WO2018012385A1 - Matériau actif d'électrode positive destiné à des batteries secondaires à électrolyte non aqueux, précurseur d'hydroxyde de métal de transition, procédé de production de précurseur d'hydroxyde de métal de transition, procédé de production de matériau actif d'électrode positive destiné à des batteries secondaires à électrolyte non aqueux, électrode destinée à des batteries secondaires à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux et dispositif de stockage d'électricité - Google Patents

Matériau actif d'électrode positive destiné à des batteries secondaires à électrolyte non aqueux, précurseur d'hydroxyde de métal de transition, procédé de production de précurseur d'hydroxyde de métal de transition, procédé de production de matériau actif d'électrode positive destiné à des batteries secondaires à électrolyte non aqueux, électrode destinée à des batteries secondaires à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux et dispositif de stockage d'électricité Download PDF

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WO2018012385A1
WO2018012385A1 PCT/JP2017/024741 JP2017024741W WO2018012385A1 WO 2018012385 A1 WO2018012385 A1 WO 2018012385A1 JP 2017024741 W JP2017024741 W JP 2017024741W WO 2018012385 A1 WO2018012385 A1 WO 2018012385A1
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transition metal
active material
positive electrode
electrolyte secondary
electrode active
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Japanese (ja)
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弘将 村松
遠藤　大輔
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GS Yuasa International 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode active material for a non-aqueous electrolyte secondary battery, a transition metal hydroxide precursor used for manufacturing a lithium transition metal composite contained in the positive electrode active material, and a method for manufacturing the transition metal hydroxide precursor
  • the present invention also relates to a method for producing a positive electrode active material using the transition metal precursor, a nonaqueous electrolyte secondary battery electrode containing the positive electrode active material, a nonaqueous electrolyte secondary battery, and a power storage device.
  • LiMeO 2 type active material Li is a transition metal
  • LiCoO Non-aqueous electrolyte secondary batteries using 2 have been widely put into practical use.
  • the discharge capacity of LiCoO 2 was about 120 to 130 mAh / g.
  • the “LiMeO 2 type” active material containing Mn as Me when the molar ratio Mn / Mn in Me exceeds 0.5, the structural change occurs to the spinel type when charged, Since the crystal structure cannot be maintained, the charge / discharge cycle performance is remarkably inferior.
  • LiMeO 2 type active materials having a Mn molar ratio Mn / Me in Me of 0.5 or less and excellent in charge / discharge cycle performance have been proposed and partially put into practical use.
  • a positive electrode active material containing LiNi 1/2 Mn 1/2 O 2 or LiNi 1/3 Co 1/3 Mn 1/3 O 2 which is a lithium transition metal composite oxide has a discharge capacity of 150 to 180 mAh / g.
  • LiMeO 2 type active material As described above, the composition ratio Li / Me of lithium (Li) with respect to the ratio of transition metal (Me) is larger than 1, for example, Li / Me is 1.2 to 1
  • Li / Me is 1.2 to 1
  • lithium-excess type active material which includes a lithium transition metal composite oxide having a composition formula of Li 1 + ⁇ Me 1- ⁇ O 2 ( ⁇ > 0). It is also known to produce the above lithium transition metal composite oxide from a hydroxide precursor (see, for example, Patent Documents 1 to 4).
  • Patent Document 1 discloses lithium having an ⁇ -NaFeO 2 type crystal structure and represented by a composition formula Li 1 + ⁇ Me 1- ⁇ O 2 (Me is a transition metal containing Co, Ni, and Mn, ⁇ > 0).
  • (Claim 2) "The method for producing a positive electrode active material for a lithium secondary battery according to claim 1 or 2, wherein precursors for the synthesis of the lithium transition metal composite oxide are Co, Ni and Mn Lithium secondary, characterized by being a transition metal hydroxide containing The manufacturing method of the positive electrode active material for batteries "(Claim 3) is described.
  • the pH in the step of producing a precursor by coprecipitation of a compound containing Co, Ni and Mn in a solution is not limited, but the coprecipitation precursor is used as a coprecipitation hydroxide precursor. In the case of production, it can be set to 10.5 to 14.
  • the tap density In order to increase the tap density, it is preferable to control the pH, and by setting the pH to 11.5 or less, the tap density can be reduced. 1.00 g / cm 3 or more can improve the high rate discharge performance, and further, by adjusting the pH to 11.0 or less, the particle growth rate can be accelerated, so It is possible to shorten the stirring time of “(paragraph [0032])”.
  • Patent Document 2 discloses that “a method for producing an active material for a lithium secondary battery according to claim 1 or 2, wherein a compound of a transition metal element Me containing Co, Ni, and Mn is coprecipitated in a solution.
  • An active material for a lithium secondary battery comprising a step of mixing so that a molar ratio of Li is 1 ⁇ (1 + ⁇ ) / (1- ⁇ ) ⁇ 1.5 and firing at 700 to 800 ° C. Manufacturing method "(Claim 3) is described.
  • the pH in the step of producing a precursor by coprecipitation of a compound containing Co, Ni and Mn in a solution is not limited, but the coprecipitation precursor is used as a coprecipitation hydroxide precursor. If it is to be produced, it can be 10-14, and if it is intended to produce the coprecipitated precursor as a coprecipitated carbonate precursor, it can be 7.5-11.
  • the pH, and for the coprecipitated carbonate precursor the tap density can be increased to 1.25 g / cc or higher by setting the pH to 9.4 or lower.
  • the high-rate discharge performance can be improved "(paragraph [0035]).
  • a lithium-containing composite oxide having an integral intensity (I 020 ) ratio (I 020 / I 003 ) of 0.02 to 0.3 and a tap density of
  • Patent Document 3 discloses that “(Example 1)... As a complexing agent, ammonium sulfate was dissolved in distilled water so as to have a concentration of 1.5 mol / kg” to obtain an aqueous ammonium sulfate solution (paragraph). [0088]), “Distilled water was put into a 2 L baffled glass reaction vessel and heated with a mantle heater to 50 ° C.
  • Example 3 is a lithium with a high tap density without crushing by increasing the tap density of the hydroxide.
  • the specific surface area of the lithium-containing composite oxide is small, the discharge capacity of the lithium secondary battery per unit mass of the positive electrode active material is low, and as a result, the positive electrode active material The discharge capacity of the lithium secondary battery per unit volume is also low ”(paragraph [0106]).
  • a positive electrode active material for a non-aqueous electrolyte secondary battery containing a lithium transition metal composite oxide that defines the half-value width of diffraction peaks on the (003) plane and the (104) plane by X-ray diffraction measurement is known (for example, And Patent Documents 4 to 6).
  • Patent Document 4 discloses that “a current collector and an active material layer including active material particles held by the current collector are provided, and the active material particles are a collection of a plurality of primary particles of a lithium transition metal oxide.
  • the secondary particle has a hollow structure having a hollow part formed inside the secondary particle and a shell part surrounding the hollow part, and the secondary particle includes the hollow part from the outside.
  • the lithium transition metal oxide is: General formula of: Li 1 + x Ni y Co z Mn (1-yz) W ⁇ M ⁇ O 2 (X, y, z, ⁇ and ⁇ in the formula (1) are 0 ⁇ x ⁇ 0.2, 0.1 ⁇ y ⁇ 0.9, 0.1 ⁇ z ⁇ 0.4, 0.0005 ⁇ It is a real number that satisfies all ⁇ ⁇ 0.01 and 0 ⁇ ⁇ ⁇ 0.01, and M is absent or Zr, Mg, Ca, Na, Fe, Cr, Zn, Si, Sn, Al, B and One or more elements selected from the group consisting of F.)
  • the lithium secondary battery according to claim 1 The lithium secondary battery according to claim 1,
  • the W addition amount is 0.5 mol% with respect to 100 mol% of the raw material having a Ni: Co: Mn molar ratio of 0.33: 0.33: 0.33.
  • the composite hydroxide particles obtained by adjusting so as to become lithium carbonate and lithium carbonate are mixed and fired so that Li / Me is about 1.15, thereby comprising a lithium transition metal composite oxide. It describes that an active material particle having a hollow structure or a solid structure was produced.
  • Patent Document 5 “Having a layered structure and having a composition represented by the following formula (1), the half-value width FWHM 003 of the (003) plane and the half-value width of the (104) plane in the powder X-ray diffraction diagram.
  • the element M is at least one element selected from the group consisting of Al, Si, Zr, Ti, Fe, Mg, Nb, Ba and V, and 1.9 ⁇ (a + b + c + d + y) ⁇ 2.1, 1.0 ⁇ y ⁇ 1.3, 0 ⁇ a ⁇ 0.3, 0 ⁇ b ⁇ 0.25, 0.3 ⁇ c ⁇ 0.7, 0 ⁇ d ⁇ 0.1, 9 ⁇ x ⁇ 2.1. ] FWHM 003 / FWHM 104 ⁇ 0.57 (2) ”(Claim 1).
  • citric acid was added to an aqueous solution of a raw material mixture such as lithium acetate dihydrate, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, nickel acetate tetrahydrate, etc., and reacted.
  • a raw material mixture such as lithium acetate dihydrate, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, nickel acetate tetrahydrate, etc.
  • the chemical composition formula of the solid solution is Li 1 + x ⁇ y Na y Co a Ni b Mn c O 2 + d (0 ⁇ y ⁇ 0.1, 0.4 ⁇ c ⁇ 0.7
  • the active material for a lithium secondary battery is characterized in that the half-width of the diffraction peak of the (114) plane is 0.50 ° or less ”(Claim 1).
  • paragraph [0052] has “half-value width of the X-ray diffraction peak described above as indicating the degree of crystallization.
  • the space group P3 1 12 In the X-ray diffraction pattern attributed to (3) it is necessary that the half width of the (003) plane diffraction peak is 0.30 ° or less and the half width of the (114) plane diffraction peak is 0.50 ° or less.
  • the half-value width of the (003) plane diffraction peak is preferably 0.17 ° to 0.30 °, and the half-value width of the (114) plane diffraction peak is preferably 0.35 ° to 0.50 °. It is described.
  • an active material obtained by mixing a coprecipitated hydroxide precursor of a transition metal, lithium hydroxide monohydrate, and sodium carbonate so as to have various compositions and firing at 1000 ° C.
  • the half-value width of the (003) plane diffraction peak was “0.19 to 0.21 °” and the half-value width of the (114) plane diffraction peak was “0.39 to 0.41”.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery containing a lithium transition metal composite oxide having a defined pore volume is known (see, for example, Patent Documents 7 to 9).
  • Patent Document 7 states that “porous particles made of a lithium composite oxide mainly composed of one or more elements selected from the group consisting of Co, Ni, and Mn and lithium, and having pores formed by mercury porosimetry.
  • Non-aqueous system comprising particles having an average pore diameter in the range of 0.1 to 1 ⁇ m in distribution measurement and a total volume of pores having a diameter of 0.01 to 1 ⁇ m of 0.01 cm 3 / g or more
  • the positive electrode active material for secondary batteries “(Claim 1) is described.
  • Patent Document 7 states that “[Example 1] obtained by mixing and pulverizing lithium hydroxide, nickel hydroxide, and cobalt hydroxide in a ball mill at a molar ratio of each metal of 105: 90: 10.
  • the mixed powder was pressure-molded under a pressure of 1 ton / cm 2 , and this molded body was used as a raw material for firing, which was fired (calcined) in an air stream at 770 ° C. for 10 hours.
  • the granulated powder was fired at 800 ° C. for 2 hours in an oxygen stream (main firing), pulverized with a mortar-type pulverizer, and then sized with a screen classifier.
  • the product was porous spherical secondary particles having a pore average diameter of 0.363 ⁇ m and a total volume of pores having a diameter of 0.01 to 1 ⁇ m and a total volume of 8.4 ⁇ 10 ⁇ 2 cm 3 / g ”(paragraph [0026]. ] ”,“ The calcination temperature was changed to 650 ° C. with respect to Example 1. Compared to Example 1, the calcination temperature was lowered to lower the crystallinity of the primary particles. Sintering between primary particles was promoted and the pore volume was controlled. The lithium composite oxide thus obtained had a pore average diameter of 0.137 ⁇ m and a total volume of pores having a diameter of 0.01 to 1 ⁇ m. Was a porous spherical secondary particle having a density of 1.8 ⁇ 10 ⁇ 2 cm 3 / g ”.
  • Patent Document 8 states that “(Example 1)... Nickel sulfate aqueous solution, cobalt sulfate aqueous solution and manganese sulfate aqueous solution has an atomic ratio of nickel atom, cobalt atom and manganese atom of 0.33: 0.33: The mixed raw material solution was adjusted by mixing to 0.33 .... Next, the mixed raw material solution and the aqueous ammonium sulfate solution were continuously added as a complexing agent to the reaction vessel with stirring.
  • a sodium hydroxide aqueous solution was added dropwise as needed so that the pH of the solution in the reaction vessel was 11.7 to obtain nickel cobalt manganese composite hydroxide particles, which were filtered, washed with water, and dried at 100 ° C. In this way, a dry powder of nickel cobalt manganese composite hydroxide was obtained ....
  • Patent Document 8 discloses that the positive electrode active material 2 has a Li: Ni: Co: Mn molar ratio of 1.10: 0.34: 0.33: 0.33 (paragraph [0151]). It was described that the pore volume was 0.030 cm 3 / g (paragraph [0154]), and the positive electrode active material 3 had a molar ratio of Li: Ni: Co: Mn of 1.05: 0.34: 0.
  • the positive electrode active material 5 has a molar ratio of Li: Ni: Co: Mn of 1.09: 0.33: 0.3. : 0.33 (paragraph [0170]), it pore volume was 0.030 cm 3 / g (paragraph [0173]) have been described.
  • Patent Document 9 states that “as the positive electrode active material 1 and the positive electrode active material 2, lithium-containing transition metal oxides having the following chemical formulas were synthesized using a composite carbonate method.
  • the starting materials include nickel, cobalt, and manganese.
  • a sulfate a 2 mol / L nickel sulfate aqueous solution, a cobalt sulfate aqueous solution and a manganese sulfate aqueous solution were prepared, a 2 mol / L sodium carbonate aqueous solution was used as a precipitating agent, and a pH adjusting agent was adjusted to a concentration of 0.8.
  • Patent Document 9 states that “the positive electrode active material 3 is composed of lithium carbonate, nickel sulfate aqueous solution, cobalt sulfate aqueous solution, and manganese sulfate so that lithium, nickel, cobalt, and manganese have the following chemical formula ratios. It was prepared in the same manner as the positive electrode active material 1 except that the aqueous solution was mixed. "(Paragraph [0248])," ⁇ Composition and physical properties of the positive electrode active material 3> Chemical formula: Li 1.5 [Ni 0.25 Co 0.
  • the positive electrode active material 4 is also mixed with lithium carbonate, nickel sulfate aqueous solution, and manganese sulfate aqueous solution so that lithium, nickel, and manganese have the following chemical formula ratios.
  • the discharge capacity of the so-called “lithium-rich” active material is generally larger than that of the so-called “LiMeO 2 type” active material, as described in Patent Documents 1-9.
  • hydroxide precursors and carbonate precursors are known as precursors of “lithium-rich” positive electrode active materials.
  • the present invention seeks to solve the above problems by using a hydroxide precursor as a precursor of a “lithium-rich” positive electrode active material.
  • a hydroxide precursor as a precursor of a “lithium-rich” positive electrode active material.
  • the hydroxide precursor has been usually produced by a method of adjusting the pH to 10 to 14 when coprecipitating from an aqueous solution of a transition metal compound.
  • the tap density is 1.25 g / cm 3 or more by a method in which the pH when coprecipitating from the aqueous solution of the transition metal compound is 9.4 or less.
  • the hydroxide precursor if the synthesis pH is lowered, the high rate discharge performance of the positive electrode active material tends to be lowered. It was not done to increase the density. Therefore, it is difficult to increase the discharge capacity per volume of the positive electrode active material.
  • Patent Documents 4 to 6 describe a positive electrode active material for a non-aqueous electrolyte secondary battery containing a lithium transition metal composite oxide that defines a half-value width of diffraction peaks on the (003) plane and the (104) plane. However, it has not been shown to increase the discharge capacity per volume of the positive electrode active material.
  • Patent Documents 7 to 9 describe a positive electrode active material for a non-aqueous electrolyte secondary battery containing a lithium transition metal composite oxide having a defined pore volume. The discharge capacity per volume of the positive electrode active material is described as follows. It is not shown to be high.
  • the present invention relates to a positive electrode active material having a large discharge capacity per volume, a high-density hydroxide precursor for producing the positive electrode active material, a nonaqueous electrolyte secondary battery electrode using the positive electrode active material, and It is an object to provide a non-aqueous electrolyte secondary battery.
  • one aspect of the present invention is “a positive electrode active material for a non-aqueous electrolyte battery including a lithium transition metal composite oxide, wherein the lithium transition metal composite oxide is ⁇ -NaFeO 2 type.
  • the molar ratio (Li / Me) of Li and transition metal (Me) constituting the lithium transition metal composite oxide having a crystal structure is greater than 1, and the transition metal (Me) is Mn and Ni, or Mn, X-rays using CuK ⁇ rays, which contain Ni and Co, have a Mn molar ratio Mn / Me in the transition metal (Me) greater than 0.5, have an X-ray diffraction pattern that can be assigned to R3-m
  • the lithium transition metal composite oxide pore volume determined by the BJH method from an adsorption isotherm using a nitrogen gas adsorption method of the particles is less than 0.05 cm 3 / g, a non-aqueous electrolyte secondary battery
  • the positive electrode active material is used.
  • transition metal hydroxide precursor used for producing a lithium transition metal composite oxide contained in the positive electrode active material for a nonaqueous electrolyte secondary battery, wherein the transition metal (Me ) Contains Mn and Ni, or Mn, Ni and Co, the molar ratio of Mn in the transition metal (Me) is Mn / Me larger than 0.5, and the tap density is 1.3 g / cm 3 or more. Transition metal hydroxide precursor.
  • Another aspect of the present invention is “a method for producing the transition metal hydroxide precursor, wherein a reaction vessel contains a transition metal (Me) -containing solution, an alkali metal hydroxide, a complexing agent, And a method for producing a transition metal hydroxide precursor, wherein an alkaline solution containing a reducing agent is added to adjust the pH of the solution in the reaction vessel to less than 9 to 9.8 to coprecipitate the transition metal hydroxide. It is.
  • Another aspect of the present invention is “having an ⁇ -NaFeO 2 type crystal structure in which the transition metal hydroxide precursor and a lithium compound are mixed and fired at 750 to 900 ° C.
  • Another aspect of the present invention is a nonaqueous electrolyte secondary battery electrode containing the positive electrode active material, and is a nonaqueous electrolyte secondary battery including the electrode.
  • a positive electrode active material having a large discharge capacity (energy density) per volume a high-density hydroxide precursor for producing the positive electrode active material, and a nonaqueous electrolyte containing the positive electrode active material.
  • a secondary battery electrode and a non-aqueous electrolyte secondary battery including the electrode can be provided.
  • the figure which shows the total pore volume of the positive electrode active material of an Example and a comparative example Figure showing the relationship between the total pore volume of the positive electrode active material and the discharge capacity per volume 1 is an external perspective view showing a nonaqueous electrolyte secondary battery according to one embodiment of the present invention.
  • the positive electrode active material for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention is a positive electrode active material containing a lithium transition metal composite oxide.
  • the composition of the lithium transition metal composite oxide contains Mn and Ni, or a transition metal element Me containing Mn, Ni and Co, and Li, and Li 1 + ⁇ Me 1- ⁇ from the viewpoint of obtaining a high discharge capacity. This is a so-called “lithium-excess type” which can be expressed as O 2 ( ⁇ > 0).
  • the transition metal element Me represented by (1 + ⁇ ) / (1- ⁇ )
  • the molar ratio Li / Me to Li is preferably 1.1 or more and less than 1.4, more preferably 1.1 or more and 1.3 or less, and 1.1 or more and 1.2 or less. Is particularly preferred. Within this range, the discharge capacity per volume of the positive electrode active material is improved.
  • the molar ratio Mn / Me of the transition metal element Me is greater than 0.5. It is preferably 0.51 or more and less than 0.7, and more preferably 0.51 to 0.60. Within this range, the tap density of the hydroxide precursor can be improved and the discharge capacity per volume is improved.
  • Co contained in the lithium transition metal composite oxide has an effect of improving the initial efficiency.
  • the tap density of the precursor is lowered and the peak differential pore volume is increased.
  • the molar ratio Co / Me of Co to the transition metal element Me is preferably 0.20 or less, and may be 0.
  • the molar ratio Ni / Me of Ni to the transition metal element Me is preferably 0.2 to 0.5, more preferably 0.25 to 0.4. Within this range, the tap density of the hydroxide precursor can be improved and the discharge capacity per volume is improved.
  • the lithium transition metal composite oxide according to this embodiment has an ⁇ -NaFeO 2 structure.
  • the lithium transition metal composite oxide after synthesis (before charge and discharge) is attributed to the space group P3 1 12 or R3-m.
  • the charge is performed and Li in the crystal is desorbed, the symmetry of the crystal changes, whereby the superlattice peak disappears and the lithium transition metal composite oxide belongs to the space group R3-m. Will come to be.
  • P3 1 12 is a crystal structure model in which the atomic positions of the 3a, 3b, and 6c sites in R3-m are subdivided, and when ordering is recognized in the atomic arrangement in R3-m, the P3 1 12 model Is adopted. Note that “R3-m” is originally represented by adding a bar “-” on “3” of “R3m”.
  • the lithium transition metal composite oxide according to the present embodiment is (003) relative to the half-value width of the diffraction peak attributed to the (104) plane.
  • the ratio of the half width of the diffraction peak attributed to the plane, that is, the value of FWHM (003) / FWHM (104) is 0.6 or less.
  • the FWHM (104) is an index of crystallinity from all directions. If it is too small, crystallization proceeds too much, the crystallite becomes large, and Li ions are not sufficiently diffused. If it is too large, the crystallinity is low, and the transport efficiency of Li ions is reduced. Therefore, the FWHM (104) is preferably in the range of 0.21 ° to 0.55 °.
  • the FWMH ratio is an index of crystallinity along the c-axis direction with respect to crystallinity from all directions in the crystal structure. If FWHM (003) / FWHM (104) is too large, the degree of crystal growth in the c-axis direction will be small, and Li ions will not be smoothly inserted and removed from the interlayer. Therefore, FWHM (003) / FWHM (104) is set to 0.6 or less. In addition, when FWHM (003) / FWHM (104) is not too small, elution of Mn due to an increase in the contact area between the crystal grain boundary and the electrolytic solution can be suppressed. Therefore, FWHM (003) / FWHM (104) is preferably set to 0.4 or more.
  • the half width of the lithium transition metal composite oxide is measured using an X-ray diffractometer (manufactured by Rigaku, model name: MiniFlex II). Specifically, it is performed according to the following conditions and procedures.
  • the radiation source is CuK ⁇ , and the acceleration voltage and current are 30 kV and 15 mA, respectively.
  • the sampling width is 0.01 deg, the scanning time is 14 minutes (scanning speed is 5.0), the divergence slit width is 0.625 deg, the light receiving slit width is open, and the scattering slit is 8.0 mm.
  • the obtained X-ray diffraction data is indexed to the (003) plane in the space group R3-m using “PDXL” which is the software attached to the X-ray diffractometer without removing the peak derived from K ⁇ 2.
  • the half-width FWHM (104) for the existing diffraction peak is determined.
  • the total pore volume determined by the BJH method from the adsorption isotherm using the nitrogen gas adsorption method is 0.05 cm 3 / g or less.
  • the total pore volume is preferably 0.04 cm 3 / g or less.
  • the peak differential pore volume is preferably 0.2mm 3 / (g ⁇ nm) or less, more preferably 0.18mm 3 / (g ⁇ nm) or less, 0.12mm 3 / (g ⁇ nm ) or less is particularly preferable.
  • Such a high-density active material can be obtained by firing a high-density transition metal hydroxide precursor and a lithium compound. In FIG.
  • the total pore volume of the lithium transition metal complex oxide particle of an Example and a comparative example is shown. Specifically, based on the measurement results of the pore distribution for lithium transition metal composite oxide particles according to Example 1, Comparative Example 1, and Comparative Example 3 described later, the horizontal axis represents the pore diameter, and the vertical axis represents the fine particle. It is the figure which plotted the total pore volume corresponding to the pore below a pore diameter.
  • the lithium transition metal composite oxide particles of Example 1 obtained from the high density hydroxide precursor were the same as the lithium transition metal composite oxide particles of Comparative Example 1 obtained from the low density hydroxide precursor, carbonic acid. Compared with the lithium transition metal composite oxide particles of Comparative Example 3 obtained from the salt precursor, the total pore volume is remarkably reduced.
  • FIG. 1 The lithium transition metal composite oxide particles of Example 1 obtained from the high density hydroxide precursor were the same as the lithium transition metal composite oxide particles of Comparative Example 1 obtained from the low density hydroxide precursor, carbonic acid. Compared with the lithium transition metal composite oxide
  • the total pore volume and the peak differential pore volume of the lithium transition metal composite oxide particles are measured by the following method.
  • P0 about 770 mmHg
  • the lithium transition metal composite oxide particles according to this embodiment preferably have a tap density of 1.6 g / cm 3 or more, and more preferably 1.7 g / cm 3 or more.
  • the tap density of the lithium transition metal composite oxide is measured by the following method. 2 g ⁇ 0.2 g of the powder of the sample to be measured is put into a 10 ⁇ 2 dm 3 graduated cylinder, and REI ELECTRIC CO. LTD. A value obtained by dividing the volume of the sample to be measured after counting 300 times by the input mass using a tapping device manufactured by the company is adopted.
  • the sample used for the above various measurements is an active material powder before electrode preparation, it is used for measurement as it is.
  • the battery is put into a discharged state by the following procedure before disassembling the battery.
  • constant current charging is performed up to a battery voltage at which the positive electrode potential becomes 4.3 V (vs. Li / Li + ) with a current of 0.1 C, and the current value decreases to 0.01 C at the same battery voltage.
  • constant current discharge is performed at a current of 0.1 C until the battery voltage reaches a positive electrode potential of 2.0 V (vs. Li / Li + ), and a discharge end state is obtained.
  • the battery may be disassembled after the battery is brought into the end-of-discharge state or the end-of-charge state, and the electrode may be taken out.
  • the battery is adjusted to the end of discharge state according to the above procedure.
  • the work from disassembly of the battery to measurement is performed in an argon atmosphere with a dew point of -60 ° C or lower.
  • the taken-out positive electrode plate uses dimethyl carbonate to sufficiently wash the electrolytic solution adhering to the electrode, and after drying at room temperature for a whole day and night, the mixture on the aluminum foil current collector is collected. This mixture is fired at 600 ° C. for 4 hours using a small electric furnace to remove the carbon as the conductive agent and the PVdF binder as the binder, and take out the lithium transition metal composite oxide particles.
  • the transition metal hydroxide precursor used for producing the lithium transition metal composite oxide includes a transition metal (Me) containing Mn and Ni, or Mn, Ni and Co, and a mole of Mn in the transition metal (Me).
  • the ratio Mn / Me is larger than 0.5
  • the crystal form is a high-density granule
  • the tap density is 1.3 g / cm 3 or more.
  • the tap density is preferably 1.4 g / cm 3 or more.
  • a hydroxide precursor having a tap density of up to 1.7 g / cm 3 can be obtained.
  • the tap density of the hydroxide precursor and the carbonate precursor is measured by the same method as the tap density of the lithium transition metal composite oxide.
  • the lithium transition metal composite oxide produced using the transition metal hydroxide precursor according to this embodiment is a “lithium-excess” active material
  • Mn of the transition metal element Me in the hydroxide precursor The molar ratio Mn / Me is greater than 0.5. Within this range, it is possible to improve the tap density of the hydroxide precursor. Further, the molar ratio Co / Me of Co to the transition metal element Me in the hydroxide precursor is preferably 0.2 or less, may be 0, but is preferably 0.1 or more. The molar ratio Ni / Me is preferably 0.2 to 0.5. Within this range, it is possible to improve the tap density of the hydroxide precursor.
  • alkali metal hydroxide sodium hydroxide, lithium hydroxide, etc.
  • complexation together with a solution containing transition metal (Me), in a reaction tank that maintains alkalinity
  • an alkali solution containing an agent and a reducing agent ammonia, ammonium sulfate, ammonium nitrate or the like can be used, and ammonia is preferable.
  • a precursor having a higher tap density can be produced by a crystallization reaction using a complexing agent.
  • a reducing agent hydrazine, sodium borohydride and the like can be used, and hydrazine is preferable.
  • sodium hydroxide or lithium hydroxide can be used for the alkali metal hydroxide (neutralizing agent).
  • Mn is easily oxidized among Ni, Co, and Mn, and Ni, Mn, or a coprecipitation precursor in which Ni, Co, and Mn are uniformly distributed in a divalent state is produced. Therefore, uniform mixing at the atomic level of Ni, Mn, or Ni, Co, and Mn tends to be insufficient.
  • the Mn ratio is higher than the Ni and Co ratios, it is particularly important to remove dissolved oxygen in the aqueous solution.
  • the method for removing dissolved oxygen include a method of bubbling a gas not containing oxygen.
  • the gas not containing oxygen is not limited, but nitrogen gas, argon gas, carbon dioxide (CO 2 ), or the like can be used.
  • the pH in the step of producing a hydroxide precursor by coprecipitation of a compound containing Ni, Mn or Ni, Co, Mn in the solution is 8 Is preferably less than 9.8, and more preferably less than 9-9.8 (9.7 or less).
  • the tap density can be 1.3 g / cm 3 or more.
  • the stirring continuation time after the raw material aqueous solution dropping is completed can be shortened.
  • the raw material of the hydroxide precursor is manganese oxide, manganese carbonate, manganese sulfate, manganese nitrate, manganese acetate, etc. as the Mn compound, and nickel hydroxide, nickel carbonate, nickel sulfate, nickel nitrate, acetic acid as the Ni compound.
  • the Co compound such as nickel and the like include cobalt sulfate, cobalt nitrate, and cobalt acetate.
  • an alkali metal hydroxide such as sodium hydroxide (neutralizing agent), a complexing agent such as ammonia, hydrazine, etc.
  • a method in which a mixed alkaline solution containing the reducing agent is appropriately dropped is preferable.
  • the concentration of the alkali metal hydroxide to be dropped is preferably 1.0 to 8.0M.
  • the concentration of the complexing agent is preferably 0.4M or more, and more preferably 0.6M or more. Moreover, it is preferable that it is 2.0M or less, It is more preferable that it is 1.6M or less, It is further more preferable to set it as 1.5M or less.
  • the concentration of the reducing agent is preferably 0.05 to 1.0M, and more preferably 0.1 to 0.5M.
  • the tap density of the hydroxide precursor can be increased by lowering the pH of the reaction vessel and setting the concentration of ammonia (complexing agent) to 0.6 M or more.
  • the manufacturing method or the manufacturing conditions described characteristically above may be combined with a configuration in which the precursor Co / Me is 0, but by combining with a configuration in which Co / Me is 0.02 or more, high density The effect
  • the Co / Me ratio is more preferably 0.05 or more, and further preferably 0.1 or more.
  • the dropping speed of the raw material aqueous solution greatly affects the uniformity of element distribution within one particle of the hydroxide precursor to be produced.
  • Mn is difficult to form a uniform element distribution with Ni or Co, so care must be taken.
  • the preferred dropping rate is influenced by the size of the reaction vessel, stirring conditions, pH, reaction temperature, etc., but is preferably 30 mL / min or less. In order to improve the discharge capacity, the dropping rate is more preferably 10 mL / min or less, and most preferably 5 mL / min or less.
  • the particles are rotated and revolved in the stirring tank by continuing the stirring after the dropwise addition of the raw material aqueous solution.
  • a complexing agent such as ammonia
  • the particles collide with each other, and the particles grow concentrically in stages. That is, the hydroxide precursor undergoes two stages of reaction: a metal complex formation reaction when the raw material aqueous solution is dropped into the reaction tank, and a precipitation formation reaction that occurs while the metal complex is retained in the reaction tank. Formed through. Therefore, a hydroxide precursor having a target particle diameter can be obtained by appropriately selecting a time for continuing stirring after the dropping of the raw material aqueous solution.
  • the preferable stirring duration after completion of dropping of the raw material aqueous solution is influenced by the size of the reaction vessel, stirring conditions, pH, reaction temperature, etc., but 0.5 h or more is required to grow the particles as uniform spherical particles. Preferably, 1 h or more is more preferable. Further, in order to reduce the possibility that the output performance in the low SOC region of the battery is not sufficient due to the particle size becoming too large, it is preferably 15 h or less, more preferably 10 h or less, and most preferably 5 h or less.
  • the preferable stirring duration time for controlling D50 which is a particle diameter at which the cumulative volume in the particle size distribution of the secondary particles of the hydroxide precursor and the lithium transition metal composite oxide is 50%, to 13 ⁇ m or less is the pH to be controlled. It depends on. For example, when the pH is controlled to 8 to 9.7, the stirring duration is preferably 0.5 to 3 h, and when the pH is controlled to 9 to 9.7, the stirring duration is 1 to 5 h. preferable.
  • the hydroxide precursor particles are prepared using a sodium compound such as sodium hydroxide as a neutralizing agent, sodium ions adhering to the particles are removed by washing in the subsequent washing step.
  • a condition that the number of washings with 100 mL of ion-exchanged water is 5 times or more can be employed.
  • the lithium transition metal composite oxide of the present embodiment can be suitably produced by a method of firing after mixing the hydroxide precursor and a lithium compound (Li compound).
  • the lithium transition metal composite oxide produced by this method has an ⁇ -NaFeO 2 type crystal structure, and the molar ratio of Li to transition metal (Me) constituting the lithium transition metal composite oxide (Li / Me) Is greater than 1, the transition metal (Me) contains Mn and Ni, or Mn, Ni and Co, and the molar ratio of Mn in the transition metal (Me) Mn / Me is greater than 0.5.
  • Li compound lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, or the like can be used.
  • the amount of the Li compound it is preferable to add an excess of about 1 to 5% in view of the disappearance of a part of the Li compound during firing.
  • the firing temperature affects the reversible capacity of the active material.
  • the firing temperature is preferably less than the temperature at which the oxygen release reaction of the active material affects.
  • the oxygen release temperature of the active material is approximately 1000 ° C. or higher in the composition range according to the present embodiment, but there is a slight difference in the oxygen release temperature depending on the composition of the active material. It is preferable to confirm. In particular, it is confirmed that the oxygen release temperature of the hydroxide precursor shifts to a lower temperature side as the amount of Co contained in the sample increases.
  • a mixture of a hydroxide precursor and a lithium compound may be subjected to thermogravimetric analysis (DTA-TG measurement) in order to simulate the firing reaction process.
  • the platinum used in the sample chamber of the measuring instrument may be corroded by the Li component volatilized, and the instrument may be damaged, so a crystallization temperature is advanced to some extent by adopting a firing temperature of about 500 ° C. in advance.
  • the composition may be subjected to thermogravimetric analysis.
  • the firing temperature is preferably higher than 700 ° C.
  • the resistance of the crystal grain boundary can be reduced and smooth lithium ion transport can be promoted.
  • the inventors have found that strain remains in the lattice in the sample synthesized at a temperature lower than 750 ° C. It was found that almost all strains can be removed by synthesis at the above temperature. It was also found that the crystallite size increased in proportion to the increase in the synthesis temperature.
  • the composition of the active material according to the present embodiment particles having almost no lattice distortion in the system and having a sufficiently grown crystallite size can be obtained, and a favorable discharge capacity can be obtained.
  • a synthesis temperature (firing temperature) and a Li / Me ratio composition in which the amount of strain affecting the lattice constant is 2% or less and the crystallite size grows to 50 nm or more.
  • the crystallite size was maintained at 30 nm or more in the charging / discharging process, although it changed due to expansion / contraction. That is, an active material having a remarkably large reversible capacity can be obtained only by selecting the firing temperature as close as possible to the oxygen release temperature of the active material.
  • the firing temperature is preferably 750 to 940 ° C., more preferably 750 to 900 ° C., in order to ensure a sufficient discharge capacity per volume.
  • the lithium transition metal composite oxide used as the positive electrode active material of the present embodiment is manufactured.
  • the negative electrode active material is not limited. Any form that can deposit or occlude lithium ions may be selected.
  • titanium-based materials such as lithium titanate having a spinel crystal structure represented by Li [Li 1/3 Ti 5/3 ] O 4 , alloy-based materials such as Si, Sb, and Sn-based lithium metal, lithium alloys (Lithium metal-containing alloys such as lithium-silicon, lithium-aluminum, lithium-lead, lithium-tin, lithium-aluminum-tin, lithium-gallium, and wood alloys), lithium composite oxide (lithium-titanium), silicon oxide
  • an alloy capable of inserting and extracting lithium a carbon material (for example, graphite, hard carbon, low-temperature fired carbon, amorphous carbon, etc.) can be used.
  • the positive electrode active material powder and the negative electrode active material powder preferably have an average particle size of 100 ⁇ m or less.
  • the positive electrode active material powder is preferably 15 ⁇ m or less for the purpose of improving the high output characteristics of the nonaqueous electrolyte battery.
  • a method for producing a precursor having a predetermined size a method using a pulverizer, a classifier, and the like.
  • a mortar, a ball mill, a sand mill, a vibrating ball mill, a planetary ball mill, a jet mill, a counter jet mill, a swirling air flow type jet mill, a sieve, or the like is used.
  • wet pulverization in the presence of water or an organic solvent such as hexane may be used.
  • an organic solvent such as hexane
  • the positive electrode active material and the negative electrode active material which are main components of the positive electrode and the negative electrode have been described in detail.
  • the positive electrode and the negative electrode include a conductive agent, a binder, a thickener, A filler etc. may be contained as another structural component.
  • the conductive agent is not limited as long as it is an electron conductive material that does not adversely affect the battery performance.
  • natural graphite such as scaly graphite, scaly graphite, earthy graphite
  • artificial graphite carbon black, acetylene black
  • Conductive materials such as ketjen black, carbon whisker, carbon fiber, metal (copper, nickel, aluminum, silver, gold, etc.) powder, metal fiber, and conductive ceramic material can be included as one kind or a mixture thereof. .
  • acetylene black is preferable from the viewpoints of electronic conductivity and coatability.
  • the addition amount of the conductive agent is preferably 0.1% by weight to 50% by weight, and particularly preferably 0.5% by weight to 30% by weight with respect to the total weight of the positive electrode or the negative electrode.
  • acetylene black is preferably used after being pulverized into ultrafine particles of 0.1 to 0.5 ⁇ m because the necessary carbon amount can be reduced.
  • These mixing methods are physical mixing, and the ideal is uniform mixing. Therefore, it is possible to mix by a dry type or a wet type using a powder mixer such as a V-type mixer, an S-type mixer, a grinding machine, a ball mill, or a planetary ball mill.
  • the binder is usually a thermoplastic resin such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • EPDM ethylene-propylene-diene terpolymer
  • SBR rubber
  • the amount of the binder added is preferably 1 to 50% by weight, particularly 2 to 30% by weight, based on the total weight of the positive electrode or the negative electrode.
  • any material that does not adversely affect battery performance may be used.
  • olefin polymers such as polypropylene and polyethylene, amorphous silica, alumina, zeolite, glass, carbon and the like are used.
  • the addition amount of the filler is preferably 30% by weight or less with respect to the total weight of the positive electrode or the negative electrode.
  • the main components positive electrode active material for the positive electrode, negative electrode material for the negative electrode
  • an organic solvent such as N-methylpyrrolidone or toluene or water.
  • the obtained liquid mixture is applied on a current collector described in detail below, or is pressed and heat-treated at a temperature of about 50 ° C. to 250 ° C. for about 2 hours.
  • roller coating such as applicator roll, screen coating, doctor blade method, spin coating, bar coater, etc. It is not limited.
  • a current collector foil such as an Al foil or a Cu foil can be used.
  • the positive electrode current collector foil is preferably an Al foil
  • the negative electrode current collector foil is preferably a Cu foil.
  • the thickness of the current collector foil is preferably 10 to 30 ⁇ m.
  • the thickness of the mixture layer is preferably 40 to 150 ⁇ m (excluding the thickness of the current collector foil) after pressing.
  • Nonaqueous electrolyte used for the nonaqueous electrolyte secondary battery according to the present embodiment is not limited, and those generally proposed for use in lithium batteries and the like can be used.
  • Nonaqueous solvents used for the nonaqueous electrolyte include cyclic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, chloroethylene carbonate, and vinylene carbonate; cyclic esters such as ⁇ -butyrolactone and ⁇ -valerolactone; dimethyl carbonate, Chain carbonates such as diethyl carbonate and ethyl methyl carbonate; chain esters such as methyl formate, methyl acetate and methyl butyrate; tetrahydrofuran or derivatives thereof; 1,3-dioxane, 1,4-dioxane, 1,2-dimethoxy Ethers such as ethane, 1,4-dibutoxyethane and methyldiglyme; Nitri
  • electrolyte salt used for the non-aqueous electrolyte examples include LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , LiSCN, LiBr, LiI, Li 2 SO 4 , Li 2 B 10 Cl 10 , NaClO 4 , NaI, NaSCN, and NaBr.
  • LiCF 3 SO 3 LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 (SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 , (CH 3 ) 4 NBF 4 , ( CH 3 ) 4 NBr, (C 2 H 5 ) 4 NClO 4 , (C 2 H 5 ) 4 NI, (C 3 H 7 ) 4 NBr, (n-C 4 H 9 ) 4 NClO 4 , (nC 4 H 9 ) 4 NI, (C 2 H 5 ) 4 N-maleate, (C 2 H 5 ) 4 N-benzoate, (C 2 H 5 ) 4 N-phthalate, Examples thereof include organic ionic salts
  • the viscosity of the electrolyte can be further reduced, Low temperature characteristics can be further improved, and self-discharge can be suppressed, which is more preferable.
  • the concentration of the electrolyte salt in the nonaqueous electrolyte is preferably from 0.1 mol / L to 5 mol / L, more preferably from 0.5 mol / L to 2 in order to reliably obtain a nonaqueous electrolyte battery having high battery characteristics. 0.5 mol / L.
  • separator it is preferable to use a porous film or a non-woven fabric exhibiting excellent high rate discharge performance alone or in combination.
  • the material constituting the separator for a nonaqueous electrolyte battery include polyolefin resins typified by polyethylene and polypropylene, polyester resins typified by polyethylene terephthalate and polybutylene terephthalate, polyvinylidene fluoride, and vinylidene fluoride-hexa.
  • Fluoropropylene copolymer vinylidene fluoride-perfluorovinyl ether copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-fluoroethylene copolymer, fluorine Vinylidene fluoride-hexafluoroacetone copolymer, vinylidene fluoride-ethylene copolymer, vinylidene fluoride-propylene copolymer, vinylidene fluoride-trifluoropropylene copolymer, vinylidene fluoride - tetrafluoroethylene - hexafluoropropylene copolymer, vinylidene fluoride - ethylene - can be mentioned tetrafluoroethylene copolymer.
  • the porosity of the separator is preferably 98% by volume or less from the viewpoint of strength. Further, the porosity is preferably 20% by volume or more from the viewpoint of charge / discharge characteristics.
  • the separator may be a polymer gel composed of a polymer such as acrylonitrile, ethylene oxide, propylene oxide, methyl methacrylate, vinyl acetate, vinyl pyrrolidone, polyvinylidene fluoride, and an electrolyte.
  • a polymer such as acrylonitrile, ethylene oxide, propylene oxide, methyl methacrylate, vinyl acetate, vinyl pyrrolidone, polyvinylidene fluoride, and an electrolyte.
  • the separator is used in combination with the above-described porous film, nonwoven fabric, or the like and a polymer gel because the liquid retention of the electrolyte is improved. That is, by forming a film in which the surface of the polyethylene microporous membrane and the microporous wall are coated with a solvophilic polymer having a thickness of several ⁇ m or less, and holding the electrolyte in the micropores of the film, Gels.
  • solvophilic polymer examples include polyvinylidene fluoride, an acrylate monomer having an ethylene oxide group or an ester group, an epoxy monomer, a polymer having a monomer having an isocyanate group, and the like crosslinked.
  • the monomer can be subjected to a crosslinking reaction by irradiation with an electron beam (EB) or heating or ultraviolet (UV) irradiation with a radical initiator added.
  • EB electron beam
  • UV ultraviolet
  • FIG. 3 is an external perspective view of a rectangular lithium secondary battery 1 which is a nonaqueous electrolyte secondary battery according to one embodiment of the present invention. In the figure, the inside of the container is seen through. In the nonaqueous electrolyte secondary battery 1 shown in FIG. 3, an electrode group 2 is housed in a battery container 3.
  • the electrode group 2 is formed by winding a positive electrode including a positive electrode active material and a negative electrode including a negative electrode active material via a separator.
  • the positive electrode is electrically connected to the positive electrode terminal 4 via the positive electrode lead 4 ′
  • the negative electrode is electrically connected to the negative electrode terminal 5 via the negative electrode lead 5 ′.
  • This embodiment can also be realized as a power storage device in which a plurality of the nonaqueous electrolyte secondary batteries are assembled.
  • a power storage device according to one embodiment of the present invention is illustrated in FIG.
  • the power storage device 30 includes a plurality of power storage units 20.
  • Each power storage unit 20 includes a plurality of nonaqueous electrolyte secondary batteries 1.
  • the power storage device 30 can be mounted as a power source for vehicles such as an electric vehicle (EV), a hybrid vehicle (HEV), and a plug-in hybrid vehicle (PHEV).
  • EV electric vehicle
  • HEV hybrid vehicle
  • PHEV plug-in hybrid vehicle
  • Example 1 ⁇ Production process of hydroxide precursor>
  • a hydroxide precursor was prepared using a reaction crystallization method. First, 315.4 g of nickel sulfate hexahydrate, 168.6 g of cobalt sulfate heptahydrate, and 530.4 g of manganese sulfate pentahydrate were weighed, and all of these were dissolved in 4 L of ion-exchanged water, and Ni: Co A 1.0 M aqueous sulfate solution having a molar ratio of: Mn of 30:15:55 was prepared.
  • reaction vessel 2 L was poured into a 5 L reaction tank, and N 2 gas was bubbled for 30 minutes to remove oxygen contained in the ion exchange water.
  • the temperature of the reaction vessel is set to 50 ° C. ( ⁇ 2 ° C.) and the reaction vessel is stirred at a rotational speed of 1500 rpm using a paddle blade equipped with a stirring motor, so that sufficient convection occurs in the reaction vessel. did.
  • the sulfate aqueous solution was dropped into the reaction vessel at a rate of 1.3 mL / min for 50 hr.
  • the pH of the aqueous solution in the reaction vessel was appropriately dropped by adding a mixed alkaline solution consisting of 4.0 M sodium hydroxide, 1.25 M ammonia, and 0.1 M hydrazine from the start to the end of the dropping.
  • a mixed alkaline solution consisting of 4.0 M sodium hydroxide, 1.25 M ammonia, and 0.1 M hydrazine from the start to the end of the dropping.
  • stirring in the reaction vessel was continued for 1 hour. After stopping stirring, the mixture was allowed to stand at room temperature for 12 hours or longer.
  • the hydroxide precursor particles generated in the reaction tank are separated, and further, sodium ions adhering to the particles are washed and removed using ion exchange water, and an electric furnace is used. Then, it was dried in an air atmosphere at 80 ° C. under normal pressure for 20 hours. Then, in order to arrange
  • the molar ratio of Li: (Ni, Co, Mn) is 120:
  • a mixed powder of 100 was prepared. Using a pellet molding machine, molding was performed at a pressure of 6 MPa to obtain pellets having a diameter of 25 mm. The amount of the mixed powder subjected to pellet molding was determined by conversion so that the mass of the assumed final product was 2.5 g.
  • One pellet was placed on an alumina boat having a total length of about 100 mm, placed in a box-type electric furnace (model number: AMF20), heated in air atmosphere at normal pressure from room temperature to 800 ° C.
  • the box-type electric furnace has internal dimensions of 10 cm in length, 20 cm in width, and 30 cm in depth, and heating wires are inserted at intervals of 20 cm in the width direction. After firing, the heater was turned off and allowed to cool naturally with the alumina boat placed in the furnace. As a result, the temperature of the furnace decreases to about 200 ° C. after 5 hours, but the subsequent temperature decrease rate is somewhat moderate. After the passage of day and night, it was confirmed that the furnace temperature was 100 ° C. or lower, and then the pellets were taken out and pulverized for several minutes in a smoked automatic mortar in order to make the particle diameter uniform. In this way, lithium transition metal composite oxide Li 1.09 Ni 0.27 Co 0.14 Mn 0.50 O 2 according to Example 1 was produced.
  • Example 2 In the firing step, 1.214 g of lithium hydroxide monohydrate is added to 2.315 g of the hydroxide precursor, and a mixed powder having a molar ratio of Li: (Ni, Co, Mn) of 110: 100 is obtained.
  • a lithium transition metal composite oxide according to Example 2 was produced in the same manner as Example 1 except that it was prepared.
  • Examples 3 and 4 Lithium transition metal composite oxides according to Examples 3 and 4 were produced in the same manner as in Example 1, except that in the firing step, the firing temperature was changed from 800 ° C. to 750 ° C. and 900 ° C., respectively.
  • Example 5 In the step of preparing the hydroxide precursor, 315.4 g of nickel sulfate hexahydrate, 112.4 g of cobalt sulfate heptahydrate, and 578.6 g of manganese sulfate pentahydrate were weighed, and all of these were ion-exchanged water.
  • a 1.0M sulfate aqueous solution having a Ni: Co: Mn molar ratio of 30:10:60 was prepared by dissolving in 4 L, and 4.0 M
  • the pH of the aqueous solution in the reaction vessel was controlled to be constantly maintained at 9.3 by appropriately dropping a mixed alkaline solution composed of sodium hydroxide, 0.6M ammonia, and 0.3M hydrazine.
  • 1.373 g of lithium hydroxide monohydrate were added to 2.211 g of the hydroxide precursor to prepare a mixed powder having a molar ratio of Li: (Ni, Co, Mn) of 130: 100 Outside, in the same manner as in Example 1 to prepare a lithium transition metal composite oxide according to Example 5.
  • Example 6 In the step of preparing the hydroxide precursor, 262.8 g of nickel sulfate hexahydrate, 224.8 g of cobalt sulfate heptahydrate, and 530.4 g of manganese sulfate pentahydrate were weighed, and all of these were ion-exchanged water.
  • a 1.0M sulfate aqueous solution having a Ni: Co: Mn molar ratio of 25:20:55 is prepared by dissolving in 4 L, and 4.0 M
  • a mixed alkaline solution consisting of sodium hydroxide, 1.5M ammonia, and 0.2M hydrazine the pH of the aqueous solution in the reaction vessel is always controlled to be 9.5 ( ⁇ 0.1).
  • a lithium transition metal composite oxide according to Example 6 was produced in the same manner as Example 1 except for the above.
  • Example 7 In the step of preparing the hydroxide precursor, a mixed alkaline solution composed of 4.0 M sodium hydroxide, 0.8 M ammonia, and 0.3 M hydrazine is added from the start to the end of the dropwise addition of the sulfate aqueous solution.
  • the lithium transition metal composite according to Example 7 was the same as Example 1 except that the pH of the aqueous solution in the reaction vessel was controlled to be always kept at 9.5 ( ⁇ 0.1) by dropping appropriately. An oxide was produced.
  • Example 8 In the step of preparing the hydroxide precursor, a mixed alkaline solution composed of 4.0 M sodium hydroxide, 2 M ammonia, and 0.3 M hydrazine is appropriately dropped from the start to the end of the dropping of the sulfate aqueous solution. Thus, the pH of the aqueous solution in the reaction vessel was controlled so as to always maintain 9.5 ( ⁇ 0.1).
  • 2.212 g of the hydroxide precursor was added to lithium hydroxide monohydrate. Lithium transition according to Example 8 in the same manner as in Example 1 except that 1.371 g of the product was added and a mixed powder having a molar ratio of Li: (Ni, Co, Mn) of 130: 100 was prepared. A metal composite oxide was produced.
  • Comparative Example 1 In the step of preparing the hydroxide precursor, a mixed alkaline solution composed of 4.0 M sodium hydroxide, 0.5 M ammonia, and 0.3 M hydrazine was added from the start to the end of the dropwise addition of the sulfate aqueous solution.
  • the lithium transition metal composite according to Comparative Example 1 was used in the same manner as in Example 1 except that the pH of the aqueous solution in the reaction vessel was controlled so as to always maintain 10.55 ( ⁇ 0.1) by dropping appropriately. An oxide was produced.
  • Comparative Example 2 In the step of preparing the hydroxide precursor, a mixed alkaline solution composed of 4.0 M sodium hydroxide, 0.5 M ammonia, and 0.3 M hydrazine was added from the start to the end of the dropwise addition of the sulfate aqueous solution.
  • the lithium transition metal composite according to Comparative Example 2 was prepared in the same manner as in Example 1 except that the pH of the aqueous solution in the reaction vessel was controlled so as to always maintain 9.8 ( ⁇ 0.1) by dropping appropriately. An oxide was produced.
  • the coprecipitated carbonate particles produced in the reaction vessel are separated, and sodium ions adhering to the particles are washed away using ion-exchanged water, and an electric furnace is used. Then, it was dried in an air atmosphere at 80 ° C. under normal pressure for 20 hours. Then, in order to arrange
  • Example 2 instead of the hydroxide precursor prepared in Example 1, the carbonate precursor prepared as described above was used, and in the firing step, 1.047 g of lithium carbonate was added to 2.204 g of the carbonate precursor.
  • the lithium transition metal composite oxide according to Comparative Example 3 was the same as Example 1 except that a mixed powder having a molar ratio of 145: 100 was prepared and fired. Was made.
  • Comparative Example 4 A lithium transition metal composite oxide according to Comparative Example 4 was produced in the same manner as in Example 2 except that the firing temperature was 1000 ° C.
  • Example 9 to 15 In the step of preparing the hydroxide precursor, the concentration of ammonia in the mixed alkali solution added from the start to the end of the dropwise addition of the sulfate aqueous solution is changed from 1.25 M to 0.4 M and 0.6 M, respectively. , 0.8M, 1M, 1.4M, 1.6M, and 2M, hydroxide precursors according to Examples 9 to 15 were produced in the same manner as in Example 1.
  • Example 16 In the step of preparing the hydroxide precursor, 473.4 g of nickel sulfate hexahydrate and 530.6 g of manganese sulfate pentahydrate were weighed, and all of these were dissolved in 4 L of ion-exchanged water, and Ni: Co: Mn A hydroxide precursor according to Example 16 was produced in the same manner as in Example 1 except that a 1.0 M sulfate aqueous solution having a molar ratio of 45: 0: 55 was produced.
  • a coating paste in which the active material, acetylene black (AB) and polyvinylidene fluoride (PVdF) were kneaded and dispersed at a mass ratio of 90: 5: 5 was prepared.
  • the coating paste was applied to one side of an aluminum foil current collector having a thickness of 20 ⁇ m to produce a positive electrode plate.
  • the application thickness of the active material applied per fixed area was unified so that the test conditions for obtaining the discharge capacity per volume between the lithium secondary batteries according to all Examples and Comparative Examples were the same.
  • the nonaqueous electrolyte secondary battery electrode thus produced was partially cut out, a test battery that was a nonaqueous electrolyte secondary battery (lithium secondary battery) was produced by the following procedure, and the battery characteristics were evaluated. .
  • LiPF 6 As an electrolytic solution, LiPF 6 was dissolved in a mixed solvent in which ethylene carbonate (EC) / ethyl methyl carbonate (EMC) / dimethyl carbonate (DMC) had a volume ratio of 6: 7: 7 so that the concentration would be 1 mol / L. The solution was used.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • the separator a polypropylene microporous film whose surface was modified with polyacrylate was used.
  • the electrode is housed so that the open ends of the positive electrode terminal and the negative electrode terminal are exposed to the outside, and the fusion margin where the inner surfaces of the metal resin composite film face each other is hermetically sealed except for the portion serving as a liquid injection hole, After injecting the electrolytic solution, the injection hole was sealed.
  • the lithium secondary battery produced by the above procedure was subjected to an initial charge / discharge process at 25 ° C. Charging was performed at a constant current and a constant voltage with a current of 0.1 C and a voltage of 4.6 V, and the charge termination condition was when the current value was attenuated to 1/6.
  • the discharge was a constant current discharge with a current of 0.1 C and a final voltage of 2.0 V. This charge / discharge was performed for two cycles. Here, a pause process of 30 minutes was provided after charging and after discharging, respectively.
  • a plurality of non-aqueous electrolyte secondary battery electrodes according to Examples 1 to 8 and Comparative Examples 1 to 4 prepared above were cut into a size of 2 cm ⁇ 2 cm, respectively, and a flat plate press (manufactured by RIKEN SEIKI Co. LTD. CDM-20M TYPE P-1B), various post-pressing electrodes having different electrode plate thicknesses were produced by applying various pressing pressures from 1 MPa to 15 MPa.
  • the mixture density (g / cm 3 ) was calculated from the thickness and weight of each post-press electrode.
  • Each pressed electrode was dried under reduced pressure for 12 h under a temperature environment of 120 ° C., and after sufficiently removing the contained water, a line connecting each midpoint of two opposing sides of a 2 cm ⁇ 2 cm square was folded. As described above, nothing was sandwiched between the valleys, and it was folded by hand to make the other two opposite sides coincide. Furthermore, the crest portion of the fold that was curved and formed into a U-shape was pressed to bring the surfaces of the electrodes into contact with each other over the entire surface. Next, the sheet is spread again to the original flat shape, the electrode is directed toward the visible light source, the bent portion is visually observed, and the portion of the mixture layer is determined depending on whether visible light is observed through the bent portion. The presence or absence of damage was confirmed.
  • the electrode which has the smallest thickness among the electrodes by which damage was not recognized was determined, and the said mixture density (g / cm ⁇ 3 >) which concerns on the said electrode is the nonaqueous electrolyte secondary which concerns on the said Example or a comparative example It was defined as “limit mixture density (g / cm 3 )” of the battery electrode.
  • the discharge capacity per unit volume “0.1 C” is obtained by multiplying the value of the discharge capacity (mAh / g) by the value of the limit mixture density (g / cm 3 ).
  • the capacity (mAh / cm 3 ) ” was calculated.
  • Li / Me ratio of lithium transition metal composite oxides according to Examples 1 to 8 and Comparative Examples 1 to 4, firing temperature, FWHM (003) / FWHM (104), total pore volume, peak differential pore volume, Table 1 shows the 0.1 C capacity of a lithium secondary battery using a lithium transition metal composite oxide as a positive electrode active material and the tap density of the lithium transition metal composite oxide (active material).
  • Ni / Me ratio, Co / Me ratio, Mn / Me ratio of precursors according to Examples 1 to 16 and Comparative Examples 1 to 4 types of precursors, pH of the reaction tank, alkaline solution dropped into the reaction tank
  • Table 2 shows the concentrations of ammonia and hydrazine and the tap density of the precursor.
  • the lithium transition according to Examples 1 to 8 having a crystal structure in which FWHM (003) / FWHM (104)) is 0.6 or less and the total pore volume is 0.05 cm 3 / g or less. It can be seen that a lithium secondary battery using a metal composite oxide has a large 0.1 C capacity, which is a discharge capacity per volume. It can also be seen that the peak differential pore volume of the lithium transition metal composite oxide is preferably 0.2 mm 3 / (g ⁇ nm) or less.
  • such crystal structure and microstructure have a composition in which Li / Me is larger than 1 and Mn / Me is larger than 0.5, and the coprecipitation precursor is a hydroxide, It can be seen that the pH of the aqueous solution in the reaction vessel in the production process of the hydroxide precursor is less than 9.8, and the lithium transition metal composite oxide is obtained when calcined at a temperature of 750 to 900 ° C. When the pH of the aqueous solution in the reaction vessel is 9 to less than 9.8, the tap density of the hydroxide precursor is 1.3 g / cm 3 or more.
  • the concentration of ammonia (complexing agent) to be dropped is preferably 0.6 M or more.
  • the tap density of the hydroxide precursor can be 1.4 g / cm 3 or more at 0.6 to 1.6M.
  • the concentration of hydrazine (reducing agent) is preferably 0.1M or higher.
  • the tap density of the hydroxide precursor is 1.3 g / cm 3 or more. do not become.
  • the lithium transition metal composite oxide obtained by firing these hydroxide precursors has a FWHM (003) / FWHM (104) of 0.6 or less, but the total pore volume is 0.05 cm 3. / C and 0.1 C capacity per volume becomes small. Further, such a lithium transition metal composite oxide has a peak differential pore volume larger than 0.2 mm 3 / (g ⁇ nm).
  • Li / Me is larger than 1
  • Mn / Me is larger than 0.5
  • FWHM (003) / FWHM (104)) is 0.6 or less
  • the total pore volume is 0.00.
  • the discharge capacity per volume is increased by using a lithium transition metal composite oxide that satisfies the requirement of not more than 05 cm 3 / g as the positive electrode active material of the nonaqueous electrolyte secondary battery.
  • the pH of the aqueous solution in the reaction vessel in the hydroxide precursor preparation step is less than 9.8, and the lithium transition metal composite oxide is heated at a temperature of 750 to 900 ° C. Obtained when fired.
  • a nonaqueous electrolyte secondary battery having a large discharge capacity per volume can be provided.
  • the battery is useful as a nonaqueous electrolyte secondary battery for hybrid vehicles and electric vehicles.
  • Nonaqueous electrolyte secondary battery lithium secondary battery
  • Electrode group 3
  • Battery container 4 Positive electrode terminal 4 ′
  • Negative electrode lead 20 Power storage unit 30

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un matériau actif d'électrode positive qui dispose d'une capacité de décharge élevée par volume unitaire ; un précurseur d'hydroxyde à haute densité pour produire ce matériau actif d'électrode positive ; une électrode pour batteries secondaires à électrolyte non aqueux, qui utilise ce matériau actif d'électrode positive ; et une batterie secondaire à électrolyte non aqueux. La solution selon l'invention concerne un matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux, qui comporte un oxyde composite de métal de transition de lithium. L'oxyde composite de métal de transition de lithium dispose d'une structure cristalline de type α-NaFeO2 ; le rapport molaire de Li au métal de transition (Me), c'est-à-dire, le rapport molaire Li/Me est supérieur à 1 ; le métal de transition (Me) comprend du Mn et du Ni, ou du Mn, du Ni et du Co, et le rapport molaire Mn/Me est supérieur à 0,5 ; l'oxyde composite de métal de transition de lithium dispose d'un diagramme de diffraction des rayons X appartenant à R3-m ; le rapport de la demi-largeur d'un pic de diffraction du plan (003) à la demi-largeur (FWHM (104)) d'un pic de diffraction du plan (104) par les indices de Miller hkl obtenus par la mesure de diffraction des rayons X à l'aide d'un rayon CuKα, c'est-à-dire (FWHM(003)/FWHM(104)) est inférieur ou égal à 0,6 ; et le volume total des pores tel qu'il a été déterminé par un procédé BJH à partir de l'isotherme d'adsorption à l'aide d'un procédé d'adsorption de gaz d'azote est inférieur ou égal à 0,05 cm3/g.
PCT/JP2017/024741 2016-07-14 2017-07-05 Matériau actif d'électrode positive destiné à des batteries secondaires à électrolyte non aqueux, précurseur d'hydroxyde de métal de transition, procédé de production de précurseur d'hydroxyde de métal de transition, procédé de production de matériau actif d'électrode positive destiné à des batteries secondaires à électrolyte non aqueux, électrode destinée à des batteries secondaires à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux et dispositif de stockage d'électricité Ceased WO2018012385A1 (fr)

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CN112771695A (zh) * 2018-06-21 2021-05-07 株式会社杰士汤浅国际 非水电解质二次电池用正极活性物质、非水电解质二次电池用正极活性物质的制造方法、非水电解质二次电池用正极、非水电解质二次电池、非水电解质二次电池的制造方法和非水电解质二次电池的使用方法
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CN113454032A (zh) * 2019-02-22 2021-09-28 住友金属矿山株式会社 锂离子二次电池用正极活性物质、锂离子二次电池用正极活性物质的制造方法、锂离子二次电池
EP3910708A4 (fr) * 2019-03-15 2022-03-30 Basf Toda Battery Materials LLC Matériau actif d'électrode positive pour accumulateur ayant un électrolyte non aqueux, électrode positive pour accumulateur ayant un électrolyte non aqueux, et accumulateur ayant un électrolyte non aqueux
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CN113161537B (zh) * 2021-03-31 2022-06-21 华南师范大学 高镍材料及其制备方法与应用
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US20190270650A1 (en) * 2016-10-31 2019-09-05 Sumitomo Chemical Company, Limited Positive electrode active material precursor for lithium secondary battery, and method for manufacturing positive electrode active material for lithium secondary battery
WO2019117281A1 (fr) * 2017-12-15 2019-06-20 株式会社Ｇｓユアサ Matériau actif d'électrode positive destiné à des batteries secondaires à électrolyte non aqueux, précurseur d'hydroxyde de métal de transition, procédé de production de précurseur d'hydroxyde de métal de transition, procédé de production de matériau actif d'électrode positive destiné à des batteries secondaires à électrolyte non aqueux, électrode positive destinée à des batteries secondaires à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
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JPWO2019117282A1 (ja) * 2017-12-15 2021-01-07 株式会社Ｇｓユアサ 非水電解質二次電池用正極活物質、非水電解質二次電池用正極活物質の製造方法、非水電解質二次電池用正極、及び非水電解質二次電池
WO2019117282A1 (fr) * 2017-12-15 2019-06-20 株式会社Ｇｓユアサ Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux, procédé de fabrication de matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux, électrode positive pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
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US11545662B2 (en) 2017-12-15 2023-01-03 Gs Yuasa International Ltd. Positive active material for nonaqueous electrolyte secondary battery, method of producing positive active material for nonaqueous electrolyte secondary battery, positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
US11251427B2 (en) 2017-12-15 2022-02-15 Gs Yuasa International Ltd. Positive active material for nonaqueous electrolyte secondary battery, transition metal hydroxide precursor, method of producing transition metal hydroxide precursor, method of producing positive active material for nonaqueous electrolyte secondary battery, positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
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