[go: up one dir, main page]

WO2013042777A1 - Procédé de fabrication pour un matériau d'électrode positive pour une batterie secondaire - Google Patents

Procédé de fabrication pour un matériau d'électrode positive pour une batterie secondaire Download PDF

Info

Publication number
WO2013042777A1
WO2013042777A1 PCT/JP2012/074269 JP2012074269W WO2013042777A1 WO 2013042777 A1 WO2013042777 A1 WO 2013042777A1 JP 2012074269 W JP2012074269 W JP 2012074269W WO 2013042777 A1 WO2013042777 A1 WO 2013042777A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
secondary battery
electrode material
compound
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/074269
Other languages
English (en)
Japanese (ja)
Inventor
義久 別府
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2013042777A1 publication Critical patent/WO2013042777A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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 method for producing a positive electrode material for a secondary battery.
  • plug-in hybrid vehicles and electric vehicles are being developed from the viewpoint of carbon dioxide emission regulations and energy saving.
  • it is required to increase the capacity and the energy density while maintaining the safety of the secondary battery.
  • Non-Patent Document 1 discloses a olivine-type silicic acid compound (Li 2 MSiO 4 ) containing two Li atoms in one molecule as a secondary battery material capable of increasing the capacity by a multi-electron reaction.
  • M Fe, Mn).
  • Non-Patent Document 2 discloses a method of obtaining a positive electrode material for a secondary battery having a predetermined crystal structure by once heating and melting a raw material mixture and then cooling it. Thus, once the raw material mixture is in a molten state, the positive electrode material for a secondary battery can be manufactured at low cost and in large quantities, and the uniformity of the chemical composition of the obtained positive electrode material can be improved.
  • Patent Document 1 discloses a method in which a raw material mixture containing a divalent transition metal compound is heated and melted at 1500 ° C. in an argon atmosphere and then rapidly cooled with a single roll to obtain an amorphous transition metal phosphate complex. Is disclosed.
  • Heat melting of the raw material mixture requires heat treatment at a high temperature, and a container used for heat melting requires characteristics such as heat resistance and corrosion resistance.
  • a raw material mixture composed of LiFePO 4 and LiF is placed in a platinum tube, the platinum tube is disposed in a quartz tube, heated by high frequency induction heating to melt the raw material mixture, and then the melt is cooled.
  • a method for obtaining an active material composed of a phosphate complex containing a transition metal such as Fe or Mn is disclosed.
  • Patent Document 3 materials such as Li 2 CO 3 , NH 4 H 2 PO 4 , and Fe (II) C 2 O 4 are put in an alumina crucible with a lid, melted at 1200 ° C., and then the melt is put on an iron plate.
  • a method for obtaining a precursor glass having a basic composition of LiFePO 4 by pouring out and pressing and quenching is disclosed.
  • Patent Document 4 a raw material composition containing Li 2 CO 3 , Fe (COO) 2 .2H 2 O, NH 4 H 2 PO 4, etc. is placed in a crucible with a nozzle made of rhodium / platinum alloy at 1300 ° C.
  • a method of obtaining olivine-type lithium iron phosphate particles by heating after melting and then rapidly cooling the melt and then heating after pulverization is disclosed.
  • Japanese Unexamined Patent Publication No. 2005-158673 Japanese Unexamined Patent Publication No. 2007-73360 Japanese Unexamined Patent Publication No. 2008-47412 Japanese Unexamined Patent Publication No. 2011-1242
  • Patent Document 2 is not suitable for mass production, and platinum components are mixed from the platinum tube into the internal melt during heating by high-frequency induction, leading to a decrease in product purity and an increase in production costs. There is a fear.
  • the corrosion resistance of alumina constituting the crucible is not necessarily high, the crucible is easily worn by erosion of Fe or the like during heating and melting, and the replacement frequency increases. Further, the alumina component is likely to be mixed into the melt from the crucible, and there is a possibility that the purity may be lowered. Furthermore, since alumina has a relatively high coefficient of thermal expansion, the crucible may be damaged due to a rapid temperature change.
  • Patent Document 4 at high temperatures, the crucible is easily worn out by the formation of an alloy between platinum and rhodium contained in the crucible and the iron component in the melt, and platinum and rhodium dissolved from the crucible are contained in the melt. It may be easily mixed into the product, resulting in a decrease in product purity and an increase in production cost.
  • An object of the present invention is to provide a method for efficiently producing a positive electrode material for a secondary battery that is reduced in the mixing of components derived from a container used for heating and melting a raw material mixture and excellent in purity at a low cost. is there.
  • the method for producing a positive electrode material for a secondary battery according to the present invention is a method for producing a positive electrode material for a secondary battery containing a compound having an olivine type, pyroxene type, or NASICON type crystal structure, wherein the raw materials are prepared. And a raw material preparation step of preparing a raw material preparation, and a melting step of melting the raw material preparation in a container formed of an electroformed refractory to obtain a melt.
  • the electrocast refractory is preferably at least one selected from the group consisting of an alumina-zirconia-silica electrocast refractory, a high zirconia electrocast refractory, and an alumina electrocast refractory. Further, the melting step is preferably performed at 900 ° C to 1700 ° C.
  • the method for producing a positive electrode material for a secondary battery of the present invention includes a cooling step of cooling the melt obtained in the melting step to obtain a solidified product. Furthermore, it is preferable to have a heating step of heating the solidified product obtained in the cooling step.
  • the phosphoric acid compound represented by following (1) Formula is mentioned.
  • A represents at least one atom selected from the group consisting of Li, Na, and K
  • M represents at least one atom selected from the group consisting of Fe, Mn, Co, and Ni
  • X 1 represents at least one atom selected from the group consisting of Zr, Ti, Nb, Ta, Mo, and W
  • Z 1 represents at least one type selected from the group consisting of Si, B, Al
  • V A is 0 ⁇ a ⁇ 0.2
  • b is 0 ⁇ b ⁇ 0.2
  • c is the numerical value of a and b
  • the silicic acid compound represented by following (2) Formula is mentioned.
  • A represents at least one atom selected from the group consisting of Li, Na, and K, M represents at least one atom selected from the group consisting of Fe, Mn, Co, and Ni;
  • X 2 represents at least one atom selected from the group consisting of Zr, Ti, Nb, Ta, Mo, and W, and
  • Z 2 represents at least one type selected from the group consisting of P, B, Al, and V D is 0 ⁇ d ⁇ 0.2, e is 0 ⁇ e ⁇ 0.2, f is the numerical value of d and e, and the valence of M, the valence of X 2 and Z It is a number that depends on the valence of 2 and satisfies electrical neutrality.
  • the present invention it is possible to efficiently produce a positive electrode material for a secondary battery that is less contaminated with components derived from a container used for heating and melting the raw material mixture and has excellent purity.
  • olivine type compound “compound having an olivine type crystal structure” is also referred to as “olivine type compound”
  • compound having a pyroxene type crystal structure” is also referred to as “pyroxene type compound”
  • “Compound having” is also referred to as “Nashikon-type compound”.
  • the “compound having an olivine type, pyroxene type, or NASICON type crystal structure” is also referred to as “compound ( ⁇ )”.
  • the phosphoric acid compound having the composition represented by the above formula (1) is also referred to as “phosphoric acid compound (1)”
  • the silicic acid compound having the composition represented by the above formula (2) is referred to as “silicic acid”. Also referred to as “compound (2)”.
  • a method for producing a positive electrode material for a secondary battery according to the present invention is a method for producing a positive electrode material for a secondary battery containing a compound having an olivine type, pyroxene type, or NASICON type crystal structure, wherein raw materials are prepared.
  • the secondary battery positive electrode material according to the present invention is preferably a compound having an olivine type, pyroxene type, or NASICON type crystal structure.
  • Examples of the olivine type compounds include those represented by the general formula AMPO 4 , AVOPO 4 , A 2 MSiO 4 , A 2 VOSiO 4 , AMBO 3 , A 2 MPO 4 F, or AVOPO 4 F.
  • examples of pyroxene-type compounds include those represented by general formulas AMSi 2 O 6 and AVSi 2 O 6 .
  • a 2 MP 2 O 7 is also included in the pyroxene-type compound.
  • Examples of NASICON compounds include those represented by the general formula A 3 M 2 (PO 4 ) 3 or A 3 V 2 (PO 4 ) 3 .
  • atom A represents an alkali metal atom such as Li, Na, and K
  • atom M represents a transition metal atom such as Fe, Mn, Co, and Ni.
  • P, Si, B, and V may each be partially substituted with each other, or these may be substituted with atoms such as Al or S.
  • the olivine-type compound, pyroxene-type compound, and nasicon-type compound described above are at least selected from Zr, Ti, Nb, Ta, Mo, and W together with the atoms A and M, in addition to the compounds represented by the general formula described above. It may contain one kind of atom.
  • the phosphoric acid compound (1) represented by the following formula (1) is preferred as the phosphoric acid compound.
  • AM 1-a X 1 a P 1-b Z 1 b O 4 + c (1)
  • A is at least one atom selected from the group consisting of Li, Na, and K
  • M is at least one atom selected from the group consisting of Fe, Mn, Co, and Ni
  • X 1 is Zr.
  • Ti, Nb, Ta, Mo, and W at least one atom selected from the group consisting of W
  • Z 1 represents at least one atom selected from the group consisting of Si, B, Al, and V.
  • a is 0 ⁇ a ⁇ 0.2
  • b is 0 ⁇ b ⁇ 0.2
  • c depends on the numerical values of a and b, and the valence of M, the valence of X 1 and the valence of Z 1 , Number that satisfies electrical neutrality.
  • the raw material preparation can be satisfactorily melted in the melting step (ii) described later, and a uniform melt can be obtained.
  • the phosphoric acid compound (1) can be obtained by the heating step (v) described below, and further, the phosphoric acid compound (1) containing an olivine type crystal structure, particularly a phosphoric acid compound (1) comprising only an olivine type crystal structure (1). ) Is preferable.
  • the value of a is more preferably 0.001 ⁇ a ⁇ 0.1, and particularly preferably 0.001 ⁇ a ⁇ 0.05.
  • the value of b is more preferably 0.001 ⁇ b ⁇ 0.1, and particularly preferably 0.001 ⁇ b ⁇ 0.05.
  • the value of c in the phosphoric acid compound (1) is a number depending on the numerical values of a and b, and the valence of M, the valence of X 1 and the valence of Z 1 , from 1/2 of the total positive charge The value obtained by subtracting 4.
  • the silicate compound (2) represented by the following formula (2) is preferred as the silicate compound.
  • A is at least one atom selected from the group consisting of Li, Na, and K
  • M is at least one atom selected from the group consisting of Fe, Mn, Co, and Ni
  • X 2 is Zr.
  • Z 2 represents at least one atom selected from the group consisting of P, B, Al, and V.
  • d represents 0.
  • f depends on the numerical values of d and e, and the valence of M, the valence of X 2 and the valence of Z 2 , It is a number that satisfies the target neutrality.
  • the raw material preparation can be melted well in the melting step (ii) described later, and a uniform melt can be obtained.
  • the silicate compound (2) can be obtained by the heating step (v) described later, and further, the silicate compound (2) having an olivine type crystal structure, particularly a silicate compound (2) having only an olivine type crystal structure (2). ) Is preferable.
  • the value of d is more preferably 0.001 ⁇ d ⁇ 0.1, and particularly preferably 0.001 ⁇ d ⁇ 0.05.
  • the value of e is more preferably 0.001 ⁇ e ⁇ 0.1, and particularly preferably 0.001 ⁇ e ⁇ 0.05.
  • the value of f in the composition of the silicate compound (2) is a number that depends on the values of d and e, and the valence of M, the valence of X 2 and the valence of Z 2 , and is 1 / The value obtained by subtracting 4 from 2.
  • the atom A is suitable as a positive electrode material for a secondary battery, it is preferable to make Li essential, and it is particularly preferable to use only Li.
  • the phosphoric acid compound (1) containing Li and the silicic acid compound (2) containing Li increase the capacity per unit volume (mass) of the secondary battery.
  • the atom M is preferably composed of only one kind or two kinds. In particular, it is preferable in terms of cost that the atom M consists of Fe alone, Mn alone, or Fe and Mn.
  • the valence of atom M in phosphoric acid compound (1) or silicic acid compound (2) is in the range of +2 to +4.
  • the valence of atom M is +2, +8/3, +3 when atom M is Fe, +2, +3, +4 when Mn, +2, +8/3, +3 when Co, +2, when Ni is Ni, +4 is preferred.
  • the valence of atom M is preferably 2 to 2.2, more preferably 2.
  • the atoms X 1 and X 2 are at least one atom selected from the group consisting of Zr, Ti, Nb, Ta, Mo and W. From the viewpoint of performance, Zr, Ti or Nb is preferable, and Zr or Ti is particularly preferable.
  • the valences of the atoms X 1 and X 2 in the phosphoric acid compound (1) or the silicic acid compound (2) are basically +4 for Zr, +2 or +4 for Ti, +2 or +5 for Nb, Ta is +2 or +5, Mo is +4 or +6, and W is +4 or +6.
  • the atom Z 1 is at least one selected from the group consisting of Si, B, Al, and V. From the viewpoint of performance, B or Al is preferable, and B is particularly preferable.
  • the atom Z 2 is at least one selected from the group consisting of P, B, Al, and V. From the viewpoint of performance, B or Al is preferable, and B is particularly preferable.
  • the valences of the atoms Z 1 and Z 2 are basically +5 for P, +3 for B, +3 for Al, and +3 for V. +3, +4, +5.
  • the silicic acid compound (2) is preferable because it can increase the capacity per unit volume (mass) of the secondary battery when used as the positive electrode material for the secondary battery.
  • a method for producing a positive electrode material for a secondary battery according to the present invention is a method for producing a positive electrode material for a secondary battery containing the compound having the olivine type, pyroxene type, or NASICON type crystal structure described above, and preparing raw materials
  • the production method of the present invention preferably further includes a cooling step (iii), a pulverizing step (iv), and a heating step (v). Each step will be specifically described below.
  • each component source of an olivine type compound, pyroxene type compound, or NASICON type compound is selected and mixed so as to be a melt having a predetermined composition.
  • the compound containing atom A includes A carbonate (A 2 CO 3 ), A hydrogen carbonate (AHCO 3 ).
  • a 2 CO 3 , AHCO 3 , or AF is more preferable because it is inexpensive and easy to handle.
  • 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 silicate MO ⁇ SiO 2 , 2MO ⁇ SiO 2 etc.
  • M phosphate M 3 (PO 4 ) 2 etc.
  • Borate M 3 (BO 3 ) 2 etc.
  • M sulfate MSO 4 , M 2 (SO 4 ) 3 etc.
  • M organic acid salt acetate (M (CH 3 COO) 2 ) and oxalate (M (COO 2 ) and M alkoxides (M (OCH 3 )
  • 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 the atom M is Fe Fe 3 O 4 and / or Fe 2 O 3 is preferable, and as the compound when the atom M is Mn, MnO 2 is preferable.
  • the compound containing atom M may be one type or two or more types.
  • SiO 2 silicon oxide
  • Si (OCH 3 ) 4 silicon alkoxide
  • a silicate, or M silicate is preferable.
  • the compound containing Si may be crystalline or amorphous. Among them, more preferable because SiO 2 is inexpensive.
  • anhydrous phosphoric acid P 2 O 5
  • ammonium hydrogen phosphate NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4
  • a or M phosphate is preferable.
  • the phosphate of A or M for example, at least one selected from the group consisting of Li 3 PO 4 , Fe 3 (PO 4 ) 2 , FePO 4 and Mn 3 (PO 4 ) 2 is preferable.
  • the compound containing P may be crystalline or amorphous. Of these, NH 4 H 2 PO 4 is more preferable because it is inexpensive.
  • Examples of the compound containing atoms X 1 and X 2 include oxides of X 1 and X 2 such as ZrO 2 , TiO 2 , Nb 2 O 5 and Ta 2 O 5. , MoO 3 or WO 3 are preferred.
  • Compounds containing atoms Z 1 and Z 2 include Z 1 , Z 2 oxides (P 2 O 5 , B 2 O 3, etc.), A or M phosphorus At least one selected from the group consisting of acid salts, A or M silicates, A or M borates, A or M aluminates, and A or M vanadates is preferred.
  • the atoms Z 1 and Z 2 contain P, at least one selected from the group consisting of Li 3 PO 4 , Fe 3 (PO 4 ) 2 , FePO 4 and Mn 3 (PO 4 ) 2 , Si SiO 2 when contained, B 2 O 3 and / or H 3 BO 3 when containing B, at least one selected from the group consisting of Al 2 O 3 , AlO (OH) and aluminosilicate when containing Al , V is preferable because vanadium oxide (VO, V 2 O 3 , VO 3 , V 2 O 5, etc.) is inexpensive.
  • a suitable combination of the raw material formulations is a carbonate or hydrogen carbonate in which the compound containing atom A is A, an oxide of M in compound containing atom M, an ammonium hydrogen phosphate or a phosphate in which compound P is contained In this case, it is a combination when the compound containing Si is silicon oxide.
  • 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 obtained melt is based on an oxide standard calculated from the charged amount of each raw material. It may be slightly different from the mol%. 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 diameter of each raw material in the raw material formulation 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 electroformed refractory is an abbreviation for electrofused cast refractory, and a selected raw material is prepared in accordance with a target component and completely melted in an electric furnace. It is a generic term for refractories produced by casting in a mold and solidifying by slow cooling. In this specification, the refractory is used in the same meaning as ceramics.
  • electrocast refractories examples include alumina-silica electrocast refractories, alumina electrocast refractories, alumina-zirconia-silica electrocast refractories, and high zirconia electrocast refractories.
  • alumina-zirconia-silica electrocast refractories, high zirconia electrocast refractories, or alumina electrocast refractories are preferably used from the viewpoint of easy availability and high corrosion resistance.
  • An alumina-zirconia-silica electrocast refractory is an electrocast refractory having a structure in which matrix glass surrounds corundum, baderite, or eutectic thereof.
  • the content of the matrix glass phase is preferably 20% by mass or less, and more preferably 16% by mass or less.
  • the chemical composition when the entire alumina-zirconia-silica electrocast refractory containing the matrix glass phase is 100% by mass in terms of oxide, Al is 45 to 55% by mass in terms of Al 2 O 3 , Zr Is preferably 35 to 45% by mass in terms of ZrO 2 , Si is 10 to 16% by mass in terms of SiO 2 , and Na is 1 to 2% by mass in terms of Na 2 O.
  • Examples of the alumina-zirconia-silica electrocast refractories include ZB-1681 (trade name of AGC Ceramics), ZB-1711 (trade name of AGC Ceramics), SCIMOS CS-3 (trade name of Saint-Gobain tee M), SCIMOS CS-5 ( Saint-Gobain tee product name).
  • a high zirconia electrocast refractory is an electrocast refractory having a zirconia (ZrO 2 ) content of 90% by mass or more, and has a structure in which a small amount of a matrix glass phase surrounds a bedrite crystal phase, for example. Preferably used.
  • the content of the matrix glass phase is preferably 4 to 12% by mass, and more preferably 4 to 7% by mass.
  • Zr is 90 to 97 in terms of mass% in terms of ZrO 2. %, Si containing 3 to 5% in terms of SiO 2 , Na containing 0.1 to 2% in terms of Na 2 O, and Al containing 0.5 to 2.5% in terms of Al 2 O 3 are preferred. It contains more than 92 to 97% in terms of ZrO 2 , Si to 3 to 4% in terms of SiO 2 , Na to 0.2 to 1% in terms of Na 2 O, and Al to 1 to 2% in terms of Al 2 O 3 preferable. Further, B may be contained in an amount of 0.1 to 0.5% in terms of B 2 O 3 , and P may be contained in an amount of 0.1 to 0.5% in terms of P 2 O 3 .
  • Examples of the high zirconia electrocast refractory include ZB-X950 (AGC Ceramics company trade name) and SCIMOS Z (Saint Govin T. M trade name).
  • Alumina electrocast refractories are electrocast refractories with a total content of ⁇ -alumina and ⁇ -alumina of 95% by mass or more, depending on the ratio of ⁇ -alumina and ⁇ -alumina contained in the electrocast refractories. , ⁇ -alumina electrocast refractory, ⁇ , ⁇ -alumina electrocast refractory or ⁇ -alumina electrocast refractory.
  • ⁇ , ⁇ -alumina electrocast refractories are easy to obtain, have sufficient strength, and have a dense structure, so that they can be suitably used as containers for heating and melting.
  • the content of the matrix glass phase is preferably 10% by mass or less, and preferably 2% by mass or less.
  • the chemical composition of the alumina electrocast refractory when the entire alumina electrocast refractory including the matrix glass phase is 100% by mass in terms of oxide, Al is 93 to 99 in terms of mass% in terms of Al 2 O 3. 0.5%, Si containing 0.1 to 1.0% in terms of SiO 2 , Na containing 0.2 to 6.5% in terms of Na 2 O, Al being preferably 94.5 in terms of Al 2 O 3 More preferably, it contains ⁇ 99%, Si contains 0.1 to 1.0% in terms of SiO 2 , and Na contains 0.2 to 5% in terms of Na 2 O.
  • alumina electrocast refractories include ⁇ -alumina electrocast refractories, MB-A (trade name of AGC Ceramics), SCIMOS A (trade name of Saint-Gobain T.M), ⁇ , ⁇ -alumina As electroformed refractories, MB-G (trade name of AGC Ceramics), SCIMOS M (trade name of Saint-Gobain tee M), Jaguar M (trade name of Societe Europian de Prodisputedy Leflectaire), ⁇ -alumina Examples of cast refractories include MB-U (trade name of AGC Ceramics), SCIMOS H (trade name of Saint-Gobain tee M), and Jaguar H (trade name of Societe Europian de Produy Leflectre).
  • alumina-zirconia-silica electrocast refractories have a dense structure composed of ⁇ -alumina, baderite, or eutectic thereof, and matrix glass surrounding these crystals. Even when a raw material composition containing a heavy metal element at a high rate is melted, it is preferable because these components are difficult to enter and problems such as leakage of contents are unlikely to occur.
  • a phosphoric acid compound having a relatively low melting temperature it is preferable to melt the raw material formulation in a container formed of a high zirconia electroformed refractory with little contamination from the refractory.
  • the fireproof temperature of the electroformed refractory used for the container is preferably 1000 ° C. or higher.
  • the melt resistance of the container used for melting may be significantly reduced.
  • the refractory temperature of the electroformed refractory is preferably in the range of 1,000 to 2,000 ° C., more preferably in the range of 1,200 to 1,800 ° C.
  • the refractory temperature of the electrocast refractory means a temperature at which no remarkable change in appearance is observed when the electrocast refractory is heated for 24 hours.
  • the surface roughness (Rmax) of the electroformed refractory is preferably 0.035 to 5 mm. If the surface roughness (Rmax) of the electroformed refractory exceeds 5 mm, the container may be easily eroded by heavy metal elements such as Fe and Mn in the melt.
  • the surface roughness (Rmax) of the electroformed refractory is more preferably 0.04 to 3 mm, and more preferably 0.05 to 1 mm.
  • the surface roughness (Rmax) of the electrocast refractory can be measured using a contact-type surface roughness meter.
  • the porosity of the electroformed refractory is preferably 0.1 to 5%.
  • An electrocast refractory having a porosity of less than 0.1% is actually difficult to manufacture.
  • the porosity of the electroformed refractory exceeds 5%, heavy metal elements such as Fe and Mn contained in the melt are likely to enter the refractory, and sufficient corrosion resistance cannot be obtained. There is a possibility that leakage of the molten material is likely to occur.
  • the porosity of this electrocast refractory can be measured using a specific gravity method.
  • the container formed of the electroformed refractory is not particularly limited in size and shape, and can be used as a small cylindrical crucible or a large melting tank.
  • the electroformed refractory may be used at least in a contact portion with the melt, and a non-contact portion with the melt, such as the upper structure of the melt tank, may be composed of other materials.
  • a small cylindrical crucible in order to prevent volatilization and evaporation of a raw material formulation or a molten material, it is preferable to heat-melt by attaching a lid to the container.
  • a heat source of a heating furnace Electricity, oil, gas, etc., or these combinations can be used. It is preferable to burn with a burner using oil or gas. The burner is preferably placed at the top of the melt tank.
  • the raw material mixture is preferably melted at a heating temperature of 900 to 1700 ° C.
  • a heating temperature refers to the temperature of the melt itself and can be measured with a thermocouple or a pyrometer. Melting means that each raw material melts and becomes transparent with the naked eye.
  • the heating temperature is 900 ° C. or higher, melting is facilitated, and when it is 1700 ° C. or lower, the raw material is hardly volatilized.
  • melting can be performed more easily, melting is more preferably performed at a heating temperature of 1000 ° C. or higher. Moreover, since wear of the electroformed refractory due to heating is suppressed, melting is more preferably performed at a heating temperature of 1500 ° C. or less.
  • the heating time can be appropriately set in consideration of the melting method, the melting scale, the uniformity of the molten metal, etc., but is preferably 0.2 to 24 hours, particularly preferably 0.5 to 2 hours.
  • the heating time is 0.5 hours or more, the uniformity of the melt is sufficient, and when it is 2 hours or less, the raw material is difficult to volatilize.
  • stirring may be performed to increase the uniformity of the melt.
  • the melt may be clarified at a temperature lower than the maximum temperature during melting until the next cooling step (iii) is performed.
  • the raw material may be charged once or a plurality of times.
  • the melting step (ii) is preferably performed in the air, in an inert atmosphere, or in a reducing atmosphere.
  • the pyroxene type or NASICON type compound containing the atom V does not require any particular control. Conditions suitable for the heating method such as the type of container and heating furnace and heat source can be selected as the melting conditions.
  • the pressure may be carried out under any conditions of normal pressure, pressurization, and reduced pressure (0.9 ⁇ 10 5 Pa or less). Furthermore, you may charge the container which put the reducing agent (for example, graphite) in the heating furnace. It is preferred that the melt is more reductive, but even if it is more oxidative, it can be reduced (for example changing from M 3+ to M 2+ ) in the subsequent heating step (v).
  • the reducing agent for example, graphite
  • the inert atmosphere is a gas condition including 99% by volume or more of at least one inert gas selected from the group consisting of noble gases such as nitrogen (N 2 ), helium (He), and argon (Ar).
  • the reducing atmosphere means that the above-described inert gas is a gas condition that contains a gas having a reducing property and does not substantially contain oxygen.
  • the reducing gas include hydrogen (H 2 ), carbon monoxide (CO), and ammonia (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.
  • the oxygen content is preferably 1% by volume or less in the gas, and more preferably 0.1% by volume or less.
  • the melting step (ii) may be performed batchwise or continuously.
  • the reduction treatment of the element M can be performed in this step, the reduction treatment can be performed by performing the heat treatment in the subsequent step. It does not have to be performed in the process.
  • the solidified product is preferably an amorphous material, but a part of the solidified product may be a crystallized product.
  • the next pulverization step (iv) can be easily performed, and the composition and particle size of the resulting compound can be easily controlled.
  • the crystallized product becomes a crystal nucleus in the heating step (v) described later, and it is easy to crystallize.
  • the amount of crystallized material in the solidified product is preferably 0 to 30% by mass with respect to the total mass of the solidified product. When a large amount of crystallized material is contained, it becomes difficult to obtain a granular or flaky solidified material. Moreover, the wear of the cooling device is accelerated, and the burden of the subsequent pulverization step (iv) is increased.
  • the cooling of the melt is preferably performed in the air, under an inert atmosphere, or under a reducing atmosphere because the equipment is simple.
  • Preferred conditions for the inert atmosphere and the reducing atmosphere are the same as those described in the melting step (ii).
  • the cooling rate is preferably more than 1 ⁇ 10 3 °C / sec from 1000 ° C. to 50 ° C., more 1 ⁇ 10 4 °C / sec is particularly preferable.
  • the cooling rate is 1 ⁇ 10 3 ° C./second or more, an amorphous material is easily obtained.
  • the faster the cooling rate the easier it is to obtain an amorphous material.
  • it is preferably 1 ⁇ 10 10 ° C./second or less, and from the point of practical use, it is 1 ⁇ 10 8 ° C./second or less. Particularly preferred.
  • Cooling methods include, for example, a method in which a melt is dropped between twin rollers rotating at high speed to obtain a flake-like solidified product, and a flake-like or plate-like solidified product by dropping the melt on a rotating single roller , A method of obtaining a lump solidified product by pressing a melt on a cooled carbon plate or metal plate, a method of obtaining a lump solidified product by spraying the melt into air or water in small particles It is preferable to adopt. 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 obtained solidified product tends to be an amorphous material, and the chemical composition of the solidified product This is preferable because uniformity is improved.
  • the so-called rapid cooling treatment at a cooling rate of 1 ⁇ 10 3 ° C./second or more may be performed as it is on the melt flowed out of the container formed of the electroformed refractory, and the melt melted in the container The product may be once cooled at a normal rate and then remelted.
  • the solidified product is preferably flaky or fibrous.
  • the average thickness is preferably 200 ⁇ m or less, and more preferably 100 ⁇ m or less.
  • the average diameter of the surface perpendicular to the flake thickness direction is not particularly limited. In the case of a fibrous form, the average diameter is preferably 50 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • the burden of the subsequent pulverization step (iv) can be reduced, and the crystallization efficiency in the heating step (v) can be increased.
  • the average thickness of the flaky solidified product can be measured with a caliper or a micrometer. Further, the average diameter of the fibrous solidified product can be measured by the above method or observation with a microscope.
  • the solidified product obtained in the cooling step (iii) usually has an advantage of being easily pulverized because it contains a lot of amorphous material or consists of an amorphous material. Further, there is an advantage that the apparatus used for pulverization can be pulverized without imposing a burden and the particle diameter can be easily controlled. For example, when a positive electrode material is obtained by a solid phase reaction, pulverization is performed after firing. In this case, residual stress may be generated by pulverization and battery characteristics may be deteriorated. In contrast, by performing the pulverization step (iv) before the heating step (v) described later, the residual stress generated by the pulverization can be reduced or removed by the heat treatment.
  • the pulverization step (iv) at least one selected from the group consisting of an organic compound and a carbon-based conductive material may be added as a carbon source. Since the organic compound or the carbon-based conductive material functions as a conductive material after the heating step (v) described later, the conductivity of the positive electrode material for the secondary battery can be increased. Further, by adding an organic compound or a carbon-based conductive material, oxidation in the pulverization step (iv) and the heating step (v) can be prevented, and further reduction can be promoted.
  • the carbon source is added in the pulverization step (iv)
  • the solidified product and the carbon source are mixed and then pulverized, the solidified product and the carbon source are pulverized and mixed, or the solidified product is added.
  • a step of adding a carbon source after pulverization is preferred.
  • a carbon source is only an organic compound, it can mix with a solidified material, without grind
  • the compound ( ⁇ ) obtained in the heating step (v) of the next step is an insulator, it is preferable to increase the electrical conductivity for use as a positive electrode material for a secondary battery.
  • the carbon-based conductive material serves as conductive carbon and covers at least a part of the surface of the compound ( ⁇ ).
  • an organic compound is used, at least a part of the organic compound is carbonized by performing the heating step (v) of the next step, and at least a part of the surface of the compound ( ⁇ ) is formed as conductive carbon. Cover. Since the conductive carbon functions as a conductive material for the compound ( ⁇ ), the electrical conductivity of the positive electrode material for a secondary battery can be increased.
  • the organic compound as the carbon source is preferably a compound that undergoes a thermal decomposition reaction when heated in an inert atmosphere or a reducing atmosphere, and oxygen and hydrogen are released and carbonized.
  • the organic compound is at least one selected from the group consisting of saccharides, amino acids, peptides, aldehydes, ketones, carboxylic acids, terpenes, heterocyclic amines, fatty acids and aliphatic acyclic polymers having functional groups. Species are preferred.
  • the carbon conductive material as the carbon source is preferably at least one selected from the group consisting of carbon black, graphite, acetylene black, carbon fiber, and amorphous carbon.
  • 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 ratio of the mass of the carbon source is such that the carbon equivalent (mass) in the carbon source is 0.1 to 20 with respect to the total mass of the mass of the solidified product and the carbon equivalent (mass) in the carbon source.
  • An amount of mass% is preferable, and an amount of 2 to 10 mass% is more preferable.
  • the organic compound and the carbon-based conductive material are adjusted so that the total amount thereof falls within the above range when used in combination. By making the amount of carbon 0.1% by mass or more, the conductivity of the positive electrode material for a secondary battery made of the compound ( ⁇ ) can be sufficiently increased. Moreover, electroconductivity can fully be improved, keeping the characteristic as a positive electrode material for secondary batteries high by making carbon amount 20 mass% or less.
  • 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 various methods stepwise depending on the particle diameter. For example, preliminarily pulverizing with a cutter mill and then pulverizing with a planetary mill or ball mill is preferable 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 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 6 hours or more, the pulverization can be sufficiently advanced, and if it is 360 hours or less, excessive pulverization can be suppressed.
  • the pulverization may be performed either dry or wet, but is preferably performed in a wet manner from the viewpoint that the particle size of the pulverized product can be reduced.
  • the pulverization step (iv) is preferably performed using a solvent (pulverization solvent).
  • a solvent pulverization solvent
  • the heating step (v) When the pulverization step (iv) is performed in a wet manner, it is preferable to carry out the heating step (v) after removing the pulverization solvent by sedimentation, filtration, drying under reduced pressure, drying by heating, or the like. However, when the ratio of the solid content with respect to the grinding solvent is 30% or more, the pulverized product containing the grinding solvent may be used in the heating step (v).
  • the pulverization solvent a solvent having an appropriate polarity that is difficult to dissolve the solidified product and is compatible with the carbon source, and does not significantly increase the viscosity when mixed with the solidified product and the carbon source is preferable.
  • Water is preferable from the viewpoint of cost and safety.
  • an organic solvent is preferable. Examples of 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 total concentration of the solidified product and the carbon source is 1 to 80%, particularly preferably 10 to 40%.
  • Productivity can be improved by making the usage-amount of a grinding
  • pulverization of a solidified material and a carbon source can be advanced efficiently because the usage-amount of a grinding
  • the average particle size of the pulverized product is preferably 10 nm to 10 ⁇ m, particularly preferably 10 nm to 5 ⁇ m in terms of volume-based median diameter, from the viewpoint of obtaining higher conductivity when applied to a positive electrode material for a secondary battery.
  • the average particle size is 10 nm or more, when the heating step (v) is performed, the particles of the compound ( ⁇ ) do not sinter and the particle size does not become too large.
  • the average particle size is 10 ⁇ m or less, it is easy to obtain a secondary battery positive electrode material exhibiting high conductivity, and it becomes easy to realize a higher capacity and a higher energy density.
  • the sintering aid acts when the heating step (v) is performed, and the average particle size after heating is increased.
  • the average particle size is obtained mainly by a laser diffraction / scattering particle size measuring device (trade name: LA-950, manufactured by Horiba, Ltd.). If this is difficult, a sedimentation method or a flow image analyzer can be used.
  • Heating step (v) After the pulverization step (iv), the obtained pulverized product is heated in an inert atmosphere or a reducing atmosphere to synthesize a compound ( ⁇ ) having a predetermined composition from the pulverized product of the solidified product (v). It is preferable to carry out.
  • the heating step (v) preferably includes relaxation of stress generated by pulverization, crystal nucleation of the pulverized product, and grain growth.
  • the heating step (v) for example, it is preferable to obtain particles of the phosphoric acid compound (1) or particles of the silicic acid compound (2), and crystal particles of the phosphoric acid compound (1) or the silicic acid compound (2) are obtained. It is more preferable to obtain, and it is particularly preferable to obtain crystal particles of the phosphoric acid compound (1) having an olivine type crystal structure or crystal particles of the silicate compound (2) having an olivine type crystal structure. It is preferable that the obtained compound does not contain an amorphous substance. When the compound does not contain an amorphous substance, a halo pattern is not detected by X-ray diffraction.
  • the organic compound or carbon-based conductive substance adhering to the surface of the pulverized product in the pulverization step (iv) is bonded to the surface of the compound ( ⁇ ), preferably its crystal particles, generated in the heating step (v), and functions as a conductive material.
  • the organic compound is thermally decomposed in the heating step (v), and at least a part thereof becomes a carbide to function as a conductive material.
  • the dispersion medium may be removed simultaneously with heating.
  • the heating temperature for synthesizing the compound ( ⁇ ) is preferably 400 to 1,000 ° C., particularly preferably 500 to 900 ° C.
  • the heating temperature is 400 ° C. or higher, a reaction is likely to occur, and when it is 1,000 ° C. or lower, the pulverized product is difficult to melt and the crystal system and particle diameter are easily controlled. Further, at the heating temperature, it becomes easy to obtain a compound ( ⁇ ) having an appropriate crystallinity, particle size, particle size distribution, etc., preferably its crystal particles, more preferably olivine type crystal particles.
  • 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.
  • 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, roller hearth kiln, rotary kiln, microwave heating furnace, or the like that uses electricity, oil, gas, or the like as a heat source.
  • the heating step (v) is preferably performed in the air, in an inert atmosphere, or in a reducing atmosphere.
  • Preferred conditions for the inert atmosphere and the reducing atmosphere are the same as those described in the melting step (ii).
  • the atmospheric pressure may be any of normal pressure, pressurization, and reduced pressure (0.9 ⁇ 10 5 Pa or less).
  • 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.
  • the cooling is preferably allowed to cool to room temperature. Cooling is preferably performed in an inert atmosphere or a reducing atmosphere.
  • Carbon source can be added in the heating step (v).
  • the pulverized product obtained in the pulverization step (iv) (preferably a pulverized product containing no carbon source) is heated to obtain the compound ( ⁇ ), and then the compound ( ⁇ ) and the carbon source are obtained. It is preferable to adopt a production method in which a pulverized product containing the following is obtained, and then the pulverized product is heated.
  • the compound ( ⁇ ) having a predetermined composition as a positive electrode material for a secondary battery is manufactured through the above-described melting, cooling, pulverization, and heating steps.
  • the compound ( ⁇ ) preferably contains crystal particles and is preferably an olivine type. With such a composition and crystal system, as described above, a multi-electron type material having a theoretical electric capacity can be obtained.
  • a silicate compound is preferable because it can increase the capacity per unit volume (mass) of the secondary battery when used as a positive electrode material for a secondary battery.
  • the silicate compound is preferably an olivine type, and the olivine type silicate compound is suitable as a positive electrode material for a secondary battery.
  • a phosphoric acid compound is preferable when used as a positive electrode material for a secondary battery because the reliability of the performance of the secondary battery can be increased.
  • the phosphate compound is preferably an olivine type, and the olivine type phosphate compound is suitable as a positive electrode material for a secondary battery.
  • the specific surface area of the positive electrode material for a secondary battery obtained by the present invention is preferably 0.2 m 2 / g to 200 m 2 / g, more preferably 1 m 2 / g to 100 m 2 / g. 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 average particle diameter of the crystal particles of the positive electrode material for a secondary battery is preferably 10 nm to 10 ⁇ m, more preferably 10 nm to 2 ⁇ m in terms of volume median diameter in order to increase the conductivity of the particles.
  • the average particle diameter of the positive electrode material for a secondary battery obtained by the present invention is preferably 10 nm to 10 ⁇ m in terms of volume median diameter even if it contains not only crystal particles but also amorphous particles. More preferably, it is ⁇ 2 ⁇ m.
  • the raw material mixture of an olivine type compound, pyroxene type compound, or NASICON type compound containing heavy metal elements such as iron and manganese is heated and melted in a container made of electroformed refractory. Therefore, erosion due to heavy metal elements such as Fe and Mn contained in the melt can be suppressed, and wear of containers used for heat melting can be prevented, reducing the frequency of maintenance and reducing the manufacturing cost of the positive electrode material for secondary batteries. can do. Moreover, it can suppress that the component derived from a container mixes in the melt in the said container, and can obtain the positive electrode material for secondary batteries excellent in purity.
  • a large melting tank is used in the melting step (ii)
  • a secondary battery positive electrode and a secondary battery By using the secondary battery positive electrode material obtained by the production method of the present invention, a secondary battery positive electrode and a secondary battery can be produced.
  • 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 material for a secondary battery obtained by the manufacturing method of the present invention.
  • a positive electrode material for a secondary battery obtained according to the present invention may be prepared by using a known binder (polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, ethylene propylene diene polymer, styrene-butadiene rubber, acrylonitrile-butadiene as required.
  • the structure of the secondary battery a structure in a known secondary battery can be adopted except that the positive electrode material 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 using the positive electrode material for a secondary battery obtained by the production method of the present invention, a nonaqueous electrolyte lithium ion secondary battery is preferable.
  • Example 1 Composition Li 2 O melt, FeO, and P 2 O 5 equivalent amount (unit: mol%) in each 25.0 mol%, 50.0 mol%, and so that 25.0 mol% , Lithium carbonate (Li 2 CO 3 ), triiron tetroxide (Fe 3 O 4 ), and ammonium hydrogen phosphate (NH 4 H 2 PO 4 ) are weighed, mixed and pulverized in a dry process, Obtained.
  • Heating step (v) The pulverized product obtained in the pulverization step (iv) was heated at 700 ° C. for 8 hours in an Ar gas atmosphere containing 3% by volume of H 2 gas using an electric furnace (manufactured by Motoyama, apparatus name; SKM-3035). Then, the mixture was cooled to room temperature to precipitate lithium iron phosphate particles.
  • the mineral phase of the obtained lithium iron phosphate particles was measured using an X-ray diffraction apparatus (manufactured by Rigaku Corporation, apparatus name: RINT TTRIII). From the diffraction pattern, it was confirmed that the obtained lithium iron phosphate particles were orthorhombic olivine type LiFePO 4 . Moreover, it was 28 m ⁇ 2 > / g when the specific surface area of the obtained lithium iron phosphate particle was measured with the specific surface area measuring apparatus (Shimadzu Corporation make, apparatus name: ASAP2020).
  • the average particle size of the obtained lithium iron phosphate particles 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 It was 0.18 ⁇ m.
  • the crucible after the cooling step (iii) was not deformed in appearance.
  • the amount of erosion was measured, it was about 50 ⁇ m. The amount of erosion is indicated by the maximum erosion depth ( ⁇ m) measured with the flux line.
  • Example 2> (Corrosion resistance test)
  • the raw material preparation step (i), the melting step (ii), and the cooling step (iii) were performed, and the obtained solidified product was coated with alumina-zirconia having an inner diameter of 20 mm and a height of 40 mm.
  • -A crucible made of siliceous electroformed refractory manufactured by AGC Ceramics, trade name: ZB-1711 was filled.
  • the crucible containing the solidified material was placed in an electric furnace (manufactured by Motoyama, apparatus name: NH-3035) equipped with a heating element made of molybdenum silicide.
  • the temperature was increased at a rate of 300 ° C./hour, and after reaching 1,300 ° C., the temperature was maintained and heated for 48 hours. After the heat treatment, the cooled crucible was cut and the amount of erosion was measured.
  • Example 3 Composition Li 2 O melt, FeO, and SiO 2 in terms of the amount (unit: mol%) in each 14.3 mol%, so that 28.6 mol%, and 57.1 mol%, carbonate Lithium (Li 2 CO 3 ), triiron tetroxide (Fe 2 O 3 ), and silicon dioxide (SiO 2 ) were weighed, mixed and pulverized in a dry process to obtain a raw material preparation (raw material preparation step (i) ).
  • the melting step (ii) was performed at 1380 ° C. using the same crucible made of alumina-zirconia-silica electrocast refractory as in Example 1, and the heating step (v) was performed in an air atmosphere.
  • the melting step (ii), the cooling step (iii), the pulverization step (iv), and the heating step (v) were performed to deposit lithium iron silicate particles.
  • the mineral phase of the obtained lithium iron silicate particles was measured using an X-ray diffractometer, it was confirmed that the particles were orthorhombic pyroxene-type LiFeSi 2 O 6 .
  • Example 4 Composition Li 2 O melt, FeO, and P 2 O 5 equivalent amount (unit: mol%) in each 37.5 mol%, 25.0 mol%, and so that 37.5 mol% , Lithium carbonate (Li 2 CO 3 ), ferric trioxide (Fe 2 O 3 ), and ammonium hydrogen phosphate (NH 4 H 2 PO 4 ) are weighed, mixed and pulverized in a dry process, Obtained (raw material preparation step (i)).
  • Li 2 O melt, FeO, and P 2 O 5 equivalent amount (unit: mol%) in each 37.5 mol%, 25.0 mol%, and so that 37.5 mol% , Lithium carbonate (Li 2 CO 3 ), ferric trioxide (Fe 2 O 3 ), and ammonium hydrogen phosphate (NH 4 H 2 PO 4 ) are weighed, mixed and pulverized in a dry process, Obtained (raw material preparation step (i)).
  • the raw material mixture was filled in a crucible made of high zirconia electrocast refractory (AGC Ceramics, trade name: ZB-X950, porosity 0.2%) having an inner diameter of 20 mm and a height of 40 mm.
  • the melting step (ii) was performed in the same manner as in Example 1 except that the raw material formulation was melted at 1,200 ° C. in the air. Moreover, it carried out similarly to Example 1, and performed the cooling process (iii) and the grinding
  • the pulverized product obtained in the pulverization step (iv) was heated in the atmosphere at 650 ° C.
  • Example 1 A raw material preparation having the same composition as in Example 1 is filled in a crucible made of platinum alloy (internal volume 100 mL) containing 20% by mass of rhodium, and in the same manner as in Example 1, the raw material preparation step (i), the melting step (Ii) The cooling step (iii) was performed to obtain a solidified product. Subsequently, the Pt content and the Rh content in the obtained solidified product were quantified as follows. That is, the solidified product was decomposed with HF-HClO 4 and then redissolved with HCl, and the Pt content and Rh content in the solution were measured by ICP emission spectroscopy.
  • the Pt content in the solidified product was 9.6 ⁇ g / g
  • the Rh content was 23 ⁇ g / g.
  • the lithium iron phosphate particles obtained in Examples 1 and 4 and the lithium iron silicate particles obtained in Example 3 were measured for the Pt content and Rh content in the same manner as described above. It was 1 ⁇ g / g or less.
  • Example 2 A raw material formulation having the same composition as in Example 1 was filled in an alumina sintered crucible (made by Nikkato, trade name: SSA-S) with an outer diameter of 46 mm and a height of 53 mm. Next, the temperature was raised under the same conditions as in Example 1, and reached 1,250 ° C., then held for 2 hours and heated to perform the melting step (ii). Thereafter, the temperature was lowered at a rate of 300 ° C./hour and cooled to room temperature. When the crucible after the cooling step (iii) was visually observed, cracks were generated on the surface of the crucible. Moreover, when a part of crucible was cut and the amount of erosion was measured, it was 600 ⁇ m.
  • the positive electrode material for secondary batteries excellent in purity can be manufactured efficiently at low cost.

Landscapes

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

Abstract

La présente invention concerne un procédé pour la fabrication efficace, à bas coût, d'un matériau d'électrode positive pour une batterie secondaire possédant un petit mélange d'un composant dérivé d'un contenant utilisé pour le chauffage et la fusion d'un mélange de matières premières, et présentant une excellente pureté. Le procédé de production pour un matériau d'électrode positive de batterie secondaire comprend un composé possédant une structure du type olivine, augite ou nasicon et comprend : une étape de mélange de matières premières dans laquelle des matières premières sont mélangées et un mélange de matières premières est préparé ; et une étape de fusion dans laquelle le mélange de matières premières est fondu dans un contenant formé à l'aide d'un produit réfractaire électrofondu, et un produit fondu est obtenu.
PCT/JP2012/074269 2011-09-22 2012-09-21 Procédé de fabrication pour un matériau d'électrode positive pour une batterie secondaire Ceased WO2013042777A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011207025 2011-09-22
JP2011-207025 2011-09-22

Publications (1)

Publication Number Publication Date
WO2013042777A1 true WO2013042777A1 (fr) 2013-03-28

Family

ID=47914536

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/074269 Ceased WO2013042777A1 (fr) 2011-09-22 2012-09-21 Procédé de fabrication pour un matériau d'électrode positive pour une batterie secondaire

Country Status (2)

Country Link
JP (1) JPWO2013042777A1 (fr)
WO (1) WO2013042777A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013258035A (ja) * 2012-06-12 2013-12-26 Denso Corp リチウムイオン二次電池用電極活物質及びリチウムイオン二次電池
WO2014050086A1 (fr) * 2012-09-28 2014-04-03 トヨタ自動車株式会社 Électrode négative pour batterie, batterie, véhicule, et appareil avec batterie montée à l'intérieur
JP2015523682A (ja) * 2012-05-29 2015-08-13 クラリアント・（カナダ）・インコーポレイテッド 結晶電極材料を作製する方法およびそれから得られる材料
US20210343996A1 (en) * 2020-04-29 2021-11-04 Schott Ag Solid-state lithium ion conductor

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS553319B2 (fr) * 1972-02-21 1980-01-24
JPH1030132A (ja) * 1996-07-19 1998-02-03 Mitsui Mining & Smelting Co Ltd 水素吸蔵合金の酸素低減方法
JPH11100214A (ja) * 1997-09-26 1999-04-13 Nippon Electric Glass Co Ltd ガラス溶融炉
JP2000247647A (ja) * 1999-02-26 2000-09-12 Asahi Glass Co Ltd 溶融ガラスの減圧脱泡装置用炉材および減圧脱泡装置
JP2008293661A (ja) * 2007-05-22 2008-12-04 Nec Tokin Corp リチウム二次電池用正極及びそれを用いたリチウム二次電池
WO2009093663A1 (fr) * 2008-01-22 2009-07-30 Agc Ceramics Co., Ltd. Particules d'agrégats pour moules
JP2011001242A (ja) * 2009-06-22 2011-01-06 Asahi Glass Co Ltd リン酸鉄リチウム粒子の製造方法とリン酸鉄リチウム粒子
JP2011076793A (ja) * 2009-09-29 2011-04-14 Furukawa Battery Co Ltd:The オリビン型ケイ酸ｍリチウムの合成方法およびリチウムイオン二次電池
WO2011065337A1 (fr) * 2009-11-24 2011-06-03 旭硝子株式会社 Procédé pour la production de composé d'acide phosphorique, et procédé pour la production d'une batterie secondaire
WO2011111628A1 (fr) * 2010-03-09 2011-09-15 旭硝子株式会社 Phosphate, électrode positive pour pile secondaire et méthode de production d'une pile secondaire

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS553319B2 (fr) * 1972-02-21 1980-01-24
JPH1030132A (ja) * 1996-07-19 1998-02-03 Mitsui Mining & Smelting Co Ltd 水素吸蔵合金の酸素低減方法
JPH11100214A (ja) * 1997-09-26 1999-04-13 Nippon Electric Glass Co Ltd ガラス溶融炉
JP2000247647A (ja) * 1999-02-26 2000-09-12 Asahi Glass Co Ltd 溶融ガラスの減圧脱泡装置用炉材および減圧脱泡装置
JP2008293661A (ja) * 2007-05-22 2008-12-04 Nec Tokin Corp リチウム二次電池用正極及びそれを用いたリチウム二次電池
WO2009093663A1 (fr) * 2008-01-22 2009-07-30 Agc Ceramics Co., Ltd. Particules d'agrégats pour moules
JP2011001242A (ja) * 2009-06-22 2011-01-06 Asahi Glass Co Ltd リン酸鉄リチウム粒子の製造方法とリン酸鉄リチウム粒子
JP2011076793A (ja) * 2009-09-29 2011-04-14 Furukawa Battery Co Ltd:The オリビン型ケイ酸ｍリチウムの合成方法およびリチウムイオン二次電池
WO2011065337A1 (fr) * 2009-11-24 2011-06-03 旭硝子株式会社 Procédé pour la production de composé d'acide phosphorique, et procédé pour la production d'une batterie secondaire
WO2011111628A1 (fr) * 2010-03-09 2011-09-15 旭硝子株式会社 Phosphate, électrode positive pour pile secondaire et méthode de production d'une pile secondaire

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015523682A (ja) * 2012-05-29 2015-08-13 クラリアント・（カナダ）・インコーポレイテッド 結晶電極材料を作製する方法およびそれから得られる材料
JP2013258035A (ja) * 2012-06-12 2013-12-26 Denso Corp リチウムイオン二次電池用電極活物質及びリチウムイオン二次電池
WO2014050086A1 (fr) * 2012-09-28 2014-04-03 トヨタ自動車株式会社 Électrode négative pour batterie, batterie, véhicule, et appareil avec batterie montée à l'intérieur
JPWO2014050086A1 (ja) * 2012-09-28 2016-08-22 トヨタ自動車株式会社 二次電池用負極、二次電池、車両および電池搭載機器
US20210343996A1 (en) * 2020-04-29 2021-11-04 Schott Ag Solid-state lithium ion conductor
US12255306B2 (en) * 2020-04-29 2025-03-18 Schott Ag Solid-state lithium ion conductor

Also Published As

Publication number Publication date
JPWO2013042777A1 (ja) 2015-03-26

Similar Documents

Publication Publication Date Title
JP6049713B2 (ja) 溶融製品の製造法
JP2014056722A (ja) リン酸化合物、二次電池用正極材料、および二次電池の製造方法
JP2011001242A (ja) リン酸鉄リチウム粒子の製造方法とリン酸鉄リチウム粒子
CN103402921A (zh) Lmo产品的生产方法
KR102444648B1 (ko) 나트륨 이온 이차전지용 정극 활물질 및 그 제조방법
WO2011162348A1 (fr) Composé d'acide silicique, électrode positive pour cellule secondaire et procédé de fabrication d'une cellule secondaire
US20210343996A1 (en) Solid-state lithium ion conductor
WO2012133584A1 (fr) Matériau actif d'électrode positive pour batterie secondaire, électrode positive pour batterie secondaire, et procédé de production de batterie secondaire
WO2011138964A1 (fr) Composé de (acide silicique)-(acide phosphorique), électrode positive pour batterie secondaire, et procédé de fabrication d'une batterie secondaire
WO2012133581A1 (fr) Matériau actif d'électrode positive pour batterie secondaire, électrode positive pour batterie secondaire, et procédé de production de batterie secondaire
WO2013042777A1 (fr) Procédé de fabrication pour un matériau d'électrode positive pour une batterie secondaire
TW201124338A (en) Process for production of phosphoric acid compound, and process for production of secondary battery
WO2012057341A1 (fr) Composé de silicate, électrode positive de batterie secondaire, batterie secondaire et leurs procédés de fabrication
WO2012067249A1 (fr) Composé de silicate, électrode positive de batterie secondaire, batterie secondaire et leurs procédés de fabrication
JP2013067543A (ja) ケイ酸化合物、二次電池用正極および二次電池の製造方法
WO2012086722A1 (fr) Composé d'acide silicique-acide vanadique, électrode positive pour batterie secondaire, et procédé de fabrication pour batterie secondaire
JP2013069526A (ja) 二次電池用正極材料の製造方法
JP2014055085A (ja) リン酸化合物、二次電池用正極材料、および二次電池の製造方法
JP2013047162A (ja) ケイ酸化合物、二次電池用正極および二次電池の製造方法
WO2013042780A1 (fr) Procédé de production de matériau d'électrode positive pour batterie secondaire
JP2013047161A (ja) ケイ酸化合物、二次電池用正極および二次電池の製造方法
WO2012057340A1 (fr) Composé de silicate-phosphate, électrode positive de batterie secondaire, batterie secondaire et leurs procédés de fabrication
WO2013042778A1 (fr) Procédé de fabrication pour un matériau d'électrode positive pour une batterie secondaire
WO2012067250A1 (fr) Composé de silicate, électrode positive de batterie secondaire, batterie secondaire et leurs procédés de fabrication
WO2011138965A1 (fr) 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

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12833467

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013534771

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12833467

Country of ref document: EP

Kind code of ref document: A1