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WO2012035648A1 - Matière active pour accumulateur à électrolyte non aqueux et accumulateur à électrolyte non aqueux - Google Patents

Matière active pour accumulateur à électrolyte non aqueux et accumulateur à électrolyte non aqueux Download PDF

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WO2012035648A1
WO2012035648A1 PCT/JP2010/066175 JP2010066175W WO2012035648A1 WO 2012035648 A1 WO2012035648 A1 WO 2012035648A1 JP 2010066175 W JP2010066175 W JP 2010066175W WO 2012035648 A1 WO2012035648 A1 WO 2012035648A1
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active material
electrolyte secondary
secondary battery
positive electrode
electrode active
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Japanese (ja)
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本棒英利
菅野正義
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Hitachi Ltd
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Hitachi Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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 an active material for a non-aqueous electrolyte secondary battery using a sodium salt, and a non-aqueous electrolyte secondary battery using the same.
  • a lithium ion battery using a lithium salt as an electrolyte has a high output density such as a high energy density, and is therefore widely used as a power source for notebook personal computers and portable devices.
  • a lithium salt as an electrolyte
  • development of electric vehicles and hybrid vehicles using lithium ion batteries is being promoted.
  • application to a storage system of a lithium ion battery is expected.
  • lithium, cobalt, and the like used in the lithium ion battery have a small amount of resources and are limited in the country of origin and region, it is necessary to develop a high performance secondary battery using a material that can be secured stably.
  • Patent Document 1 discloses a negative electrode active material using sodium / lead alloy and a positive electrode active material using sodium / cobalt oxide. .
  • an object of the present invention is to provide a novel positive electrode active material and negative electrode active material capable of stably and reversibly occluding and releasing sodium ions having a larger ionic radius than lithium ions.
  • the present invention includes the following inventions.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery comprising a composite metal oxide containing Na, Ni and Mn.
  • the composite metal oxide has the general formula (I): Na ⁇ Ni ⁇ -g Mn ⁇ -h M ′ g + h O 2 (I) [Where M ′ is at least one selected from the group consisting of Al, Mg and Co; ⁇ is in the range of 0 ⁇ ⁇ 0.5, ⁇ is in the range of 2/9 ⁇ ⁇ ⁇ 1/4, ⁇ is in the range of 3/4 ⁇ ⁇ ⁇ 7/9, g is in the range of 0 ⁇ g ⁇ 0.045, h is in the range of 0 ⁇ h ⁇ 0.045, ⁇ + ⁇ + g + h is 1]
  • the positive electrode active material for nonaqueous electrolyte secondary batteries according to (1) represented by:
  • the composite metal oxide has the general formula (II): Na 4-a Ni 2-x Mn 7-y M ′ x + y O 18 (II) [Where M ′ is at least one selected from the group consisting of Al, Mg and Co; a is in the range of 0 ⁇ a ⁇ 4, x is in the range of 0 ⁇ x ⁇ 0.4, y is in the range of 0 ⁇ y ⁇ 0.4]
  • the positive electrode active material for a non-aqueous electrolyte secondary battery according to (2) represented by:
  • the composite metal oxide has the general formula (III): Na 2-b Ni 1-p Mn 3-q M ′ p + q O 8 (III) [Where M ′ is at least one selected from the group consisting of Al, Mg and Co; b is in the range of 0 ⁇ b ⁇ 2, p is in the range of 0 ⁇ p ⁇ 0.1, q is within the range of 0 ⁇ q ⁇ 0.1]
  • the positive electrode active material for a non-aqueous electrolyte secondary battery according to (2) represented by:
  • Nonaqueous electrolyte solution 2 having a positive electrode containing the positive electrode active material for a nonaqueous electrolyte secondary battery according to any one of (1) to (4) and a negative electrode capable of reversibly occluding and releasing sodium ions.
  • the nonaqueous electrolyte secondary battery according to (5), wherein the negative electrode reversibly occluding and releasing sodium ions includes a compound having at least one aromatic carboxylic acid sodium salt structure as a negative electrode active material.
  • a compound having at least one aromatic carboxylic acid sodium salt structure is represented by the general formula (IV): C 6 H 4 (CO 2 Na 1 + c ) 2 (IV) [Wherein c is in the range of 0 ⁇ c ⁇ 1]
  • the nonaqueous electrolyte secondary battery according to (6) represented by:
  • a negative electrode active material for a nonaqueous electrolyte secondary battery comprising a compound having at least one aromatic carboxylic acid sodium salt structure.
  • the compound having at least one aromatic carboxylic acid sodium salt structure is represented by the general formula (IV): C 6 H 4 (CO 2 Na 1 + c ) 2 (IV) [Wherein c is in the range of 0 ⁇ c ⁇ 1]
  • the negative electrode active material for a nonaqueous electrolyte secondary battery according to (8) represented by:
  • a nonaqueous electrolyte secondary battery comprising a negative electrode comprising the negative electrode active material for a nonaqueous electrolyte secondary battery according to (8) or (9) and a positive electrode capable of reversibly occluding and releasing sodium ions.
  • the active material material for nonaqueous electrolyte secondary batteries excellent in the reversibility of charging / discharging using sodium as an ion carrier of a nonaqueous electrolyte, and a nonaqueous electrolyte secondary using the same Battery can be provided.
  • the cathode active material for a non-aqueous electrolyte secondary battery according to the present invention is a composite metal oxide containing Na, Ni and Mn, and preferably has the general formula (I): Na ⁇ Ni ⁇ -g Mn ⁇ -h M ′ g + h O 2 (I) [Where M ′ is at least one selected from the group consisting of Al, Mg and Co; ⁇ is in the range of 0 ⁇ ⁇ 0.5, ⁇ is in the range of 2/9 ⁇ ⁇ ⁇ 1/4, ⁇ is in the range of 3/4 ⁇ ⁇ ⁇ 7/9, g is in the range of 0 ⁇ g ⁇ 0.045, h is in the range of 0 ⁇ h ⁇ 0.045, ⁇ + ⁇ + g + h is 1] It is a complex metal oxide represented by.
  • the value of ⁇ representing the amount of Na varies depending on charging / discharging. That is, the deintercalation of Na ions occurs due to charging, and the value of ⁇ decreases, and the intercalation of Na ions occurs due to discharge, and the value of ⁇ increases.
  • M ′ is at least one selected from the group consisting of Al, Mg and Co; a is in the range of 0 ⁇ a ⁇ 4, x is in the range of 0 ⁇ x ⁇ 0.4, y is in the range of 0 ⁇ y ⁇ 0.4]
  • the composite metal oxide represented by these can be mentioned.
  • the value of a representing the amount of Na varies depending on charging and discharging. That is, Na ion deintercalation occurs due to charging, and the value of a increases, and Na ion intercalation occurs due to discharge, and the value of a decreases.
  • Na 4-a Ni 2-x Mn 7-y M ′ x + y O 18 is an oblique view of Na 4 Mn 4 Ti 5 O 18 reported in Acta Crystallographica Section B, Vol. 24, pages 1114 to 1120 (1968). Similar to crystal structure. This crystal is a complex oxide of trivalent and tetravalent metals and Na, and has a large tunnel space in the crystal structure.
  • the positive electrode active material of the present invention is mainly a Ni-containing composite metal oxide to which Ni and Mn, and in some cases, a metal M ′ for stabilizing the crystal structure is added. Presumed to be divalent (Ni 2+ ) and tetravalent (Mn 4+ ).
  • the valence of Ni is considered to change from divalent to tetravalent (Ni 4+ ). At this time, it is considered that Na ions move through the large tunnel space in the crystal structure and are released to the electrolyte side. On the other hand, in the discharge, it is considered that a reaction occurs in which the valence of Ni changes from tetravalent to divalent. On the other hand, the valence of tetravalent Mn does not change, and thus it is thought that this maintains a stable crystal structure that is not affected by large Na ions.
  • Ni oxidation-reduction reaction Ni 2+ ⁇ Ni 4+ + 2e ⁇
  • Ni 2+ ⁇ Ni 4+ + 2e ⁇ the potential of Ni oxidation-reduction reaction
  • M ′ is an additive element as described above, and is at least one selected from Al, Mg, and Co.
  • the bonding strength with oxygen is large, and by substituting these with a part of the Ni or Mn site, the crystal structure becomes more stable and desirable.
  • the value of x + y representing the added amount of M ′ is preferably in the range of 0 ⁇ x + y ⁇ 0.8, and more preferably in the range of 0 ⁇ x + y ⁇ 0.4.
  • the range of 0 ⁇ x + y ⁇ 0.8 is desirable, and the range of 0 ⁇ x + y ⁇ 0.4 is more desirable. desirable.
  • M ′ is at least one selected from the group consisting of Al, Mg and Co; b is in the range of 0 ⁇ b ⁇ 2, p is in the range of 0 ⁇ p ⁇ 0.1, q is within the range of 0 ⁇ q ⁇ 0.1]
  • the composite metal oxide represented by these can be mentioned.
  • the value of b representing the amount of Na varies depending on charging and discharging. That is, deintercalation of Na ions occurs due to charging, the value of b increases, and intercalation of Na ions occurs due to discharge, and the value of b decreases.
  • Na 2-b Ni 1-p Mn 3-q M ′ p + q O 8 has a spinel crystal structure, mainly containing Ni and Mn, and in some cases, a metal M ′ for stabilizing the crystal structure. This is an added Na-containing composite metal oxide.
  • Ni is a metal that forms a complex oxide with stable tetravalent Mn.
  • Ni is presumed to be mainly divalent (Ni 2+ ) in a discharged state, and it is considered that the deintercalation of Na ions, which is a charging reaction, changes from divalent to tetravalent (Ni 4+ ). In discharge, conversely, it is considered that a reaction occurs in which the valence of Ni changes from tetravalent to divalent.
  • Such an oxidation-reduction reaction (Ni 2+ ⁇ Ni 4+ + 2e ⁇ ) has a high reaction potential and excellent reversibility, and as a result, a secondary battery having a high voltage and a long life can be obtained.
  • Mn is presumed to be tetravalent (Mn 4+ ), and is inactive in the charge / discharge reaction, so that it maintains tetravalence and thus contributes to stabilization of the crystal structure.
  • M ′ is an additive element and is at least one selected from Al, Mg and Co.
  • the bonding strength with oxygen is large, and by substituting these with a part of the Ni or Mn site, the crystal structure becomes more stable and desirable.
  • the values of p and q representing the substitution amount to the Ni or Mn site are desirably in the range of 0 ⁇ p ⁇ 0.1 and 0 ⁇ q ⁇ 0.1.
  • impurities such as by-products and unreacted raw materials remain, and the reversibility is impaired.
  • the value of p + q representing the amount of M ′ added is preferably in the range of 0 ⁇ p + q ⁇ 0.2. In order to stabilize the crystal structure and further improve the reversibility of charge / discharge, it is desirable that the range is 0 ⁇ p + q ⁇ 0.2.
  • Nonaqueous electrolyte negative active material for a secondary battery according to the anode active material present invention is composed of a compound having at least one aromatic carboxylic acid sodium salt structure.
  • aromatic carboxylic acid sodium salt structure means a structure in which a carboxyl group is directly bonded to an aromatic ring and the carboxyl group forms a sodium salt.
  • the compound having at least one aromatic carboxylic acid sodium salt structure preferably has 1-10, more preferably 1-5, and particularly preferably one. preferable.
  • aromatic ring examples include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene and pyrene, and aromatic heterocycles such as pyridine, pyrazine and pyrimidine.
  • the compound having at least one aromatic carboxylic acid sodium salt structure preferably has an even number (particularly two) of sodium carboxylate groups substituted on the aromatic ring.
  • the distance between even number (particularly two) carboxyl groups includes the carbon atoms substituted, An even number is preferable, and 2, 4, or 6 is particularly preferable.
  • the reaction potential at this time is about 1.0 V noble potential from the equilibrium potential of Na metal, there is a feature that precipitation of Na hardly occurs.
  • the reaction potential at this time is about 1.0 V noble potential from the equilibrium potential of Na metal, there is a feature that precipitation of Na hardly occurs.
  • the negative electrode active material of the present invention does not cause such a side reaction and has excellent reversibility.
  • Examples of the compound having at least one aromatic carboxylic acid sodium salt structure include, for example, the following formula:
  • R1 and R2 are independently of each other hydrogen, an alkyl group, an aryl group, or an alkoxyl group, preferably hydrogen, a C1-3 alkyl group, a phenyl group, or a C1-3 alkoxyl group, particularly Preferred is hydrogen]
  • R3 and R4 independently of each other, are hydrogen, an alkyl group, an aryl group, or an alkoxyl group, preferably hydrogen, a C1-3 alkyl group, a phenyl group, or a C1-3 alkoxyl group, particularly Preferred is hydrogen]
  • n is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, particularly preferably 1.
  • R5 and R6, independently of each other, are hydrogen, an alkyl group, an aryl group, or an alkoxyl group, preferably hydrogen, a C1-3 alkyl group, a phenyl group, or a C1-3 alkoxyl group, particularly Preferred is hydrogen]
  • the compound represented by these can be mentioned.
  • a negative electrode active material represented by the chemical formula C 6 H 4 (CO 2 Na 1 + c ) 2 (0 ⁇ c ⁇ 1) is particularly desirable because of its excellent reversibility and large Na storage / release capacity.
  • the value of c representing the amount of Na varies depending on charging and discharging. That is, the value of c is increased when Na ions are bound by charging, and the value of c is decreased when Na ions are dissociated by discharging.
  • Non-aqueous electrolyte secondary battery includes only one of a positive electrode including the positive electrode active material according to the present invention and a negative electrode including the negative electrode active material according to the present invention. You may have as a positive electrode or a negative electrode, and both the positive electrode and negative electrode may contain the active material which concerns on this invention.
  • electrolyte used in the non-aqueous electrolyte secondary battery according to the present invention.
  • the electrolyte concentration is preferably 0.5 to 1.5 M (mol / l).
  • the use of the reversibly chargeable / dischargeable battery according to the present invention is not particularly limited.
  • FIG. 1 is a diagram showing an outline of a cylindrical nonaqueous electrolyte secondary battery.
  • 10 is a positive electrode
  • 11 is a separator
  • 12 is a negative electrode
  • 13 is a battery can
  • 14 is a positive electrode tab
  • 15 is a negative electrode tab
  • 16 is an inner lid
  • 17 is an internal pressure release valve
  • 18 is a gasket
  • 19 is a PTC element.
  • 20 is an outer lid.
  • FIG. 2 is a diagram showing an outline of a coin-type non-aqueous electrolyte secondary battery.
  • 21 is a positive electrode
  • 22 is a negative electrode
  • 23 is a separator
  • 24 is a coin case
  • 25 is an upper lid
  • 26 is a gasket.
  • Example 1 Na 2 CO 3 , NiO, and MnO 2 were used as raw materials for the Na 4 Mn 4 Ti 5 O 18 type orthorhombic positive electrode active material of this example.
  • Na 2 CO 3 , NiO, and MnO 2 were mixed at a weight ratio (wt%) of 21.9: 15.4: 62.7 and mixed at room temperature for 15 h using a ball mill. This was held at 150 ° C. for 1 h in the air atmosphere and further held at 470 ° C. for 5 h, and then fired in an oxygen atmosphere at 1050 ° C. for 20 h.
  • the composition of the obtained positive electrode active material is Na 4 Ni 2 Mn 7 O 18 .
  • the positive electrode active material of Example 1 whose average particle diameter is 11 micrometers was obtained by grind
  • Example 2 Each of Al, Mg, and Co was added as a substitution element to the positive electrode active material synthesized in Example 1.
  • Al (OH) 3 , MgO, or Co 3 O 4 was used as a raw material.
  • Na 2 CO 3 , NiO, and MnO 2 were combined at a weight ratio (wt%) of 22.7: 16.0: 61.4, and mixed at room temperature for 15 hours using a ball mill to prepare a mixed raw material.
  • this mixed raw material and Al (OH) 3 , MgO, or Co 3 O 4 were mixed at a weight ratio (wt%) of 96.8: 3.2, 98.3: 1.7, or 96.7: 3.3, respectively, and three types
  • the substitution element addition mixed raw material of this was prepared. Each was held at 150 ° C. for 1 h in the air atmosphere and further held at 470 ° C. for 5 h, and then calcined by holding at 1050 ° C. for 20 h in an oxygen atmosphere.
  • the composition of the obtained three types of positive electrode active materials is Na 4 Ni 2 Mn 6.6 Al 0.4 O 18 , Na 4 Ni 2 Mn 6.6 Mg 0.4 O 18 , or Na 4 Ni 2 Mn 6.6 Co 0.4 O 18 .
  • the positive electrode active material of Example 2 whose average particle diameter is 10 micrometers was obtained by grind
  • Example 3 A positive electrode active material was synthesized in the same manner as in Example 2. First, Na 2 CO 3 , NiO, and MnO 2 were combined at a weight ratio (wt%) of 22.5: 12.7: 64.7, and mixed at room temperature for 15 hours using a ball mill to prepare a mixed raw material. Next, this mixed raw material and Al (OH) 3 , MgO, or Co 3 O 4 were mixed at a weight ratio (wt%) of 96.8: 3.2, 98.3: 1.7, or 96.7: 3.3, respectively, and three types The substitution element addition mixed raw material of this was prepared. Each was held at 150 ° C. for 1 h in the air atmosphere and further held at 470 ° C.
  • the composition of the obtained three types of positive electrode active materials is Na 4 Ni 1.6 Mn 7 Al 0.4 O 18 , Na 4 Ni 1.6 Mn 7 Mg 0.4 O 18 , or Na 4 Ni 1.6 Mn 7 Co 0.4 O 18 .
  • the positive electrode active material of Example 3 whose average particle diameter is 11 micrometers was obtained by grind
  • Example 4 A positive electrode active material was synthesized in the same manner as in Example 2. Na 2 CO 3 , NiO, and MnO 2 were combined at a weight ratio (wt%) of 21.9: 15.4: 62.7, and mixed for 15 h at room temperature using a ball mill to prepare a mixed raw material. Next, the mixed raw material and Co 3 O 4 were mixed at a weight ratio (wt%) of 96.7: 3.3 and 93.4: 6.6, respectively, to prepare two kinds of mixed element addition mixed raw materials. Each was held at 150 ° C. for 1 h in the air atmosphere and further held at 470 ° C. for 5 h, and then calcined by holding at 1050 ° C. for 20 h in an oxygen atmosphere.
  • the composition of the obtained two types of positive electrode active materials is Na 4 Ni 1.8 Mn 6.8 Co 0.4 O 18 and Na 4 Ni 1.6 Mn 6.6 Co 0.8 O 18 . Then, the positive electrode active material of Example 4 whose average particle diameter is 9 micrometers was obtained by grind
  • Comparative Example 1 Na 2 CO 3 , NiO, and MnO 2 were combined at a weight ratio (wt%) of 21.9: 15.4: 62.7, and mixed for 15 h at room temperature using a ball mill to prepare a mixed raw material. Next, this mixed raw material and Co 3 O 4 were mixed at a weight ratio (wt%) of 91.7: 8.3 to prepare a mixed element-added mixed raw material. After holding at 150 ° C. for 1 hour in an air atmosphere and further holding at 470 ° C. for 5 hours, firing was carried out by holding at 1050 ° C. for 20 hours in an oxygen atmosphere. The composition of the obtained positive electrode active material is Na 4 Ni 1.5 Mn 6.5 Co 1.0 O 18 . Then, the positive electrode active material of the comparative example 1 whose average particle diameter is 11 micrometers was obtained by grind
  • Example 5 Na 2 CO 3 , NiO, and MnO 2 were used as raw materials for the spinel-type positive electrode active material of this example.
  • Na 2 CO 3 , NiO, and MnO 2 were mixed at a weight ratio (wt%) of 24.0: 16.9: 59.1 and mixed at room temperature for 15 h using a ball mill. This was held at 150 ° C. for 1 h in the air atmosphere and further held at 470 ° C. for 5 h, and then calcined by holding at 750 ° C. for 20 h in an oxygen atmosphere.
  • the composition of the obtained positive electrode active material is Na 4 Ni 2 Mn 7 O 18 .
  • the positive electrode active material of Example 5 whose average particle diameter is 9 micrometers was obtained by grind
  • Example 6 Each of Al, Mg, and Co was added as a substitution element to the positive electrode active material synthesized in Example 5.
  • Al (OH) 3 , MgO, or Co 3 O 4 was used as a raw material.
  • Na 2 CO 3 , NiO, and MnO 2 were combined at a weight ratio (wt%) of 24.5: 17.3: 58.3, and mixed at room temperature for 15 hours using a ball mill to prepare a mixed raw material.
  • the mixed raw material and Al (OH) 3 , MgO, or Co 3 O 4 were mixed at a weight ratio (wt%) of 98.2: 1.8, 99.1: 0.9, or 98.2: 1.8, respectively, and three types were mixed.
  • the substitution element addition mixed raw material of this was prepared. Each was held at 150 ° C. for 1 h in the air atmosphere and further held at 470 ° C. for 5 h, and then calcined by holding at 750 ° C. for 20 h in an oxygen atmosphere.
  • the composition of the obtained three types of positive electrode active materials is Na 2 NiMn 2.9 Al 0.1 O 8 , Na 2 NiMn 2.9 Mg 0.1 O 8 , or Na 2 NiMn 2.9 Co 0.1 O 8 .
  • the positive electrode active material of Example 6 whose average particle diameter is 8 micrometers was obtained by grind
  • Example 7 A positive electrode active material was synthesized in the same manner as in Example 6. First, Na 2 CO 3 , NiO, and MnO 2 were combined at a weight ratio (wt%) of 24.4: 15.5: 60.1, and mixed at room temperature for 15 hours using a ball mill to prepare a mixed raw material. Next, this mixed raw material and Al (OH) 3 , MgO, or Co 3 O 4 were mixed at a weight ratio (wt%) of 98.2: 1.8, 99.1: 0.9, or 98.2: 1.8, respectively, and three types were mixed. The substitution element addition mixed raw material of this was prepared. Each was held at 150 ° C. for 1 h in the air atmosphere and further held at 470 ° C.
  • the composition of the obtained three types of positive electrode active materials is Na 2 Ni 0.9 Mn 3 Al 0.1 O 8 , Na 2 Ni 0.9 Mn 3 Mg 0.1 O 8 , or Na 2 Ni 0.9 Mn 3 Co 0.1 O 8 .
  • the positive electrode active material of Example 7 whose average particle diameter is 9 micrometers was obtained by grind
  • Example 8 A positive electrode active material was synthesized in the same manner as in Example 6. Na 2 CO 3 , NiO, and MnO 2 were combined at a weight ratio (wt%) of 24.0: 16.9: 59.1 and mixed at room temperature for 15 h using a ball mill to prepare a mixed raw material. Next, this mixed raw material and Co 3 O 4 were mixed at a weight ratio (wt%) of 96.4: 3.6 to prepare a mixed element-added mixed raw material. After holding at 150 ° C. for 1 hour in the air atmosphere and further holding at 470 ° C. for 5 hours, firing was carried out by holding at 750 ° C. for 20 hours in an oxygen atmosphere.
  • the composition of the obtained positive electrode active material is Na 2 Ni 0.9 Mn 2.9 Co 0.2 O 8 . Then, the positive electrode active material of Example 8 whose average particle diameter is 10 micrometers was obtained by grind
  • Comparative Example 2 Na 2 CO 3 , NiO, and MnO 2 were combined at a weight ratio (wt%) of 24.0: 16.9: 59.1 and mixed at room temperature for 15 h using a ball mill to prepare a mixed raw material. Next, this mixed raw material and Co 3 O 4 were mixed at a weight ratio (wt%) of 92.7: 7.3 to prepare a mixed element-added mixed raw material. After holding at 150 ° C. for 1 hour in the air atmosphere and further holding at 470 ° C. for 5 hours, firing was carried out by holding at 750 ° C. for 20 hours in an oxygen atmosphere. The composition of the obtained positive electrode active material is Na 2 Ni 0.8 Mn 2.8 Co 0.4 O 8 . Then, the positive electrode active material of the comparative example 2 whose average particle diameter is 10 micrometers was obtained by grind
  • Reference example 1 Na 2 CO 3 and Co 3 O 4 were combined at a weight ratio (wt%) of 30.7: 69.3, and mixed at room temperature for 15 h using a ball mill to prepare a mixed raw material. After holding at 150 ° C. for 1 h in the air atmosphere and further holding at 470 ° C. for 5 h, firing was carried out by holding at 650 ° C. for 20 h in an oxygen atmosphere. The composition of the obtained positive electrode active material is Na 0.67 CoO 2 . Then, the positive electrode active material of the reference example 1 whose average particle diameter is 10 micrometers was obtained by grind
  • Example 9 As the negative electrode active material, disodium terephthalate (chemical formula: C 6 H 4 (CO 2 Na) 2 , manufactured by Aldrich) was used. To this, acetylene black as a conductive material and PVDF as a binder were weighed to a weight ratio of 88: 7: 5 and mixed with a rake machine for 30 minutes to prepare a negative electrode mixture slurry. Thereafter, each negative electrode mixture slurry was applied to one side or both sides of a 10 ⁇ m thick copper foil and sufficiently dried at 120 ° C. The dry coated electrode was press-molded at a pressure of 100 MPa to obtain a negative electrode of Example 9.
  • disodium terephthalate chemical formula: C 6 H 4 (CO 2 Na) 2 , manufactured by Aldrich
  • acetylene black as a conductive material and PVDF as a binder were weighed to a weight ratio of 88: 7: 5 and mixed with a rake machine for 30 minutes to prepare a negative electrode mixture slurry
  • Example 10 1,5-naphthalenedicarboxylic acid (chemical formula: C 10 H 6 (CO 2 H) 2 , manufactured by Aldrich) was added to an aqueous solution containing an excess of 5% sodium hydroxide in terms of equivalent amount, and Na ion exchange was performed. This solution was added to a large excess of methanol to reprecipitate sodium 1,5-naphthalenedicarboxylate. Further, it was thoroughly washed with methanol and vacuum-dried at 80 ° C. Using this as a negative electrode active material, a negative electrode of Example 10 was obtained in the same manner as Example 9.
  • Example 11 A negative electrode of Example 11 was obtained in the same manner as Example 9 using 2,6-naphthalenedicarboxylic acid (chemical formula: C 10 H 6 (CO 2 H) 2 , manufactured by Aldrich).
  • Reference example 2 A negative electrode of Reference Example 2 was obtained in the same manner as Example 9 using amorphous carbon (manufactured by Kureha Chemical, Carbotron P (registered trademark)) as the negative electrode active material.
  • amorphous carbon manufactured by Kureha Chemical, Carbotron P (registered trademark)
  • Example 12 A coin-type non-aqueous electrolyte secondary battery shown in FIG. 2 is manufactured by the following procedure by combining the positive electrode coated on one side with the positive electrode active material prepared in Example 1 and the negative electrode coated on one side prepared in Reference Example 2. did. The positive electrode and the negative electrode were each punched out to a diameter of 15 mm and dried under the conditions of 120 ° C. and vacuum. A microporous polypropylene film was used for the separator, and the positive electrode, the separator, and the negative electrode were placed in a coin case in this order.
  • a mixture of ethylene carbonate and ethyl methyl carbonate in a volume ratio of 1: 3, NaPF 6 as a sodium salt, and a sodium concentration of 1 mol / l were prepared.
  • the upper lid of the coin case was caulked and completely sealed to obtain a nonaqueous electrolyte secondary battery of Example 12.
  • charge and discharge cycles were repeated under a charging condition with a constant current of 0.5 mA and 4.0 V and a termination condition of 5 hours with a constant current of 0.5 mA and a discharge condition of 2.0 V with a termination condition of 0.5 mA. Sex was evaluated.
  • FIG. 3 shows the change in the maintenance rate with respect to the rated capacity as the cycle progresses.
  • the nonaqueous electrolyte secondary battery of Example 12 showed excellent reversibility, and the capacity retention rate after 50 cycles was 75%.
  • Example 13 The coin-type non-aqueous electrolyte secondary battery shown in FIG. 2 was combined with the positive electrode on which the positive electrode active material prepared in Example 5 was applied on one side and the negative electrode on the single side applied in Reference Example 2 as in Example 12. It produced similarly. Further, in the same manner as in Example 12, the change in the maintenance ratio with respect to the rated capacity with the progress of the cycle was examined. As shown in FIG. 3, the nonaqueous electrolyte secondary battery of Example 13 exhibited excellent reversibility, and the capacity retention rate after 50 cycles was 79%.
  • Example 14 The coin-type non-aqueous electrolyte secondary battery shown in FIG. 2 was combined with the negative electrode with a single-side coating produced in Example 9 and the positive electrode with a single-sided coating of the positive electrode active material produced in Reference Example 1 together with Example 12 It produced similarly.
  • the negative electrode produced in Example 9 has a feature that Na precipitation is unlikely to occur because the reaction potential of occlusion and release of Na ions is about 1.0 V noble potential from the equilibrium potential of Na metal. Since the operating potential is different from that of Example 12, the charging / discharging conditions were changed to charging at 0.5 mA and 3.5 V constant current constant voltage for 5 hours and discharging at 0.5 mA constant current at 1.0 V termination.
  • Example 14 the change in the maintenance ratio with respect to the rated capacity as the cycle progressed was examined. As shown in FIG. 4, the nonaqueous electrolyte secondary battery of Example 14 showed excellent reversibility, and the capacity retention rate after 50 cycles was 83%.
  • Example 15 The coin-type non-aqueous electrolyte secondary battery shown in FIG. 2 was combined with the negative electrode with a single-side coating produced in Example 10 and the positive electrode with a single-sided coating of the positive electrode active material produced in Reference Example 1 as in Example 12. It produced similarly.
  • the negative electrode produced in Example 10 has a feature that Na precipitation is unlikely to occur because the reaction potential of occlusion and release of Na ions is about 1.0 V noble potential from the equilibrium potential of Na metal.
  • Example 14 the change in the maintenance ratio with respect to the rated capacity with the progress of the cycle was examined.
  • the nonaqueous electrolyte secondary battery of Example 15 showed excellent reversibility, and the capacity retention rate after 50 cycles was 78%.
  • Example 16 The coin-type non-aqueous electrolyte secondary battery shown in FIG. 2 is combined with the negative electrode with a single-side coating prepared in Example 11 and the positive electrode with a single-side coating of the positive electrode active material prepared in Reference Example 1 as in Example 12. It produced similarly.
  • the negative electrode produced in Example 11 has a feature that the reaction potential of the storage and release of Na ions is about 1.0 V noble potential from the equilibrium potential of Na metal, so that precipitation of Na hardly occurs.
  • the change in the maintenance ratio with respect to the rated capacity with the progress of the cycle was examined.
  • the nonaqueous electrolyte secondary battery of Example 16 showed excellent reversibility, and the capacity retention rate after 50 cycles was 80%.
  • Example 17 The coin-type non-aqueous electrolyte secondary battery shown in FIG. 2 was combined with the positive electrode obtained by applying the positive electrode active material prepared in Example 1 on one side and the single-sided negative electrode prepared in Example 9 with Example 12. It produced similarly. Further, in the same manner as in Example 14, the change in the maintenance ratio with respect to the rated capacity with the progress of the cycle was examined. As shown in FIG. 5, the nonaqueous electrolyte secondary battery of Example 17 showed excellent reversibility, and the capacity retention rate after 100 cycles was 70%.
  • Example 18 The coin-type non-aqueous electrolyte secondary battery shown in FIG. 2 is combined with the positive electrode on which the positive electrode active material manufactured in Example 5 is applied on one side and the negative electrode on the single side applied in Example 9 as in Example 12. It produced similarly. Further, in the same manner as in Example 14, the change in the maintenance ratio with respect to the rated capacity with the progress of the cycle was examined. As shown in FIG. 5, the nonaqueous electrolyte secondary battery of Example 18 exhibited excellent reversibility, and the capacity retention rate after 100 cycles was 79%.
  • Example 19 A positive electrode formed by adding one substitution element to each of three types of Examples 2 and 3, two types of Example 4, and a total of eight types of positive electrode active materials, and a single-sided negative electrode prepared in Example 9 In combination, the coin-type non-aqueous electrolyte secondary battery shown in FIG. Further, a charge / discharge test was conducted in the same manner as in Example 14 to examine the maintenance ratio relative to the rated capacity after 100 cycles.
  • Comparative Example 3 A coin-type non-aqueous electrolyte secondary solution shown in FIG. 2 is formed by combining the positive electrode active material of Comparative Example 1 coated on one side and the single-sided coated negative electrode fabricated in Reference Example 2 produced by adding a substitution element in excess. A battery was produced in the same manner as in Example 12. Further, a charge / discharge test was conducted in the same manner as in Example 12, and the maintenance rate relative to the rated capacity after 50 cycles was examined.
  • Table 1 shows a comparison of the maintenance rate with respect to the rated capacity after the cycle of the eight types of nonaqueous electrolyte secondary batteries of Example 19 and the nonaqueous electrolyte secondary battery of Comparative Example 3 is shown. It was found that all of the eight types of nonaqueous electrolyte secondary batteries of Example 19 had a higher retention rate after 100 cycles than Example 17 and were desirable. On the other hand, the non-aqueous electrolyte secondary battery of Comparative Example 3 was found to have a lower maintenance rate after 50 cycles than Example 12. That is, reversibility can be further improved by adding a substitution element in an appropriate range.
  • Example 20 A positive electrode formed by adding one substitution element to each of three types of Examples 6 and 7, one type of Example 8, and a total of seven types of positive electrode active materials, and a single-sided negative electrode prepared in Example 9 In combination, the coin-type non-aqueous electrolyte secondary battery shown in FIG. Further, a charge / discharge test was conducted in the same manner as in Example 14 to examine the maintenance ratio relative to the rated capacity after 100 cycles.
  • Comparative Example 4 A coin-type non-aqueous electrolyte secondary shown in FIG. 2 is formed by combining the positive electrode active material of Comparative Example 2 coated on one side and the single-sided coated negative electrode fabricated in Reference Example 2 prepared by adding a substitution element in excess. A battery was produced in the same manner as in Example 12. Further, a charge / discharge test was conducted in the same manner as in Example 12, and the maintenance rate relative to the rated capacity after 50 cycles was examined.
  • Table 2 shows a comparison of the maintenance rate with respect to the rated capacity after the cycle of the seven types of nonaqueous electrolyte secondary batteries of Example 20 and the nonaqueous electrolyte secondary battery of Comparative Example 4. It was found that all of the seven types of nonaqueous electrolyte secondary batteries of Example 20 had a higher maintenance rate than Example 18 and were desirable. On the other hand, the nonaqueous electrolyte secondary battery of Comparative Example 4 was found to have a lower maintenance rate than Example 13. That is, reversibility can be further improved by adding a substitution element in an appropriate range.
  • Example 21 The cylindrical non-aqueous electrolyte secondary battery shown in FIG. 1 is manufactured by the following procedure by combining the positive electrode coated on both sides of the positive electrode active material prepared in Example 5 and the negative electrode coated on both sides manufactured in Example 9. did.
  • the positive electrode and the negative electrode were formed into strips, and the positive electrode tab and the negative electrode tab were welded to one end of each, and further dried under conditions of 120 ° C. and vacuum.
  • a microporous polypropylene film was used as a separator, and the film was wound in the order of a positive electrode, a separator, a negative electrode, and a separator, and inserted into a battery can.
  • the negative electrode tab was welded to the battery can, and the positive electrode tab was welded to the inner lid.
  • a mixture of ethylene carbonate and ethyl methyl carbonate in a volume ratio of 1: 3, NaPF 6 as a sodium salt, and a sodium concentration of 1 mol / l were prepared.
  • the battery lid was caulked and completely sealed to obtain a nonaqueous electrolyte secondary battery having a diameter of 14 mm and a height of 50 mm.
  • the direct current resistance and power density of the battery were determined by the following method. In an environment of 50 ° C., discharge was performed for 10 seconds in the order of currents 4CA, 8CA, 12CA, and 16CA. The relationship between the discharge current at that time and the voltage at 10 seconds was plotted, and the DC resistance was determined from the slope of the obtained straight line. Also, the current value at 1.0 V on the straight line was obtained, and the power density was obtained by dividing the battery weight by the product of 1.0 V and the current value.
  • the initial output density and the rate of increase in resistance after 50,000 pulse cycles were 2300 W / k and 108%, respectively, and it was found that they had high output and excellent life characteristics.

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Abstract

Cette invention concerne une matière active pour un accumulateur à électrolyte non aqueux à base de sel de sodium et présentant une excellente réversibilité. L'invention concerne en outre un accumulateur à électrolyte non aqueux doté de ladite matière active. Une matière active de cathode, dans laquelle un oxyde contenant du Mn et du Ni retient le Na à grand rayon ionique et structure cristalline stable dans un oxyde métallique combiné contenant du Na. Ladite matière active de cathode présente une réversibilité excellente de la réaction d'absorption et de désorption des ions Na lors de la charge et de la décharge. De plus, une matière active d'électrode négative comprend un composé présentant au moins une structure de sel de sodium d'acide carboxylique aromatique qui n'encourage pas le dépôt métallique. Ladite matière active d'électrode négative présente une réversibilité excellente de la réaction de charge et de décharge. Lesdites matières actives conviennent donc bien à l'utilisation préconisée.
PCT/JP2010/066175 2010-09-17 2010-09-17 Matière active pour accumulateur à électrolyte non aqueux et accumulateur à électrolyte non aqueux Ceased WO2012035648A1 (fr)

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JP2012221754A (ja) * 2011-04-08 2012-11-12 Toyota Central R&D Labs Inc リチウム二次電池用負極及びリチウム二次電池
JP2013225413A (ja) * 2012-04-20 2013-10-31 Toyota Central R&D Labs Inc 電極活物質、非水系二次電池用電極及び非水系二次電池
JPWO2012053553A1 (ja) * 2010-10-21 2014-02-24 株式会社豊田中央研究所 非水系二次電池用電極、それを備えた非水系二次電池及び組電池
JP2014120235A (ja) * 2012-12-13 2014-06-30 Kyocera Corp 活物質およびそれを用いた二次電池
WO2014115772A1 (fr) * 2013-01-23 2014-07-31 学校法人東京理科大学 Oxyde métallique combiné, substance active pour électrode positive pour batterie rechargeable au sodium, électrode positive pour batterie rechargeable au sodium et batterie rechargeable au sodium
JP2014216211A (ja) * 2013-04-26 2014-11-17 株式会社豊田中央研究所 電極及び非水系二次電池
JP2014229452A (ja) * 2013-05-21 2014-12-08 独立行政法人産業技術総合研究所 ナトリウム二次電池正極材料、該ナトリウム二次電池正極材料の製造方法、該ナトリウム二次電池正極材料を用いるナトリウム二次電池用電極、該ナトリウム二次電池用電極を備えるナトリウム二次電池、及び該ナトリウム二次電池を用いる電気機器
JP2015022845A (ja) * 2013-07-17 2015-02-02 株式会社豊田中央研究所 電極活物質の製造方法、電極活物質及びそれを用いた非水系二次電池
JP2015037016A (ja) * 2013-08-12 2015-02-23 トヨタ自動車株式会社 ナトリウムイオン電池用負極活物質、ナトリウムイオン電池およびナトリウムイオン電池用負極活物質の製造方法
JP2015037014A (ja) * 2013-08-12 2015-02-23 トヨタ自動車株式会社 ナトリウムイオン電池用負極活物質およびナトリウムイオン電池
JP2015198007A (ja) * 2014-04-01 2015-11-09 株式会社豊田中央研究所 非水系二次電池用電極及び非水系二次電池
CN105047865A (zh) * 2015-06-10 2015-11-11 长安大学 一种用于电极材料的新型苯三酸盐及其制备方法
JP2016076342A (ja) * 2014-10-03 2016-05-12 株式会社豊田中央研究所 非水系二次電池用電極及び非水系二次電池
JP2017508697A (ja) * 2014-01-09 2017-03-30 ファラディオン リミテッド 硬質カーボン電極のためのドープされたニッケル酸塩化合物
JP2020042944A (ja) * 2018-09-07 2020-03-19 株式会社豊田中央研究所 電極活物質、蓄電デバイス及び電極活物質の製造方法
CN119742366A (zh) * 2024-12-25 2025-04-01 深圳珈钠能源科技有限公司 一种防过充型钠离子电池正极片

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JP2001057238A (ja) * 1999-08-19 2001-02-27 Mitsui Chemicals Inc 非水電解液およびそれを用いた二次電池
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Cited By (17)

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JPWO2012053553A1 (ja) * 2010-10-21 2014-02-24 株式会社豊田中央研究所 非水系二次電池用電極、それを備えた非水系二次電池及び組電池
JP2012221754A (ja) * 2011-04-08 2012-11-12 Toyota Central R&D Labs Inc リチウム二次電池用負極及びリチウム二次電池
JP2013225413A (ja) * 2012-04-20 2013-10-31 Toyota Central R&D Labs Inc 電極活物質、非水系二次電池用電極及び非水系二次電池
JP2014120235A (ja) * 2012-12-13 2014-06-30 Kyocera Corp 活物質およびそれを用いた二次電池
WO2014115772A1 (fr) * 2013-01-23 2014-07-31 学校法人東京理科大学 Oxyde métallique combiné, substance active pour électrode positive pour batterie rechargeable au sodium, électrode positive pour batterie rechargeable au sodium et batterie rechargeable au sodium
JP2014216211A (ja) * 2013-04-26 2014-11-17 株式会社豊田中央研究所 電極及び非水系二次電池
JP2014229452A (ja) * 2013-05-21 2014-12-08 独立行政法人産業技術総合研究所 ナトリウム二次電池正極材料、該ナトリウム二次電池正極材料の製造方法、該ナトリウム二次電池正極材料を用いるナトリウム二次電池用電極、該ナトリウム二次電池用電極を備えるナトリウム二次電池、及び該ナトリウム二次電池を用いる電気機器
JP2015022845A (ja) * 2013-07-17 2015-02-02 株式会社豊田中央研究所 電極活物質の製造方法、電極活物質及びそれを用いた非水系二次電池
JP2015037016A (ja) * 2013-08-12 2015-02-23 トヨタ自動車株式会社 ナトリウムイオン電池用負極活物質、ナトリウムイオン電池およびナトリウムイオン電池用負極活物質の製造方法
JP2015037014A (ja) * 2013-08-12 2015-02-23 トヨタ自動車株式会社 ナトリウムイオン電池用負極活物質およびナトリウムイオン電池
JP2017508697A (ja) * 2014-01-09 2017-03-30 ファラディオン リミテッド 硬質カーボン電極のためのドープされたニッケル酸塩化合物
JP2015198007A (ja) * 2014-04-01 2015-11-09 株式会社豊田中央研究所 非水系二次電池用電極及び非水系二次電池
JP2016076342A (ja) * 2014-10-03 2016-05-12 株式会社豊田中央研究所 非水系二次電池用電極及び非水系二次電池
CN105047865A (zh) * 2015-06-10 2015-11-11 长安大学 一种用于电极材料的新型苯三酸盐及其制备方法
JP2020042944A (ja) * 2018-09-07 2020-03-19 株式会社豊田中央研究所 電極活物質、蓄電デバイス及び電極活物質の製造方法
JP7087855B2 (ja) 2018-09-07 2022-06-21 株式会社豊田中央研究所 電極活物質、蓄電デバイス及び電極活物質の製造方法
CN119742366A (zh) * 2024-12-25 2025-04-01 深圳珈钠能源科技有限公司 一种防过充型钠离子电池正极片

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