.
  • the silicic acid-boric acid compound represented by the formula (1) is a compound having a composition represented by the formula (3) and is a crystal particle because it can be produced at low cost.
  • Li x (Fe m Mn 1-m ) y Si 1-a B a O z (3) (Wherein, x, y, z and a are the same numerical values as described above, and m is 0 ⁇ m ⁇ 1).
  • the silicic acid-boric acid compound having the composition represented by the formula (3) is a compound having the composition represented by the formula (4), a material exhibiting good characteristics can be produced at low cost. Is particularly preferred. LiFe m Mn 1-m Si 1-a B a O z (4) (In the formula, z, a and m are respectively the same numerical values as described above.)
  • the silicic acid-boric acid-phosphoric acid compound having the composition represented by the formula (2) is a compound having the composition represented by the formula (5) and is a crystal particle, it can be produced at low cost. Therefore, it is preferable.
  • the silicic acid-boric acid-phosphoric acid compound represented by the formula (5) is a compound having the composition represented by the formula (6), a material exhibiting good characteristics can be produced at a low cost. Is particularly preferred. LiFe m Mn 1-m Si 1- (a + b) B a P b O z (6) (In the formula, z, a, b and m are respectively the same numerical values as described above.)
  • Step (14) or step (24) is preferably performed in an inert gas or a reducing gas.
  • the pressure may be normal pressure, increased pressure (1.1 ⁇ 10 5 Pa or more), and reduced pressure (0.9 ⁇ 10 5 Pa or less).
  • the container containing the reducing agent (for example, graphite) and the pulverized material is loaded in the heating furnace, reduction of M ions in the pulverized material (for example, change from M 3+ to M 2+ ). Can be promoted.
  • the silicic acid-boric acid compound having the composition represented by the formula (1) and the silicic acid-boric acid-phosphoric acid compound having the composition represented by the formula (2) can be obtained with good reproducibility.
  • the heating temperature is preferably 500 to 1,000 ° C., particularly preferably 600 to 900 ° C.
  • the heating temperature is 1,000 ° C. or less, the pulverized product is difficult to melt and the crystal diameter and particle diameter can be easily controlled.
  • the heating temperature is within this range, silicic acid-boric acid compound and silicic acid-boric acid-phosphoric acid compound having an appropriate crystallinity, particle size, particle size distribution, etc., preferably crystalline particles thereof can be easily obtained. .
  • the step (14) or the step (24) may be performed at a constant temperature or by changing the 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 a desired particle size.
  • the inert gas is a gas containing 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, more preferably 1 to 10% by volume of the reducing gas 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.
  • cooling After the heating in the step (14) or the step (24) is completed, usually cooling to room temperature.
  • 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 crystalline particles, the target product can be obtained while maintaining the crystal structure.
  • the cooling can be performed without using a cooling means.
  • the cooling may be left to cool to room temperature. Cooling is preferably performed in an inert gas or a reducing gas.
  • the organic compound and the carbon-based conductive active material adhering to the surface of the pulverized product in the step (13) or the step (23) are the silicic acid-boric acid compound or the silicic acid-boron produced in the step (14) or the step (24). It can bind to the particle surface of the acid-phosphate compound and function as a conductive material.
  • the organic compound is thermally decomposed in the step (14) or the step (24), and at least a part of the organic compound becomes a carbide to function as a conductive material.
  • the thermal decomposition of the organic compound is preferably performed at 400 ° C. or lower, and the carbonization is preferably performed at 600 ° C. or lower. When pyrolysis is performed at 600 ° C.
  • volume change associated with the pyrolysis reaction can be reduced. Bonds uniformly and firmly on the surface of acid-boric acid compound or silicic acid-boric acid-phosphoric acid compound particles, or between silicic acid-boric acid compound particles or between silicic acid-boric acid-phosphoric acid compound particles .
  • the particles of silicic acid-boric acid compound have a conductive carbonaceous layer of 0.1 to 20% by mass based on the total mass of the silicic acid-boric acid compound and the conductive carbonaceous layer. Alternatively, it is preferably contained at the interface between the particles, and particularly preferably 2 to 10% by mass.
  • the conductive carbonaceous layer in which the particles of silicic acid-boric acid-phosphoric acid compound are 0.1 to 20% by mass with respect to the total mass of the silicic acid-boric acid-phosphoric acid compound and the conductive carbonaceous layer Is preferably contained at the surface of the particles or at the interface between the particles, and particularly preferably 2 to 10% by mass.
  • the silicic acid-boric acid compound having the composition represented by the formula (1) or the formula (2) A silicic acid-boric acid-phosphoric acid compound having the composition shown is produced.
  • the silicic acid-boric acid compound and the silicic acid-boric acid-phosphoric acid compound are preferably particles, more preferably crystal particles, and particularly preferably olivine type crystal particles.
  • the particles include both primary particles and secondary particles.
  • a crystal particle of silicic acid-boric acid compound and silicic acid-boric acid-phosphoric acid compound is formed, and at the same time, an organic compound or a carbon-based conductive active material is formed on the surface. It is possible to manufacture a material in which conductive materials based on the above are uniformly and firmly bonded. This powder material is suitable for a positive electrode material for a secondary battery.
  • secondary particles are present in the obtained silicic acid-boric acid compound and silicic acid-boric acid-phosphoric acid compound particles or powder material containing the same, they are crushed and pulverized to the extent that the primary particles are not destroyed. May be.
  • the crystal particles are olivine-based crystals and preferably do not include crystals composed of cristobalite, boric acid M, and phosphoric acid M.
  • the average particle diameter of the silicic acid-boric acid compound and silicic acid-boric acid-phosphoric acid compound particles of the present invention is preferably 10 nm to 10 ⁇ m, particularly preferably 10 nm to 2 ⁇ m, in terms of volume median diameter. By making the average particle diameter within this range, the conductivity of the powder of silicic acid-boric acid compound and silicic acid-boric acid-phosphoric acid compound particles becomes higher.
  • the average particle diameter can be determined by, for example, observation with an electron microscope or measurement with a laser diffraction particle size distribution meter.
  • the specific surface area can be measured by, for example, a specific surface area measuring apparatus using a nitrogen adsorption method.
  • the crystal particles are preferably composed only of primary particles.
  • the method for producing silicic acid-boric acid compound and silicic acid-boric acid-phosphoric acid compound of the present invention is excellent in manufacturability and composition controllability of silicic acid-boric acid compound and silicic acid-boric acid-phosphoric acid compound.
  • the olivine type silicic acid-boric acid compound and the silicic acid-boric acid-phosphoric acid compound can be produced inexpensively and efficiently.
  • the productivity of crystal particles of silicic acid-boric acid compound and silicic acid-boric acid-phosphoric acid compound can be improved.
  • a positive electrode for a secondary battery By using the silicic acid-boric acid compound and the silicic acid-boric acid-phosphoric acid compound obtained by the production method of the present invention as a positive electrode material for a secondary battery, a positive electrode for a secondary battery can be produced.
  • the silicic acid-phosphoric acid compound and the silicic acid-boric acid-phosphoric acid compound of the present invention are used as a positive electrode material for a secondary battery, when the atom M is, for example, Fe and / or Mn, these divalent / trivalent compounds It works by utilizing the redox reaction for charging and discharging.
  • the positive electrode for a secondary battery of the present invention can be manufactured according to a known electrode manufacturing method except that the silicic acid-boric acid compound and the silicic acid-boric acid-phosphoric acid compound obtained by the manufacturing method of the present invention are used.
  • a silicic acid-phosphoric acid compound powder may be added to a known binder (polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, ethylene propylene diene polymer, styrene-butadiene rubber, acrylonitrile-butadiene rubber, fluorine if necessary.
  • the mixed powder thus obtained may be compression-molded on a support made of stainless steel or filled in a metal container.
  • the mixed powder is mixed with an organic solvent (N-methylpyrrolidone, toluene, cyclohexane, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, methyl acrylate, diethyltriamine, NN-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran.
  • organic solvent N-methylpyrrolidone, toluene, cyclohexane, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, methyl acrylate, diethyltriamine, NN-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran.
  • a metal substrate such as aluminum, nickel, stainless steel, or copper can also be employed.
  • a secondary battery can be manufactured using the silicic acid-boric acid compound and the silicic acid-boric acid-phosphoric acid compound obtained by the manufacturing method of the present invention as a positive electrode material for a secondary battery.
  • 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 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 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 non-aqueous electrolyte lithium ion secondary battery is preferable.
  • the secondary battery manufacturing method of the present invention by applying the secondary battery positive electrode obtained by the secondary battery positive electrode manufacturing method of the present invention to the secondary battery positive electrode, characteristics and reliability can be improved. An excellent secondary battery can be obtained.
  • Step (11) Lithium carbonate (Li 2 CO 3 ), so that the composition of the melt is a Li 2 O, FeO, MnO, SiO 2 and B 2 O 3 conversion amount (unit: mol%), and the ratio shown in Table 1 respectively.
  • Triiron tetroxide (Fe 3 O 4 ), manganese dioxide (MnO 2 ), silicon dioxide (SiO 2 ), and boron oxide (B 2 O 3 ) are weighed, mixed and pulverized in a dry process, Obtained.
  • the obtained raw material mixture was filled in a platinum crucible containing 20% by mass of rhodium.
  • the crucible was placed in an electric furnace (model name: NH-3035, manufactured by Motoyama) equipped with a heating element made of molybdenum silicide.
  • the electric furnace was heated at a rate of 300 ° C./hour and heated at 1,350 to 1,450 ° C. for 0.5 hour while flowing N 2 gas at a flow rate of 1 L / min. Each melt was obtained after confirming that it became transparent visually.
  • Step (12) the melt is cooled at ⁇ 1 ⁇ 10 5 ° C./sec by passing the melt in the crucible through a stainless steel double roller having a diameter of about 15 cm and rotating at 400 revolutions per minute to obtain a flaky solidified product. It was.
  • the obtained solidified product was a glassy substance.
  • the thickness of the flaky solidified material obtained in each example was measured with a micrometer and found to be 50 to 150 ⁇ m.
  • Step (13) The obtained flaky solidified product was lightly kneaded and coarsely pulverized, and then coarsely pulverized using a pestle and mortar. Further, the pulverization medium was made into balls made of zirconia and mixed and pulverized by a dry method using a planetary mill to obtain a pulverized product.
  • the particle diameter of the pulverized product of Example 5 was measured using a laser diffraction / scattering particle size analyzer (manufactured by Horiba, Ltd., apparatus name: LA-950). The median diameter in terms of volume was 2.5 ⁇ m. .
  • Step (14) The crushed materials of Examples 1 to 13 after sieving were heated in 3% by volume H 2 —Ar gas at 700 ° C. for 8 hours, whereby silicic acid-boron each having the composition represented by formula (1) Acid compound particles were obtained. Further, in each example, each pulverized product was heated at 600 ° C. for 8 hours and heated at 800 ° C. for 8 hours in 3% by volume H 2 —Ar gas. Silica-boric acid compound particles having the same composition represented by the formula (1) as in the case of heating for 8 hours were obtained. The average particle diameter of the silicic acid-boric acid compound particles obtained by heating at 600 ° C., and the median diameter in terms of volume was 3.3 ⁇ m. Furthermore, it was 2.1 m ⁇ 2 > / g when the specific surface area was measured with the specific surface area measuring apparatus (Shimadzu Corporation make, apparatus name: ASAP2020).
  • composition analysis The chemical composition of the resulting silicic acid-boric acid compound particles was measured. First, silicic acid-boric acid compound particles were heated and sealed and decomposed with a 2.5 mol / L NaOH solution at 120 ° C., and the decomposed solution was dried under hydrochloric acid acidity and filtered again as an acidic hydrochloric acid solution. A residue was obtained. Fe, Mn, Si, B and P in the filtrate used an inductively coupled emission spectrophotometer (Seiko Instruments Inc., apparatus name: SPS3100), and Li in the filtrate was an atomic absorption photometer (manufactured by Hitachi High-Technologies Corporation, Device name: Z-2310) was used for quantification.
  • Example 14 to 22 Lithium carbonate (Li 2 CO 2 ) so that the composition of the melt is a Li 2 O, FeO, SiO 2 , B 2 O 3, and P 2 O 5 equivalent amount (unit: mol%) and the ratio shown in Table 3 respectively. 3 ), triiron tetroxide (Fe 3 O 4 ), silicon dioxide (SiO 2 ), boron oxide (B 2 O 3 ), and ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), respectively, And mixed and pulverized to obtain a raw material formulation. In the same manner as in Example 1, the raw material formulation was subjected to steps (21) to (24) to obtain a silicic acid-boric acid-phosphoric acid compound.
  • Example 4 The chemical composition of the obtained silicic acid-boric acid-phosphoric acid compound particles was measured in the same manner as in Example 1.
  • Table 4 shows the chemical compositions of the silicic acid-boric acid-phosphoric acid compound particles obtained by heating at 700 ° C. for 8 hours in Examples 14-22.
  • Example 2 The mineral phase of the obtained silicic acid-boric acid compound particles was examined in the same manner as in Example 1.
  • the X-ray diffraction patterns of the silicic acid-boric acid-phosphoric acid compound particles obtained by heating at 700 ° C. for 8 hours in Example 19 and Example 21 are shown in FIGS. 3a) and b), respectively.
  • Example 23 Manufacture of positive electrode for Li ion secondary battery and evaluation battery
  • carbon black and glucose aqueous solution
  • carbon black and glucose aqueous solution
  • the obtained pulverized product was heated at 700 ° C. for 8 hours in Ar gas in the same manner as in Example 1.
  • the chemical composition of the obtained particles was measured in the same manner as in Example 1.
  • the chemical composition was Li 1.01 Fe 0.98 Si 0.65 B 0.35 O 3.31 .
  • the carbon content of the obtained particles was measured using a carbon analyzer (manufactured by Horiba, Ltd., apparatus name: EMIA-920A), it was 2.8% based on the C mass.
  • grains was 1.5 micrometers in median diameter of volume conversion.
  • the obtained carbon-containing particles were used as an active material, and these, polyvinylidene fluoride resin as a binder, and acetylene black as a conductive material were weighed in a mass ratio of 85: 5: 10, and N—
  • a slurry was prepared by thoroughly mixing methylpyrrolidone as a solvent. Next, the slurry was applied to an aluminum foil having a thickness of 30 ⁇ m with a bar coater. The solvent was removed by drying at 120 ° C. in the air, and then the coating layer was consolidated by a roll press and cut into strips each having a width of 10 mm and a length of 40 mm.
  • the coating layer was peeled off leaving a 10 ⁇ 10 mm tip of strip-shaped aluminum foil, which was used as an electrode.
  • the coating thickness of the obtained electrode after roll pressing was 20 ⁇ m.
  • the obtained electrode was vacuum-dried at 150 ° C., then carried into a glove box filled with purified argon gas, and opposed to a counter electrode in which lithium foil was pressure-bonded to a nickel mesh with a porous polyethylene film separator, Both sides were fixed with a polyethylene plate.
  • the counter electrode was put in a polyethylene beaker, and a nonaqueous electrolyte solution in which lithium hexafluorophosphate was dissolved in a mixed solvent of ethylene carbonate and ethyl methyl carbonate (1: 1 volume ratio) at a concentration of 1 mol / L was injected. Fully impregnated. The electrode after impregnation with the electrolytic solution was taken out from the beaker, put in an aluminum laminate film bag, the lead wire part was taken out and sealed to form a half battery. The characteristics of these half cells were measured as follows.
  • This charge / discharge cycle was repeated 10 cycles.
  • the discharge capacity at the fifth cycle of the half cell using the active material of Example 15 was 105 mAh / g. Further, the charge / discharge cycle was repeated 10 cycles in the same manner at 60 ° C.
  • the discharge capacity at the fifth cycle was 135 mAh / g.
  • composition of the melt is 25.0%, 50.0%, 0.5% and 24.5% in terms of Li 2 O, FeO, SiO 2 and B 2 O 3 (unit: mol%), respectively.
  • Lithium carbonate (Li 2 CO 3 ), triiron tetroxide (Fe 3 O 4 ), silicon dioxide (SiO 2 ) and boron oxide (B 2 O 3 ) were weighed so that The raw material formulation was obtained by grinding. Although it melted at 1,350 ° C. in the same manner as in Example 1, a complete melt could not be obtained.
  • Li 2 O melt, FeO as represented by mol% of B 2 O 3 and P 2 O 5 in terms of, respectively, 10.0% 60.0%, and 15.0% and 15.0% Lithium carbonate (Li 2 CO 3 ), triiron tetroxide (Fe 3 O 4 ), boron oxide (B 2 O 3 ), and ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), respectively
  • a silicic acid-boric acid compound and a silicic acid-boric acid-phosphoric acid compound could be produced efficiently. Further, it was confirmed that the produced silicic acid-boric acid compound and silicic acid-boric acid-phosphoric acid compound have excellent characteristics as a positive electrode material for a secondary battery and further as a secondary battery.
  • the method for producing a silicic acid-boric acid compound and a silicic acid-boric acid-phosphoric acid compound according to the present invention is easy to control the composition of the silicic acid-boric acid compound and the silicic acid-boric acid-phosphoric acid compound. It is useful because it is easy.
  • the obtained silicic acid-boric acid compound and silicic acid-boric acid-phosphoric acid compound are useful when applied to a positive electrode material for a secondary battery and further to a secondary battery.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

L'invention concerne des procédés de production d'un composé (acide silicique)-(acide borique) et d'un composé (acide silicique)-(acide borique)-(acide phosphorique) qui ont d'excellentes propriétés de batterie et une excellente fiabilité à faible coût et avec une grande efficacité. Un composé (acide silicique)-(acide borique) ayant une composition chimique représentée par la formule suivante : AxMySi1-aBaOz (0,8 < x < 1,2, 0,8 < y < 1,2 et 0,05 ≤ a ≤ 0,7) peut être produit par solidification d'un matériau fondu par refroidissement, broyage du produit solidifié, et chauffage du produit broyé, où le matériau fondu est produit par chauffage d'une préparation de matériau brut qui comprend au moins un atome (A) sélectionné parmi le groupe constitué de Li, Na et K, au moins un atome (M) sélectionné parmi le groupe constitué de Fe, Mn, Co et Ni, Si et B et qui contient ces atomes dans des quantités qui sont exprimées en termes des teneurs en oxyde suivantes (% en mole) : 15% < A2O < 30%, 35% < MO < 55%, 3% < SiO2 < 50% et 1% < B2O3 < 20%, où le rapport A2O/(0,5 SiO2+B2O3) est de 0,8 à 1,2 exclusivement et le rapport A2O/0,5 MO est de 0,8 à 1,2 exclusivement.
PCT/JP2011/060603 2010-05-06 2011-05-06 Composé (acide silicique)-(acide borique), composé (acide silicique)-(acide borique)-(acide phosphorique), électrode positive pour batterie secondaire, et procédé pour la production de batterie secondaire Ceased WO2011138965A1 (fr)

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CN2011800228192A CN102884000A (zh) 2010-05-06 2011-05-06 硅酸-硼酸化合物和硅酸-硼酸-磷酸化合物、二次电池用正极、以及二次电池的制造方法
JP2012513833A JPWO2011138965A1 (ja) 2010-05-06 2011-05-06 ケイ酸−ホウ酸化合物およびケイ酸−ホウ酸−リン酸化合物、二次電池用正極、および二次電池の製造方法

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