WO2017150504A1 - スピネル型リチウムマンガン含有複合酸化物 - Google Patents

スピネル型リチウムマンガン含有複合酸化物 Download PDF

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WO2017150504A1
WO2017150504A1 PCT/JP2017/007698 JP2017007698W WO2017150504A1 WO 2017150504 A1 WO2017150504 A1 WO 2017150504A1 JP 2017007698 W JP2017007698 W JP 2017007698W WO 2017150504 A1 WO2017150504 A1 WO 2017150504A1
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Prior art keywords
spinel
composite oxide
lithium manganese
type lithium
containing composite
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French (fr)
Japanese (ja)
Inventor
恭平 山口
徹也 光本
松嶋　英明
蔭井　慎也
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Mitsui Kinzoku Co Ltd
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Mitsui Mining and Smelting Co Ltd
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Priority to JP2017562778A priority Critical patent/JP6391857B2/ja
Priority to US16/080,175 priority patent/US10468677B2/en
Priority to CN201780003954.XA priority patent/CN108352523B/zh
Priority to EP17759970.1A priority patent/EP3425705B1/en
Publication of WO2017150504A1 publication Critical patent/WO2017150504A1/ja
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    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
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Definitions

  • the present invention relates to a spinel-type lithium manganese-containing composite oxide that can be used as a positive electrode active material of a lithium secondary battery, and in particular, a 5V-class spinel-type lithium manganese-containing composite having an operating potential of 4.5 V or more at a metal Li reference potential. Relates to oxides.
  • Lithium secondary batteries have features such as high energy density and long life. For this reason, lithium secondary batteries are widely used as power sources for home appliances such as video cameras, portable electronic devices such as notebook computers and mobile phones, and power tools such as power tools. (EV) and hybrid electric vehicles (HEV) are also applied to large batteries.
  • EV electric and hybrid electric vehicles (HEV) are also applied to large batteries.
  • a lithium secondary battery is a secondary battery with a structure in which lithium is melted as ions from the positive electrode during charging, moves to the negative electrode and is stored, and reversely, lithium ions return from the negative electrode to the positive electrode during discharging. It is known to be caused by the potential of the positive electrode material.
  • Examples of the positive electrode active material for this type of lithium secondary battery include lithium transition metal oxides such as LiCoO 2 , LiNiO 2 and LiMnO 2 having a layer structure, and manganese such as LiMn 2 O 4 and LiNi 0.5 Mn 1.5 O 4.
  • a spinel-type lithium manganese-containing composite oxide having a spinel structure (Fd-3m) is known.
  • This type of spinel-type lithium manganese-containing composite oxide has low raw material price, is non-toxic and safe, and has a strong property against overcharge. It is attracting attention as a next-generation positive electrode active material for large batteries.
  • spinel lithium transition metal oxide (LMO) capable of three-dimensional Li ion insertion / extraction is superior in output characteristics to lithium transition metal oxides such as LiCoO 2 having a layer structure. Therefore, it is expected to be used in applications that require excellent output characteristics such as EV batteries and HEV batteries.
  • Patent Document 1 as a positive electrode active material of a lithium secondary battery exhibiting a 5V class electromotive force, high capacity obtained by adding spinel-type lithium manganese composite oxide with chromium as an essential additive component and further adding nickel or cobalt.
  • a spinel type lithium manganese composite oxide positive electrode active material is disclosed.
  • Patent Document 2 discloses a spinel crystal LiMn 2-yz Ni y M z O 4 that charges and discharges at a potential of 4.5 V or more with respect to Li metal (where M: Fe, Co, Ti, V , Mg, Zn, Ga, Nb, Mo, Cu, at least one selected from the group consisting of 0.25 ⁇ y ⁇ 0.6, 0 ⁇ z ⁇ 0.1) is disclosed.
  • Patent Document 3 as a positive electrode active material capable of generating an electromotive force of 4.5 V or more and maintaining a discharge capacity, a general formula: Lia (M x Mn 2-xy A y ) O 4 ( In the formula, 0.4 ⁇ x, 0 ⁇ y, x + y ⁇ 2, 0 ⁇ a ⁇ 1.2 M is selected from the group consisting of Ni, Co, Fe, Cr and Cu, and contains at least Ni A includes at least one metal element, A includes at least one metal element selected from Si and Ti, provided that when A includes only Ti, the value of the ratio y of A is 0.1 ⁇ y
  • the positive electrode active material for secondary batteries characterized by including the spinel type lithium manganese complex oxide represented by this is disclosed.
  • Patent Document 4 in a spinel-type lithium manganese-containing composite oxide having an operating potential of 4.5 V or more at a metal Li reference potential, a part of Mn sites in LiMn 2 O 4- ⁇ contains Li and Ni.
  • a metal element M1 (M1 is a metal element containing at least one of Ni, Co and Fe) and another metal element M2 (M2 is Ti or Ti and Mg, Al, Ba, Cr and
  • M1 is a metal element containing at least one of Ni, Co and Fe
  • M2 is Ti or Ti and Mg, Al, Ba, Cr
  • a spinel type lithium manganese-containing composite oxide is disclosed.
  • Spinel-type lithium manganese-containing composite oxide having an operating potential of 4.5 V or more (also referred to as “5V-class spinel”) is a problem that hardly occurs with 4V-class spinel-type lithium manganese-containing composite oxide, It has a characteristic problem that the amount of gas generated by the reaction is large. In order to solve this problem, that is, to suppress the gas generation amount, it has been proposed to suppress the gas generation amount by increasing the primary particle diameter of the 5V class spinel and reducing the specific surface area (SSA). . However, when the specific surface area is reduced, the contact area with the electrolytic solution is reduced, which causes a problem that output characteristics are deteriorated.
  • SSA specific surface area
  • the present invention relates to a 5V class spinel, and provides a new spinel-type lithium manganese-containing composite oxide that can improve gas output while simultaneously improving output characteristics and further improving life characteristics. It is something to be done. This is the first problem of the present invention.
  • the present inventor further searched for a positive electrode active material capable of improving gas generation and life characteristics while maintaining or improving output characteristics.
  • a positive electrode active material capable of improving gas generation and life characteristics while maintaining or improving output characteristics.
  • it has been proposed to coat the particle surface of the spinel-type lithium manganese-containing composite oxide with a metal or a metal oxide.
  • the present invention achieves an improvement in rate characteristics while maintaining improvement in cycle characteristics and suppression of gas generation as compared with the positive electrode active material that has been subjected to surface treatment that has been conventionally proposed, in addition to the first problem. It is an object of the present invention to provide a new spinel-type lithium manganese-containing composite oxide. This is the second problem of the present invention.
  • the present inventor has also sought a positive electrode active material that can achieve both expansion of a high potential capacity region and reduction of gas generation while maintaining or improving output characteristics.
  • 5V class spinel has been found to expand the plateau region around 4.5V and expand the high potential capacity region, while increasing the amount of gas generated. For this reason, it has been difficult for the 5V-class spinel to simultaneously increase the energy density by expanding the high potential capacity region and to suppress the amount of gas generated.
  • the present invention is to provide a new spinel-type lithium manganese-containing composite oxide capable of achieving both the expansion of the high potential capacity region and the suppression of gas generation in addition to the first problem. This is the third problem of the present invention.
  • the present invention provides a spinel lithium manganese having an operating potential of 4.5 V or more at a metallic Li reference potential, containing at least Li, Mn, and O and two or more other elements.
  • Containing complex oxide, Regarding D50, mode diameter, and D10 (referred to as “D50”, “mode diameter”, and “D10”, respectively) by volume particle size distribution measurement obtained by measuring by the laser diffraction / scattering particle size distribution measurement method, D50 is 0.5 ⁇ m to 9 ⁇ m.
  • the present invention also provides, as means for solving the first problem, a spinel type lithium having an operating potential of 4.5 V or more at a metallic Li reference potential, containing at least Li, Mn, and O and two or more other elements.
  • a manganese-containing composite oxide, Regarding D50, mode diameter and D10, D50 is 0.5 ⁇ m to 9 ⁇ m, and the value of (
  • the average primary particle diameter calculated from the SEM image and the average primary particle diameter / D50 calculated from the D50 are 0.20 to 0.99, Spinel-type lithium manganese having a crystallite size of 80 nm to 490 nm and a crystallite size / average primary particle diameter calculated from the crystallite size and the primary particle diameter of 0.01 to 0.32 Proposed complex oxides are proposed.
  • the present invention also provides a spinel type lithium having a working potential of 4.5 V or more at a metal Li reference potential, which includes at least Li, Mn, and O and two or more elements other than these as a solution to the second problem.
  • a manganese-containing composite oxide, Regarding D50, mode diameter, and D10 (referred to as “D50”, “mode diameter”, and “D10”, respectively) by volume particle size distribution measurement obtained by measuring by the laser diffraction / scattering particle size distribution measurement method, D50 is 0.5 ⁇ m to 9 ⁇ m.
  • / mode diameter) ⁇ 100 is 0 to 25%
  • / mode diameter) ⁇ 100 is 20 to 58%
  • the average primary particle diameter calculated from an SEM image (referred to as “SEM image”) obtained by a scanning electron microscope (SEM) and the average primary particle diameter / D50 calculated from the D50 was 0.20 to 0.99.
  • the primary particles are polycrystalline, At least a part of the surface of lithium manganese composite oxide particles (also referred to as “core particles”) operating at a charging voltage in the region exceeding 4.5 V at a metal Li reference potential, at least titanium, aluminum, zirconium, or these Proposed is a positive electrode active material for a lithium secondary battery comprising a layer containing two or more of them (referred to as “A layer”).
  • the present invention also provides a spinel type lithium having a working potential of 4.5 V or more at a metal Li reference potential, which includes at least Li, Mn, and O and two or more elements other than these as a solution to the second problem.
  • a manganese-containing composite oxide, Regarding D50, mode diameter and D10, D50 is 0.5 ⁇ m to 9 ⁇ m, and the value of (
  • the average primary particle diameter calculated from the SEM image and the average primary particle diameter / D50 calculated from the D50 are 0.20 to 0.99,
  • the crystallite size is 80 nm to 490 nm, and the crystallite size / average primary particle diameter calculated from the crystallite size and the primary particle diameter is 0.01 to 0.32.
  • At least a part of the surface of lithium manganese composite oxide particles (also referred to as “core particles”) operating at a charging voltage in the region exceeding 4.5 V at a metal Li reference potential, at least titanium, aluminum, zirconium, or these Proposed is a positive electrode active material for a lithium secondary battery comprising a layer containing two or more of them (referred to as “A layer”).
  • the present invention also provides, as a means for solving the third problem, spinel lithium having an operating potential of 4.5 V or more at a metallic Li reference potential, containing at least Li, Mn, and O and two or more other elements.
  • a manganese-containing composite oxide, Regarding D50, mode diameter, and D10 (referred to as “D50”, “mode diameter”, and “D10”, respectively) by volume particle size distribution measurement obtained by measuring by the laser diffraction / scattering particle size distribution measurement method, D50 is 0.5 ⁇ m to 9 ⁇ m.
  • / mode diameter) ⁇ 100 is 0 to 25%
  • / mode diameter) ⁇ 100 is 20 to 58%
  • the average primary particle diameter calculated from an SEM image (referred to as “SEM image”) obtained by a scanning electron microscope (SEM) and the average primary particle diameter / D50 calculated from the D50 was 0.20 to 0.99.
  • the primary particles are polycrystalline, Proposal of a spinel-type lithium manganese-containing composite oxide characterized in that a peak exists between 2 ⁇ and 14.0 to 16.5 ° in an X-ray diffraction pattern measured by a powder X-ray diffractometer (XRD) To do.
  • the present invention also provides, as a means for solving the third problem, spinel lithium having an operating potential of 4.5 V or more at a metallic Li reference potential, containing at least Li, Mn, and O and two or more other elements.
  • a manganese-containing composite oxide, Regarding D50, mode diameter and D10, D50 is 0.5 ⁇ m to 9 ⁇ m, and the value of (
  • the average primary particle diameter calculated from the SEM image and the average primary particle diameter / D50 calculated from the D50 are 0.20 to 0.99,
  • the crystallite size is 80 nm to 490 nm, and the crystallite size / average primary particle diameter calculated from the crystallite size and the primary particle diameter is 0.01 to 0.32.
  • the spinel-type lithium manganese-containing composite oxide proposed by the present invention has an operating potential of 4.5 V or more at the metal Li reference potential, and yet simultaneously improves output characteristics and life characteristics while suppressing gas generation. be able to.
  • Example 3 is a volume particle size distribution obtained by measuring the spinel type lithium manganese-containing composite oxide obtained in Example 2 by a laser diffraction scattering type particle size distribution measuring method.
  • a spinel-type lithium manganese-containing composite oxide (referred to as “the present 5V class spinel”) according to an example of the embodiment of the present invention is fitted with a cubic crystal structure model of the space group Fd-3m (Origin Choice 2) and observed.
  • Rwp which represents the degree of coincidence of strength and calculated strength, is a lithium manganese-containing composite oxide in which Rwp ⁇ 10 or S ⁇ 2.5, and has an operating potential of 4.5 V or more at the metal Li reference potential 5V spinel.
  • “having an operating potential of 4.5 V or higher at the metal Li reference potential” does not need to have only an operating potential of 4.5 V or higher as the plateau region, It is intended to include the case of having a part.
  • the present invention is not limited to the lithium manganese-containing composite oxide composed only of “5V class lithium manganese-containing composite oxide” having an operating potential of 4.5 V or more as a plateau region.
  • a “4V class lithium manganese-containing composite oxide” having an operating potential of less than 4.5 V as the plateau region may be included.
  • the 5V-class lithium manganese-containing composite oxide only needs to occupy 30% by mass or more, preferably 50% by mass or more, and particularly preferably 80% by mass or more (including 100% by mass).
  • a lithium-manganese-containing composite oxide is allowed.
  • the present 5V-class spinel is a spinel-type lithium manganese-containing composite oxide containing at least Li, Mn, and O and two or more elements other than these.
  • At least one element of the above “two or more other elements” may be an element M1 selected from the group consisting of Ni, Co, and Fe, and the other element may be Na, Mg, Al , K, Ca, Ti, V, Cr, Fe, Co, Cu, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, and Ce may be used.
  • spinel type lithium having a crystal structure in which a part of the Mn site in LiMn 2 O 4- ⁇ is replaced with Li, a metal element M1, and another metal element M2. The thing containing a manganese containing complex oxide can be mentioned.
  • the metal element M1 is a substitution element that mainly contributes to developing an operating potential of 4.5 V or higher at the metal Li reference potential, and examples thereof include Ni, Co, and Fe. It may be included, and other metal elements may be included as M1.
  • the metal element M2 is a substitution element that contributes mainly to stabilizing the crystal structure and enhancing the characteristics.
  • a substitution element that contributes to improving the capacity retention rate for example, Na, Mg, Al, K, Ca, Ti , V, Cr, Fe, Co, Cu, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, Ce, and the like.
  • these selected from the group consisting of Na, Mg, Al, K, Ca, Ti, V, Cr, Fe, Co, Cu, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, and Ce As long as it contains at least one of the above, and M2 may contain other metal elements.
  • the M2 metal element contained in the structure is an element type different from the M1 metal element.
  • Equation (1) Li x (M1 y M2 z Mn 2-x-y-z) O 4- ⁇ by include those containing spinel-type lithium manganese-containing composite oxide represented Can do.
  • M1 and M2 in the formula (1) are as described above.
  • “x” may be 1.00 to 1.20, particularly 1.01 or more and 1.10 or less, and more preferably 1.02 or more and 1.08 or less. Even more preferred.
  • “Y” indicating the content of M1 may be 0.20 to 1.20, particularly 0.30 or more and 1.10 or less, and more preferably 0.35 or more and 1.05 or less. Even more preferred.
  • “Z” indicating the content of M2 may be 0.001 to 0.400, more preferably 0.002 or more and 0.400 or less, particularly 0.005 or more and 0.30 or less, and more preferably 0. More preferably, it is 10 or more. In particular, the amount of gas generation can be more effectively suppressed by setting it to 0.10 or more.
  • ⁇ is preferably 0 or more and 0.2 or less, more preferably 0.1 or less, and even more preferably 0.05 or less.
  • the present 5V class spinel may contain components other than Li, Mn, M1, M2 and O.
  • other elements may be contained as long as each is 0.5 wt% or less. This is because this amount is considered to have little influence on the performance of the present 5V class spinel.
  • x may be 1.00 to 1.20, particularly 1.01 or more and 1.10 or less, and more preferably 1.02 or more and 1.08 or less. Even more preferred.
  • “y” is preferably 0.20 to 0.70, particularly 0.30 or more and 0.60 or less, and more preferably 0.35 or more and 0.55 or less. Is even more preferable.
  • M is Na, Mg, Al, K, Ca, Ti, V, Cr, Fe, Co, Cu, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, and It is preferably one kind selected from the group consisting of Ce or a combination of two or more elements.
  • “z” indicating the molar ratio of M is preferably larger than 0 and not larger than 0.5, more preferably larger than 0.01 or not larger than 0.45. It is more preferably 0.5 or more and 0.40 or less, and even more preferably 0.1 or more and 0.35 or less.
  • “4- ⁇ ” in the above formula (2) indicates that oxygen deficiency may be included.
  • part of oxygen may be substituted with fluorine or another element.
  • ⁇ is preferably 0 or more and 0.2 or less, more preferably 0.1 or less, and even more preferably 0.05 or less.
  • the present 5V class spinel may contain components other than Li, Mn, M, M1, M2 and O described above.
  • other elements may be contained as long as each is 0.5 wt% or less. This is because this amount is considered to have little influence on the performance of the present 5V class spinel.
  • this 5V class spinel may contain B.
  • B may contain a complex oxide phase containing Ni, Mn and B in addition to the spinel crystal phase.
  • the complex oxide phase containing Ni, Mn, and B include a crystal phase of Ni 5 MnO 4 (BO 3 ) 2 .
  • the fact that the crystal phase of Ni 5 MnO 4 (BO 3 ) 2 is contained means that the diffraction pattern obtained by X-ray diffraction (XRD) is collated with a PDF (Powder Diffraction File) number “01-079-1029”. Can be confirmed.
  • the composite oxide containing Ni, Mn and B is presumed to exist on the surface and grain boundaries of the present 5V class spinel particles.
  • the composite oxide phase is contained so that the content of B element in the present 5V class spinel is 0.02 to 0.80 mass%.
  • the composite oxide phase should be contained so that the content is 0.05% by mass or more or 0.60% by mass or less, particularly 0.30% by mass or less, and particularly 0.25% by mass or less. Further preferred. If the content of B element is 0.02% by mass or more, the discharge capacity at a high temperature (for example, 45 ° C.) can be maintained, and if the content of B element is 0.80% by mass or less, rate characteristics Can be maintained, which is preferable.
  • the primary particles of the 5V class spinel are preferably not a single crystal but a polycrystal.
  • a single crystal means a particle in which the primary particles are composed of one crystallite
  • a polycrystal means a particle in which a plurality of crystallites are present in the primary particle.
  • Whether or not the present 5V-class spinel is a polycrystal is a range in which the ratio of crystal size to primary particle size (crystallite size / average primary particle size) is close to 0, specifically greater than 0 and less than 1. It can also be determined by confirming that it is within. A value close to 0 indicates that a large number of crystallites are contained in the primary particles. However, it is not limited to this determination method.
  • the “primary particle” in the present invention means the smallest unit particle surrounded by a grain boundary when observed with an SEM (scanning electron microscope, for example, 500 to 5000 times). Then, the average diameter of the primary particles is observed with an SEM (scanning electron microscope, for example, 500 to 5000 times), and 30 primary particles are arbitrarily selected, and image analysis software is used to select the selected primary particles. The average particle diameter is calculated, and the 30 primary particle diameters are averaged to obtain the “average primary particle diameter”.
  • “secondary particles” mean particles that agglomerate such that a plurality of primary particles share a part of their outer periphery (grain boundary) and are isolated from other particles. .
  • Crystallite means the largest group that can be regarded as a single crystal, and can be obtained by XRD measurement and Rietveld analysis.
  • the mode diameter of the present 5V class spinel that is, the mode diameter by volume particle size distribution measurement obtained by measuring by the laser diffraction / scattering particle size distribution measurement method is preferably 0.4 ⁇ m to 11 ⁇ m.
  • the mode diameter of the 5V class spinel is preferably 0.4 ⁇ m to 11 ⁇ m, especially 1 ⁇ m or more or 10 ⁇ m or less, especially 2 ⁇ m or more or 9 ⁇ m or less, and more preferably less than 8 ⁇ m. preferable.
  • the D50 of the present 5V class spinel that is, the D50 by volume particle size distribution measurement obtained by measurement by the laser diffraction / scattering particle size distribution measurement method is preferably 0.5 ⁇ m to 9 ⁇ m.
  • the D50 of the present 5V class spinel is preferably 0.5 ⁇ m to 9 ⁇ m, and more preferably 0.6 ⁇ m or more and 8 ⁇ m or less, of which, more than 1 ⁇ m, less than 8 ⁇ m, of which particularly greater than 2 ⁇ m or 7 ⁇ m. More preferably, it is less than.
  • / mode diameter) ⁇ 100 is preferably 0 to 25%. That the value of (
  • / mode diameter) ⁇ 100 is preferably 0 to 25% for the present 5V class spinel, more than 0% or less than 24%, of which 23% In the following, it is particularly preferable that the content is more than 1% or less than 20%.
  • the D10 of the present 5V class spinel that is, the D10 by volume particle size distribution measurement obtained by measuring by the laser diffraction / scattering particle size distribution measuring method is preferably 0.2 ⁇ m to 4.0 ⁇ m. Regarding this 5V class spinel, gas generation can be suppressed by adjusting D10 to the above range. From this point of view, the D10 of the present 5V class spinel is preferably 0.2 ⁇ m to 4.0 ⁇ m, more preferably 0.25 ⁇ m or more or 4.0 ⁇ m or less, and particularly preferably 0.3 ⁇ m or more or less than 4.0 ⁇ m. Is particularly preferred.
  • / mode diameter) ⁇ 100 is preferably 20 to 58%.
  • / mode diameter) ⁇ 100 of 20 to 58% indicates that the distribution width from the mode diameter of this 5V class spinel to D10 is narrow.
  • the particle size distribution Is close to the normal distribution and has a sharp distribution. That is, the sizes of the primary particles and the secondary particles can be made uniform. This indicates that the proportion of the fine powder region in the entire particle size distribution can be reduced. Since the fine powder adversely affects the gas generation and life characteristics, the gas generation and life characteristics can be improved by reducing the proportion of the fine powder.
  • / mode diameter) ⁇ 100 is preferably 20 to 58% for the present 5V class spinel, more preferably 22% or more or 57% or less, of which 25%. It is more preferably not less than 56%, more preferably not less than 30% or less than 52%, particularly preferably not less than 35% or less than 50%.
  • the Dmin of the present 5V class spinel that is, the Dmin by volume particle size distribution measurement obtained by measurement by the laser diffraction / scattering particle size distribution measurement method is preferably 0.1 ⁇ m to 2.0 ⁇ m.
  • gas generation can be suppressed if Dmin is in the above range.
  • the Dmin of the present 5V class spinel is 0.1 ⁇ m to 2.0 ⁇ m, especially 0.15 ⁇ m or more and 2.0 ⁇ m or less, especially 0.2 ⁇ m or more or less than 2.0 ⁇ m. Above all, it is particularly preferable that the diameter is larger than 0.6 ⁇ m.
  • firing and pulverization may be performed, and heat treatment may be performed after the pulverization.
  • heat treatment may be performed after the pulverization.
  • the average primary particle size of the present 5V class spinel that is, the average primary particle size calculated from the SEM image is preferably 0.3 to 6.0 ⁇ m.
  • the primary particle diameter of the 5V-class spinel is preferably 0.3 ⁇ m to 6.0 ⁇ m, more preferably 0.7 ⁇ m or more or 5.5 ⁇ m or less, and particularly preferably 1.0 ⁇ m or more or 5.0 ⁇ m or less. Furthermore, it is especially preferable that it is less than 4.5 micrometers among them.
  • the ratio of the average primary particle diameter to the D50 is preferably 0.20 to 0.99.
  • the average primary particle diameter / D50 is preferably 0.20 to 0.99.
  • the dispersibility of the primary particles can be enhanced. Therefore, compared with the case where a secondary particle occupies half or more of a particle size distribution, each primary particle can fully contact with electrolyte solution. Thereby, while the reaction area of Li and particle
  • the primary particle size / D50 of the present 5V class spinel is preferably 0.20 to 0.99, more preferably 0.21 or more and 0.98 or less, and especially 0.22 or more or 0.97. The following is even more preferable.
  • the firing temperature is adjusted, or a material that increases the reactivity during firing, such as a boron compound or a fluorine compound, is added and fired. It is preferable to manufacture this 5V class spinel. However, it is not limited to this method.
  • the crystallite size is preferably 80 nm to 490 nm.
  • the ionic conductivity in the crystallite can be increased, and the output can be increased. Further, by improving the output, it is possible to suppress the polarization during the cycle, and it is possible to suppress the discharge capacity from gradually decreasing with repeated charge and discharge at a high temperature.
  • the crystallite size of the present 5V class spinel is preferably 80 nm to 490 nm, more preferably 81 nm or more and 350 nm or less, and particularly preferably 82 nm or more or 250 nm or less.
  • crystallite means the largest group that can be regarded as a single crystal, and can be obtained by performing XRD measurement and performing Rietveld analysis.
  • the ratio of the average primary particle diameter to the crystallite size is preferably 0.01 to 0.32.
  • the crystallite size / average primary particle diameter is less than 1, and within the above range, the dispersibility of primary particles in the powder is good.
  • the contact area between the primary particles and the electrolyte increases, and the resistance at the interface between the primary particles in the secondary particles can be reduced, leading to improved output characteristics.
  • the crystallite size / average primary particle diameter is preferably 0.01 to 0.32, of which 0.011 or more and 0.22 or less, of which 0.012 is particularly preferred. It is particularly preferable that the value is 0.11 or less.
  • the numerical value of the strain obtained by Rietveld analysis is 0.00 to 0.35 in the line diffraction pattern measured by the powder X-ray diffraction device (XRD). If the strain is small to this extent, the skeleton of the spinel type lithium transition metal oxide is sufficiently strong, and when used as a positive electrode active material of a lithium secondary battery, output characteristics and cycle life characteristics can be further enhanced. . From this point of view, the strain of this 5V class spinel is preferably 0.00 to 0.35, more preferably 0.30 or less, of which 0.25 or less, and even more preferably 0.20 or less. preferable.
  • heat treatment may be performed under preferable conditions. However, it is not limited to these methods.
  • the specific surface area of the 5V class spinel is preferably 0.4 to 6.0 m 2 / g from the viewpoint of reactivity with the electrolyte, and more preferably 0.5 m 2 / g or more or 5.0 m 2 / g. More preferably, it is 4.5 m 2 / g or less, more preferably 4.0 m 2 / g or less, and particularly preferably 2.0 m 2 / g or less.
  • the present 5V class spinel has a peak between 2 ⁇ and 14.0 to 16.5 °. .
  • 2 ⁇ is 14.0 to 16.5 in the X-ray diffraction pattern of a 5V class spinel containing Li, Mn and O and two or more elements other than these.
  • Whether or not there is a peak between 2 ⁇ and 14.0 to 16.5 ° is the average value of cps of 14.0 to 14.5 ° and 16.0 to 16.5 ° in the XRD pattern. Is the intensity A of the background (BG) and the maximum value of cps from 14.5 ° to 16.0 ° is the peak intensity B, and if the difference (BA) is 25 cps or more, the peak is It can be determined that it exists. Since it is considered that the effect of the present invention can be enjoyed as the difference is larger, it is preferably 30 cps or more, more preferably 40 cps or more, and further preferably 50 cps or more.
  • This 5V-class spinel is further present in the X-ray diffraction pattern in which 2 ⁇ is between 14.0 and 16.5 ° with respect to the peak intensity of the highest peak among 2 ⁇ between 18 and 19 °.
  • the peak intensity ratio of the highest peak (P14-P16 ° / P18-19 °) is preferably greater than 0.05%, more preferably 0.05% or more or 2.0% or less. More preferably, 0.05% or more or 1.5% or less is even more preferable.
  • a 5V-class spinel-type lithium manganese-containing composite oxide is used as an object to be processed. It is preferable to perform the pressure heat treatment (pressure heat treatment after pulverization). However, it is not limited to this method.
  • This 5V class spinel is made of titanium (Ti) or aluminum (Al) on a part of the surface of the present 5V class spinel particles (primary particles or secondary particles), that is, lithium manganese composite oxide particles (also referred to as “core particles”).
  • core particles lithium manganese composite oxide particles
  • Zr zirconium
  • the A layer may further contain phosphorus (P).
  • P phosphorus
  • Examples of the A layer containing phosphorus (P) include an A layer containing Ti and P, an A layer containing Al and P, an A layer containing Zr and P, and an A layer containing Ti, Al, and P.
  • the A layer may contain other elements in addition to Ti, Al, Zr, and P.
  • the A layer may partially exist on the surface of the core particle, and there may be a portion where the A layer does not exist.
  • side reaction between the core particle and the electrolytic solution can be suppressed, and both improvement in rate characteristics and suppression of gas generation can be achieved.
  • another layer may be interposed between the core particle surface and the A layer.
  • a layer containing an oxide of titanium may be interposed.
  • another layer may be present on the surface side of the A layer.
  • the thickness of the layer A is preferably from 0.01 nm to 200 nm, from the viewpoint of improving the rate characteristics and enhancing the gas generation suppressing effect, and more preferably 0.1 nm or more and 190 nm or less, and more preferably 0.1 nm or more or 180 nm or less. Is preferred.
  • Such an A layer can be formed, for example, by surface-treating the core particles.
  • a coupling agent material containing titanium (Ti), aluminum (Al), zirconium (Zr) or two or more of these, 300 ° C. or higher, preferably higher than 300 ° C.
  • It can be formed by heat treatment at 820 ° C. or lower, preferably higher than 500 ° C. or 800 ° C. or lower, more preferably 600 ° C. or higher or lower than 800 ° C.
  • ⁇ Method for producing the present 5V-class spinel> As an example of the manufacturing method of this 5V class spinel, the manufacturing method provided with the raw material mixing process, the wet grinding process, the granulation process, the baking process, the heat processing process, the washing
  • the raw material for producing the spinel-type lithium manganese-containing composite oxide represented by O 4 ⁇ ] include a lithium raw material, a nickel raw material, a manganese raw material, an M metal raw material, and other examples such as a boron raw material.
  • lithium raw material examples include lithium hydroxide (LiOH, LiOH.H 2 O), lithium carbonate (Li 2 CO 3 ), lithium nitrate (LiNO 3 ), lithium oxide (Li 2 O), other fatty acid lithium and lithium halide. Etc.
  • Examples of the manganese raw material include manganese carbonate, manganese nitrate, manganese chloride, manganese dioxide, dimanganese trioxide, and trimanganese tetraoxide. Among these, manganese carbonate and manganese dioxide are preferable. Among these, electrolytic manganese dioxide obtained by an electrolytic method is particularly preferable.
  • Examples of the M1 metal raw material, M2 metal raw material and M metal raw material include carbonates, nitrates, chlorides, oxyhydroxides, hydroxides and oxides of M metal.
  • a boron compound can also be mix
  • any compound containing boron (B element) may be used.
  • boric acid or lithium borate is preferably used.
  • lithium borate include lithium metaborate (LiBO 2 ), lithium tetraborate (Li 2 B 4 O 7 ), lithium pentaborate (LiB 5 O 8 ), and lithium perborate (Li 2 B 2 O 5 ).
  • the composite oxide phase containing Ni, Mn and B for example, a crystal phase of Ni 5 MnO 4 (BO 3 ) 2 may be generated in addition to the crystal phase of the present 5V class spinel. is there.
  • the mixing of raw materials is not particularly limited as long as the raw materials can be mixed uniformly.
  • each raw material may be added simultaneously or in an appropriate order using a known mixer such as a mixer, and mixed by stirring in a wet or dry manner to obtain a raw material mixed powder.
  • a known mixer such as a mixer
  • wet mixing examples include a mixing method using a precision mixer that rotates the raw material mixed powder at a high speed.
  • examples of the wet mixing include a method in which the raw material mixed powder is added to a liquid medium such as water or a dispersant and wet mixed to form a slurry.
  • the raw material may be put into a liquid medium such as water and pulverized. It can be wet pulverized before mixing the raw materials, or can be wet pulverized after mixing the raw materials.
  • a liquid medium such as water or a dispersant and wet-mix to make a slurry as described above, and then grind the resulting slurry with a wet-grinding machine do it. At this time, it is particularly preferable to grind to submicron order.
  • the respective raw materials may be wet pulverized and mixed, and then further wet pulverized as necessary.
  • the nickel compound alone or, if necessary, the nickel compound and the manganese compound are pulverized and classified so that the maximum particle size (Dmax) of the nickel compound or the manganese compound is 10 ⁇ m or less, particularly 5 ⁇ m or less, and more preferably 4 ⁇ m or less. It is preferable to adjust to.
  • the raw materials mixed as described above are preferably baked after being granulated to a predetermined size as required.
  • granulation is not necessarily required.
  • the granulation method may be either wet or dry as long as the various raw materials pulverized in the previous step are dispersed in the granulated particles.
  • wet granulation it is necessary to sufficiently dry before firing.
  • the drying method it may be dried by a known drying method such as a spray heat drying method, a hot air drying method, a vacuum drying method, a freeze drying method, etc.
  • the spray heat drying method is preferable.
  • the spray heat drying method is preferably performed using a heat spray dryer (spray dryer).
  • a thermal spray dryer spray dryer
  • the particle size distribution can be made sharper, and the secondary particles can be aggregated (secondary particles) to contain agglomerated particles (secondary particles).
  • Forms can be prepared.
  • Firing is performed at a temperature higher than 750 ° C. and lower than or equal to 1000 ° C., particularly 800 to 1000 ° C. in a firing furnace in an air atmosphere, an atmosphere adjusted for oxygen partial pressure, a carbon dioxide gas atmosphere, or other atmosphere. It is preferable to perform the firing so as to hold for 0.5 hours to 300 hours in (: means the temperature when a thermocouple is brought into contact with the fired product in the firing furnace). At this time, it is preferable to select firing conditions in which the transition metal is solid-solved at the atomic level and exhibits a single phase.
  • the firing temperature is higher than 750 ° C., preferably 800 ° C. or higher, and more preferably 840 ° C. or higher. However, if the firing temperature is too high, oxygen vacancies increase and the strain cannot be recovered even by heat treatment. Therefore, firing is preferably performed at 1000 ° C. or less, particularly 980 ° C. or less.
  • the firing temperature means the product temperature of the fired product measured by bringing a thermocouple into contact with the fired product in the firing furnace.
  • the firing time that is, the time for maintaining the firing temperature may be 0.5 to 100 hours, although it depends on the firing temperature.
  • the type of firing furnace is not particularly limited. For example, it can be fired using a rotary kiln, a stationary furnace, or other firing furnace.
  • the firing temperature is preferably higher than 750 ° C., more preferably 800 ° C. or higher, and particularly preferably 820 ° C. or higher.
  • firing is preferably performed at 980 ° C. or lower, and particularly at 960 ° C. or lower. Is more preferable.
  • firing is preferably performed at a temperature higher than 800 ° C., more preferably 820 ° C. or more, and particularly preferably firing at 840 ° C. or more.
  • firing temperature is preferably performed at 1000 ° C. or lower, and particularly at 980 ° C. or lower. Is more preferable.
  • the heat treatment is performed in an atmosphere of 500 ° C. to 800 ° C., preferably 700 ° C. or higher or 800 ° C. or lower for 0.5 to 300 hours in an air atmosphere, an atmosphere in which oxygen partial pressure is adjusted, or other atmosphere. It is preferable to facilitate the uptake of oxygen. At this time, if the temperature is lower than 700 ° C., it is difficult to obtain the effect of the heat treatment and oxygen may not be taken in. On the other hand, if the heat treatment is performed at a temperature higher than 800 ° C., the desorption of oxygen starts and the intended effect of the present invention cannot be obtained.
  • the heat treatment atmosphere may be an atmosphere in which the total pressure of the treatment atmosphere is larger than atmospheric pressure (0.1 MPa), for example, greater than 0.19 MPa, and more preferably 0.20 MPa or more. .
  • atmospheric pressure is 1.5 MPa or less, especially 1.0 MPa or less. It is preferable to heat-treat with. By performing heat treatment in such a pressurized state, it becomes easier to take in oxygen and oxygen deficiency can be further suppressed.
  • the degree of crushing is preferably such that the secondary particles are not broken. And it is preferable to classify after crushing.
  • the cleaning step it is preferable to clean the object to be processed (also referred to as “processed powder”) with a polar solvent so that impurities contained in the processed powder are released.
  • the treated powder may be mixed with a polar solvent and stirred to form a slurry, and the resulting slurry may be solid-liquid separated by filtration or the like to remove impurities. At this time, solid-liquid separation may be performed in a later step.
  • the slurry means a state in which the treated powder is dispersed in a polar solvent.
  • water is preferably used as a polar solvent used for washing.
  • the water may be city water, but is preferably ion-exchanged water or pure water that has been passed through a filter or a wet magnetic separator.
  • the pH of water is preferably 4 to 10, and more preferably 5 or more and 9 or less.
  • the battery characteristics become better if the liquid temperature at the time of washing is low. From this viewpoint, it is preferably 5 to 70 ° C., and more preferably 60 ° C. or less. It is even more preferable that the temperature is 45 ° C. or less. In particular, the temperature is 40 ° C. or lower. Furthermore, it is even more preferable that the temperature is 30 ° C. or less.
  • the reason why the battery characteristics are better if the liquid temperature during washing is low is that if the liquid temperature is too high, lithium in the lithium manganese-containing composite oxide is ion-exchanged with protons of ion-exchanged water and the lithium is released, resulting in a high temperature. It can be estimated that this is because it affects the characteristics.
  • the amount of the polar solvent brought into contact with the object to be treated (treated powder) is adjusted so that the mass ratio (also referred to as “slurry concentration”) of the lithium manganese-containing composite oxide to the polar solvent is 10 to 70 wt%.
  • the mass ratio (also referred to as “slurry concentration”) of the lithium manganese-containing composite oxide to the polar solvent is 10 to 70 wt%.
  • the amount of the polar solvent is 10 wt% or more, it is easy to elute impurities such as SO 4 , and conversely if it is 60 wt% or less, a cleaning effect corresponding to the amount of the polar solvent can be obtained.
  • the supernatant may be removed by adding it to the washing liquid and stirring it, and then allowing it to stand.
  • the spinel-type lithium manganese-containing composite oxide is preferably added to the cleaning liquid, stirred for 20 minutes, and then allowed to stand for 10 minutes to remove the spinel-type lithium manganese-containing composite oxide contained in the supernatant.
  • the impurity amount of the spinel type lithium manganese-containing composite oxide for example, the sulfur content can be reduced.
  • pulverization is preferably performed using an airflow pulverizer or a collision pulverizer with a classification mechanism, such as a jet mill or a counter jet mill with a classification rotor. If it is pulverized by a jet mill, it is possible to pulverize a portion where aggregation between primary particles or weak sintering occurs.
  • a pulverizer such as a pin mill or a planetary ball mill can also be used.
  • An example of a jet mill is a counter jet mill with a classification rotor.
  • the counter jet mill is known as a pulverizer using a collision of compressed gas flow.
  • the raw material fed into the mill from the raw material hopper is fluidized by the jet air from the nozzle.
  • the number of revolutions of the classifier of the counter jet mill is 7000 rpm or more, more preferably 8000 rpm or more or 18000 rpm or less, and particularly preferably 9000 rpm or more or 18000 rpm or less.
  • heat treatment may be performed in an oxygen-containing atmosphere as necessary.
  • oxygen-containing atmosphere By performing a heat treatment in an oxygen-containing atmosphere after the pulverization step, oxygen can be taken into the structure, and distortion caused by pulverization can be reduced.
  • the entire pressure of the treatment atmosphere is atmospheric pressure or higher than atmospheric pressure, and the oxygen partial pressure in the atmosphere is higher than the oxygen partial pressure in the atmosphere.
  • the heat treatment is preferably performed at a temperature higher than 500 ° C. and lower than 850 ° C.
  • oxygen is incorporated into the structure of the present 5V spinel, oxygen deficiency is reduced, and the structure is stabilized.
  • distortion in the structure can be removed, and output and cycle characteristics can be improved.
  • the pressure atmosphere higher than the atmospheric pressure includes a case where the pressure rises to a pressure higher than the atmospheric pressure by heating the inside of the sealed container and raising the temperature of the gas in a certain volume.
  • the total pressure of the atmosphere is higher than the atmospheric pressure (0.1 MPa), for example, greater than 0.19 MPa, and in particular, the pressure of the atmosphere of 0.20 MPa or more. Is particularly preferred.
  • the atmospheric pressure is 1.5 MPa or less, especially 1.0 MPa or less. It is preferable to heat-treat with. Thus, by heat-treating in an oxygen-containing atmospheric pressure state, it becomes easier to take in oxygen, and oxygen vacancies can be further suppressed.
  • the total pressure of the atmosphere during the oxygen-containing atmosphere pressure heat treatment is preferably controlled to be greater than 0.19 MPa and not more than 1.5 MPa, more preferably not less than 0.20 MPa or not more than 1.3 MPa, and more preferably 1.0 MPa.
  • the following control is preferable.
  • the atmosphere in an atmosphere having a pressure higher than atmospheric pressure preferably has an oxygen partial pressure higher than, for example, 0.19 MPa, and particularly preferably has an oxygen partial pressure of 0.20 MPa or higher.
  • the oxygen partial pressure is 1.5 MPa or less, particularly 1.0 MPa or less. It is preferable to heat-treat with.
  • the oxygen partial pressure in the oxygen-containing atmosphere heat treatment step after pulverization is preferably controlled to be greater than 0.19 MPa and 1.5 MPa, more preferably 0.20 MPa or more or 1.3 MPa or less, and particularly 1.0 MPa or less. It is preferable to control.
  • the heat treatment temperature in the oxygen-containing atmosphere heat treatment step after pulverization is preferably controlled to a temperature higher than 500 ° C. and lower than 850 ° C. If the heat treatment temperature in this step is higher than 500 ° C., the oxygen can be taken into the crystal structure and strain can be effectively reduced by performing the heat treatment while forcibly supplying oxygen. From this viewpoint, the heat treatment temperature is preferably higher than 500 ° C., more preferably 600 ° C. or higher, particularly 700 ° C. or higher, and particularly preferably higher than 700 ° C. On the other hand, if the heat treatment temperature is too high, oxygen vacancies may increase and strain may not be recovered even by heat treatment.
  • the heat treatment temperature is preferably lower than 850 ° C., and particularly 820 ° C. or less. Among them, the temperature is particularly preferably 800 ° C. or lower.
  • this heat processing temperature means the product temperature of the processed material measured by making a thermocouple contact the processed material in a furnace.
  • the overall pressure of the treatment atmosphere is a pressure higher than atmospheric pressure and an oxygen partial pressure higher than 0.19 MPa, higher than 500 ° C. and higher than 850 ° C.
  • the conditions include oxygen-containing atmosphere pressure heat treatment at a low temperature, in particular, 600 ° C. or higher or lower than 850 ° C., among them a temperature higher than 700 ° C. or 800 ° C. or lower.
  • the heating rate at the time of heating to the above heat treatment temperature, that is, the holding temperature is preferably 0.1 ° C./min to 20 ° C./min, particularly 0.25 ° C./min or more or 10 ° C./min or less, In particular, it is more preferably 0.5 ° C./min or more or 5 ° C./min or less.
  • the time for maintaining the heat treatment temperature needs to be at least 1 minute. In order to fully incorporate oxygen into the crystal structure, at least one minute is considered necessary. From this viewpoint, the time for maintaining the heat treatment temperature is preferably 5 minutes or more, particularly preferably 10 minutes or more. In addition, it is considered that the effect of incorporating oxygen into the crystal structure by heat treatment is sufficiently effective when the holding time is 200 hours or less.
  • the temperature lowering rate after the heat treatment is preferably slow cooling at a cooling rate of 10 ° C./min or less to at least 500 ° C., particularly 0.1 ° C./min to 8 ° C./min, especially 0.2 ° C./min to More preferably, it is controlled to 5 ° C./min. Since oxygen taken in around 500 ° C. is considered to be stabilized, it can be considered that it is preferable to cool slowly at a rate of temperature decrease of 10 ° C./min or less until at least 500 ° C.
  • the heat treatment in the post-grinding oxygen-containing atmosphere heat treatment step is performed using a device such as a pressurizing furnace (pressurizable pressure 1.0 MPa), so that the overall pressure of the treatment atmosphere is higher than atmospheric pressure. Heating can be performed in a treatment atmosphere having a pressure and an oxygen partial pressure in the atmosphere higher than the oxygen partial pressure in the atmosphere.
  • a pressurizing furnace pressurizable pressure 1.0 MPa
  • a layer formation process Surface treatment of titanium coupling agent, aluminum coupling agent, zirconium coupling agent, titanium / aluminum coupling agent, aluminum / zirconium coupling agent, etc. for the present 5V class spinel (powder) obtained as described above.
  • the A layer can be formed by mixing the agent with an organic solvent, performing a surface treatment, drying to volatilize the organic solvent, and then performing a heat treatment at 300 ° C. or higher.
  • formation of A layer may be performed after the crushing process after heat processing, may be performed after a crushing process, and may be performed after a water washing process.
  • the coupling agent may be a compound having an organic functional group and a hydrolyzable group in the molecule, and among them, a compound having phosphorus (P) in the side chain is preferable. Since the coupling agent having phosphorus (P) in the side chain has better compatibility with the binder, it has excellent binding properties with the binder.
  • heating is preferably performed at 300 ° C. or higher, preferably higher than 300 ° C. or 820 ° C. or lower, preferably higher than 500 ° C. or 800 ° C. or lower, more preferably 600 ° C. or higher or lower than 800 ° C.
  • 300 ° C. or higher the amount of carbon in the A layer can be reduced and the A layer can be oxidized.
  • the rate characteristics and life characteristics can be further improved. There is.
  • the heat treatment after drying is preferably performed in an oxygen-existing atmosphere. This is because heat treatment after drying removes the side chain of the organic solvent and the coupling agent, and oxygen in the active material may also escape. It is because it is preferable to replenish. From such a viewpoint, it is preferable to perform in an air atmosphere or an oxygen atmosphere in an oxygen-existing atmosphere.
  • the oxygen atmosphere refers to an atmosphere having a larger oxygen abundance than the air atmosphere.
  • This 5V class spinel can be effectively used as a positive electrode active material for various lithium batteries after being crushed and classified as necessary.
  • this 5V class spinel is used as a positive electrode active material for various lithium batteries, for example, this 5V class spinel, a conductive material made of carbon black or the like, and a binder made of Teflon (registered trademark) binder or the like are mixed. Thus, a positive electrode mixture can be produced.
  • Such a positive electrode mixture is used for the positive electrode, a material that can occlude and desorb lithium such as lithium or carbon is used for the negative electrode, and a lithium salt such as lithium hexafluorophosphate (LiPF 6 ) is used for the non-aqueous electrolyte.
  • a lithium battery can be formed by using a material in which is dissolved in a mixed solvent such as ethylene carbonate-dimethyl carbonate.
  • Lithium batteries configured in this way include, for example, notebook computers, mobile phones, cordless phones, video movies, LCD TVs, electric shavers, portable radios, headphone stereos, backup power supplies, memory cards, and other electronic devices, pacemakers, hearing aids It can be used as a drive power source for medical equipment such as electric vehicles.
  • mobile phones that require excellent cycle characteristics
  • portable computers such as PDAs (personal digital assistants) and notebook computers
  • electric vehicles including hybrid vehicles
  • power sources for driving power storage etc. It is valid.
  • Example 1 Lithium carbonate having an average particle size (D50) of 7 ⁇ m, electrolytic manganese dioxide having an average particle size (D50) of 23 ⁇ m and a specific surface area of 40 m 2 / g, nickel hydroxide having an average particle size (D50) of 22 ⁇ m, an average particle size ( D50) 2 ⁇ m of titanium oxide and 60 ⁇ m of average particle diameter (D50) lithium tetraborate were weighed.
  • An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • the added amount of the dispersant was 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material and B raw material, and was sufficiently dissolved and mixed in ion-exchanged water. Then, the weighed Ni and Mn raw materials are added to the ion-exchanged water in which the dispersant is dissolved in advance, mixed and stirred, and then pulverized with a wet pulverizer at 1300 rpm for 120 minutes to obtain an average particle diameter. A pulverized slurry having (D50) of 0.60 ⁇ m or less was obtained.
  • the remaining raw materials were added to the slurry, stirred, and then pulverized at 1300 rpm for 120 minutes to obtain a pulverized slurry having an average particle size (D50) of 0.60 ⁇ m or less.
  • the solid content concentration at this time was 40 wt%.
  • the obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Chemical Co., Ltd.). At this time, a twin jet nozzle was used for spraying, granulation drying was performed by adjusting the temperature so that the spray pressure was 0.46 MPa, the slurry supply amount was 340 ml / min, and the inlet temperature of the drying tower was 200 to 280 ° C. .
  • the obtained granulated powder was baked in an atmospheric atmosphere using a stationary electric furnace so as to maintain 880 ° C. for 37 hours, and then pulverized (Orient solid pulverizer, manufactured by Orient Crusher Co., Ltd.). It was crushed.
  • heat treatment first heat treatment
  • a static electric furnace so that the temperature is maintained at 750 ° C. for 37 hours in an air atmosphere
  • a crusher Orient Solid Crusher, manufactured by Orient Crusher Co., Ltd.
  • the mixture was put into a plastic beaker (capacity 5000 mL) containing ion exchange water 2000 mL with a pH of 6 to 7 and a temperature of 25 ° C., and a rotation of 400 to 550 rpm using a stirrer (propeller area 33 cm 2 ) for 20 minutes. Stir. After stirring, stirring was stopped and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant liquid was removed by decantation, and the precipitate was collected from the remainder using a suction filter (filter paper No. 131), and the collected precipitate was dried in a 120 ° C. environment for 12 hours. Then, it dried for 7 hours in the state heated so that product temperature might be 500 degreeC.
  • Example 2 In Example 1 above, spinel-type lithium manganese-containing composite oxide powder obtained by crushing and classifying with a counter jet mill was allowed to flow at an oxygen supply rate of 0.5 L / min in a tubular static oven. Then, the furnace set temperature was set to 725 ° C., and heat treatment (second heat treatment) was performed so as to be held for 5 hours. The powder after the second heat treatment was classified with a sieve having an opening of 300 ⁇ m, and the sieve was collected to obtain a spinel-type lithium manganese-containing composite oxide powder (sample).
  • Example 3 In the said Example 1, surface treatment was implemented as follows with respect to the spinel type lithium manganese containing complex oxide powder obtained by crushing and classifying with a counter jet mill. That is, 100 parts by mass of the spinel-type lithium manganese-containing composite oxide powder, 3.0 parts by mass of a zirconium coupling agent (Kenrich Petrochemicals Ken-React (registered trademark) NZ12) as a surface treatment agent, and a solvent 7.6 parts by mass of isopropyl alcohol was mixed using a cutter mill (Milcer 720G manufactured by Iwatani Corporation). Subsequently, the mixed spinel-type lithium manganese-containing composite oxide powder was placed in a dryer under a vacuum atmosphere at 100 ° C.
  • a zirconium coupling agent Kelrich Petrochemicals Ken-React (registered trademark) NZ12
  • the spinel lithium manganese-containing composite oxide powder thus obtained was observed with a transmission electron microscope (“JEM-ARM200F” manufactured by JEOL Ltd.) in the vicinity of the particle surface.
  • a layer (referred to as “A layer”) was partially present on the surface of the oxide core. Further, when the A layer was analyzed by EDS, it was found to contain zirconium (Zr) and phosphorus (P). Further, the thickness of the A layer was different depending on the location, and the thin part was 0.1 nm and the thick part was 30 nm.
  • Example 4 The spinel-type lithium manganese-containing composite oxide powder was changed in the same manner as in Example 3 except that the raw material composition was changed to the composition shown in Table 1, the B raw material was not used, and the counter jet mill classifier rotation speed was changed to 13000 rpm. Sample).
  • the spinel lithium manganese-containing composite oxide powder (sample) thus obtained was observed with a transmission electron microscope (“JEM-ARM200F” manufactured by JEOL Ltd.) in the vicinity of the particle surface.
  • a layer (referred to as “A layer”) partially existed on the surface of the core portion made of the manganese-containing composite oxide. Further, when the A layer was analyzed by EDS, it was found to contain zirconium (Zr) and phosphorus (P). The thickness of the A layer was different depending on the location, and the thin part was 0.1 nm and the thick part was 30 nm.
  • Example 5> instead of the second heat treatment in Example 2 above, an oxygen-containing atmosphere pressure heat treatment was performed as follows using a pressure furnace (manufactured by Hiroki Co., Ltd.). That is, in Example 1 above, 200 g of a spinel-type lithium manganese-containing composite oxide powder obtained by crushing and classifying with a counter jet mill was filled in a magnetic crucible, and this magnetic crucible was placed in a pressure furnace. installed. Thereafter, oxygen gas (oxygen concentration 99%) was introduced into the pressurizing furnace to adjust the oxygen partial pressure to 0.20 MPa and the overall pressure of the processing atmosphere to 0.21 MPa, and the temperature was increased by 1.7 ° C./min. The powder was heated to 730 ° C.
  • a pressure furnace manufactured by Hiroki Co., Ltd.
  • Example 6 surface treatment was implemented as follows with respect to the spinel type lithium manganese containing complex oxide powder obtained by crushing and classifying with a counter jet mill. That is, 100 parts by mass of the spinel-type lithium manganese-containing composite oxide powder, 3.0 parts by mass of an aluminum coupling agent (Ajino Fine Techno Co., Ltd. Preneact (registered trademark) AL-M) as a surface treatment agent, and as a solvent 7.6 parts by mass of isopropyl alcohol was mixed using a cutter mill (Milcer 720G manufactured by Iwatani Corporation). Next, the mixed spinel-type lithium manganese-containing composite oxide powder is dried in a drier at 100 ° C.
  • the spinel lithium manganese-containing composite oxide powder (sample) thus obtained was observed with a transmission electron microscope (“JEM-ARM200F” manufactured by JEOL Ltd.) in the vicinity of the particle surface.
  • a layer (referred to as “A layer”) partially existed on the surface of the core portion made of the manganese-containing composite oxide. Further, when the A layer was analyzed by EDS, it was found to contain aluminum (Al) and phosphorus (P). Further, the thickness of the A layer was different depending on the location, and the thin part was 0.1 nm and the thick part was 30 nm.
  • Example 7 Lithium carbonate having an average particle size (D50) of 7 ⁇ m, nickel hydroxide having an average particle size (D50) of 22 ⁇ m, electrolytic manganese dioxide having an average particle size (D50) of 23 ⁇ m and a specific surface area of 40 m 2 / g, and an average particle size ( D50) 2 ⁇ m titanium oxide, average particle diameter (D50) 2 ⁇ m aluminum hydroxide, average particle diameter (D50) 12 ⁇ m cobalt oxyhydroxide, and average particle diameter (D50) 60 ⁇ m lithium tetraborate each weighed did.
  • An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • the addition amount of the dispersant is 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material, Al raw material, Co raw material, and B raw material, and is sufficient in ion-exchanged water. Dissolved and mixed. Then, the weighed raw materials were added to the ion-exchanged water in which the dispersant was dissolved in advance, and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%.
  • the obtained granulated powder was baked in an atmospheric atmosphere using a stationary electric furnace so as to maintain 880 ° C. for 37 hours, and then pulverized (Orient solid pulverizer, manufactured by Orient Crusher Co., Ltd.). It was crushed. After the crushing, heat treatment (first heat treatment) is carried out using a static electric furnace so that the temperature is maintained at 740 ° C. for 37 hours in an air atmosphere, and a crusher (Orient Solid Crusher, manufactured by Orient Crusher Co., Ltd.) It was crushed at.
  • the mixture was put into a plastic beaker (capacity 5000 mL) containing ion exchange water 2000 mL with a pH of 6 to 7 and a temperature of 25 ° C., and a rotation of 400 to 550 rpm using a stirrer (propeller area 33 cm 2 ) for 20 minutes. Stir. After stirring, stirring was stopped and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant liquid was removed by decantation, and the precipitate was collected from the remainder using a suction filter (filter paper No. 131), and the collected precipitate was dried in a 120 ° C. environment for 12 hours. Then, it dried for 7 hours in the state heated so that product temperature might be 500 degreeC.
  • Example 8 Lithium carbonate having an average particle size (D50) of 7 ⁇ m, nickel hydroxide having an average particle size (D50) of 22 ⁇ m, electrolytic manganese dioxide having an average particle size (D50) of 23 ⁇ m and a specific surface area of 40 m 2 / g, and an average particle size ( D50) 2 ⁇ m titanium oxide, average particle diameter (D50) 2 ⁇ m aluminum hydroxide, and average particle diameter (D50) 60 ⁇ m lithium tetraborate were weighed. An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • SN Dispersant 5468 manufactured by San Nopco Co., Ltd.
  • the added amount of the dispersant is 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material, Al raw material and B raw material, and is sufficiently dissolved and mixed in ion-exchanged water.
  • the weighed raw materials were added to the ion-exchanged water in which the dispersant was dissolved in advance, and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%. Then, it grind
  • the obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Chemical Co., Ltd.). At this time, a twin jet nozzle was used for spraying, and granulation drying was performed by adjusting the temperature so that the spray pressure was 0.44 MPa, the slurry supply amount was 320 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C. .
  • a thermal spray dryer spray dryer, “RL-10” manufactured by Okawara Chemical Co., Ltd.
  • the obtained granulated powder was baked in an atmospheric atmosphere using a stationary electric furnace so as to maintain 880 ° C. for 37 hours, and then pulverized (Orient solid pulverizer, manufactured by Orient Crusher Co., Ltd.). It was crushed. After the crushing, heat treatment (first heat treatment) is carried out using a static electric furnace so that the temperature is maintained at 740 ° C. for 37 hours in an air atmosphere, and a crusher (Orient Solid Crusher, manufactured by Orient Crusher Co., Ltd.) It was crushed at.
  • the mixture was put into a plastic beaker (capacity 5000 mL) containing ion exchange water 2000 mL with a pH of 6 to 7 and a temperature of 25 ° C., and a rotation of 400 to 550 rpm using a stirrer (propeller area 33 cm 2 ) for 20 minutes. Stir. After stirring, stirring was stopped and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant liquid was removed by decantation, and the precipitate was collected from the remainder using a suction filter (filter paper No. 131), and the collected precipitate was dried in a 120 ° C. environment for 12 hours. Then, it dried for 7 hours in the state heated so that product temperature might be 500 degreeC.
  • Example 9 Lithium carbonate having an average particle size (D50) of 7 ⁇ m, nickel hydroxide having an average particle size (D50) of 22 ⁇ m, electrolytic manganese dioxide having an average particle size (D50) of 23 ⁇ m and a specific surface area of 40 m 2 / g, and an average particle size ( D50) 2 ⁇ m of titanium oxide and 60 ⁇ m of average particle diameter (D50) lithium tetraborate were weighed. An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • SN Dispersant 5468 manufactured by San Nopco Co., Ltd.
  • the added amount of the dispersant was 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material and B raw material, and was sufficiently dissolved and mixed in ion-exchanged water. Then, the weighed raw materials were added to the ion-exchanged water in which the dispersant was dissolved in advance, and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%. Then, it grind
  • the obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Chemical Co., Ltd.). At this time, a twin jet nozzle was used for spraying, granulation drying was performed by adjusting the temperature so that the spray pressure was 0.45 MPa, the slurry supply amount was 310 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C. .
  • a thermal spray dryer spray dryer, “RL-10” manufactured by Okawara Chemical Co., Ltd.
  • the obtained granulated powder was baked in an atmospheric atmosphere using a stationary electric furnace so as to maintain 880 ° C. for 37 hours, and then pulverized (Orient solid pulverizer, manufactured by Orient Crusher Co., Ltd.). It was crushed. After the crushing, heat treatment (first heat treatment) is carried out using a static electric furnace so that the temperature is maintained at 740 ° C. for 37 hours in an air atmosphere, and a crusher (Orient Solid Crusher, manufactured by Orient Crusher Co., Ltd.) It was crushed at.
  • the mixture was put into a plastic beaker (capacity 5000 mL) containing ion exchange water 2000 mL with a pH of 6 to 7 and a temperature of 25 ° C., and a rotation of 400 to 550 rpm using a stirrer (propeller area 33 cm 2 ) for 20 minutes. Stir. After stirring, stirring was stopped and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant liquid was removed by decantation, and the precipitate was collected from the remainder using a suction filter (filter paper No. 131), and the collected precipitate was dried in a 120 ° C. environment for 12 hours. Then, it dried for 7 hours in the state heated so that product temperature might be 500 degreeC.
  • Example 10 Lithium carbonate having an average particle size (D50) of 7 ⁇ m, nickel hydroxide having an average particle size (D50) of 22 ⁇ m, electrolytic manganese dioxide having an average particle size (D50) of 23 ⁇ m and a specific surface area of 40 m 2 / g, and an average particle size ( D50) 2 ⁇ m of titanium oxide and aluminum hydroxide having an average particle diameter (D50) of 2 ⁇ m were weighed.
  • An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • the added amount of the dispersant was 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material and Al raw material, and was sufficiently dissolved and mixed in ion-exchanged water.
  • the weighed raw materials only the Ni raw material, the Mn raw material, and the Al raw material were added to the ion-exchanged water in which the dispersant was dissolved in advance, and mixed and stirred to obtain a slurry.
  • the obtained slurry was pulverized with a wet pulverizer at 1300 rpm for 120 minutes.
  • a Li raw material and a Ti raw material were added, mixed and stirred, and a slurry with a solid content concentration of 40 wt% was prepared.
  • the mixture was further pulverized with a wet pulverizer at 1300 rpm for 120 minutes to obtain a pulverized slurry having an average particle size (D50) of 0.44 ⁇ m or less.
  • the obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Chemical Co., Ltd.).
  • a twin jet nozzle was used for spraying, granulation drying was performed by adjusting the temperature so that the spray pressure was 0.43 MPa, the slurry supply amount was 320 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C. .
  • the obtained granulated powder was baked in an atmospheric atmosphere using a stationary electric furnace so as to maintain 880 ° C. for 37 hours, and then pulverized (Orient solid pulverizer, manufactured by Orient Crusher Co., Ltd.). It was crushed. After the crushing, heat treatment (first heat treatment) is carried out using a static electric furnace so that the temperature is maintained at 740 ° C. for 37 hours in an air atmosphere, and a crusher (Orient Solid Crusher, manufactured by Orient Crusher Co., Ltd.) It was crushed at.
  • the mixture was put into a plastic beaker (capacity 5000 mL) containing ion exchange water 2000 mL with a pH of 6 to 7 and a temperature of 25 ° C., and a rotation of 400 to 550 rpm using a stirrer (propeller area 33 cm 2 ) for 20 minutes. Stir. After stirring, stirring was stopped and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant liquid was removed by decantation, and the precipitate was collected from the remainder using a suction filter (filter paper No. 131), and the collected precipitate was dried in a 120 ° C. environment for 12 hours. Then, it dried for 7 hours in the state heated so that product temperature might be 500 degreeC.
  • Example 11 Lithium carbonate having an average particle size (D50) of 7 ⁇ m, nickel hydroxide having an average particle size (D50) of 22 ⁇ m, electrolytic manganese dioxide having an average particle size (D50) of 23 ⁇ m and a specific surface area of 40 m 2 / g, and an average particle size ( D50) 2 ⁇ m of titanium oxide and aluminum hydroxide having an average particle diameter (D50) of 2 ⁇ m were weighed.
  • An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • the added amount of the dispersant was 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material and Al raw material, and was sufficiently dissolved and mixed in ion-exchanged water.
  • the weighed raw materials only the Ni raw material, the Mn raw material, and the Al raw material were added to the ion-exchanged water in which the dispersant was dissolved in advance, and mixed and stirred to obtain a slurry.
  • the obtained slurry was pulverized with a wet pulverizer at 1300 rpm for 120 minutes.
  • a Li raw material and a Ti raw material were added, mixed and stirred, and a slurry with a solid content concentration of 40 wt% was prepared.
  • the mixture was further pulverized with a wet pulverizer at 1300 rpm for 120 minutes to obtain a pulverized slurry having an average particle size (D50) of 0.44 ⁇ m or less.
  • the obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Chemical Co., Ltd.).
  • a twin jet nozzle was used for spraying, granulation drying was performed by adjusting the temperature so that the spray pressure was 0.46 MPa, the slurry supply amount was 310 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C. .
  • the obtained granulated powder was baked in an atmospheric atmosphere using a stationary electric furnace so as to maintain 880 ° C. for 37 hours, and then pulverized (Orient solid pulverizer, manufactured by Orient Crusher Co., Ltd.). It was crushed. After the crushing, heat treatment (first heat treatment) is carried out using a static electric furnace so that the temperature is maintained at 740 ° C. for 37 hours in an air atmosphere, and a crusher (Orient Solid Crusher, manufactured by Orient Crusher Co., Ltd.) It was crushed at.
  • the mixture was put into a plastic beaker (capacity 5000 mL) containing ion exchange water 2000 mL with a pH of 6 to 7 and a temperature of 25 ° C., and a rotation of 400 to 550 rpm using a stirrer (propeller area 33 cm 2 ) for 20 minutes. Stir. After stirring, stirring was stopped and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant liquid was removed by decantation, and the precipitate was collected from the remainder using a suction filter (filter paper No. 131), and the collected precipitate was dried in a 120 ° C. environment for 12 hours. Then, it dried for 7 hours in the state heated so that product temperature might be 500 degreeC.
  • the obtained spinel-type lithium manganese-containing composite oxide powder was subjected to a heat treatment (second heat treatment) so as to be kept at 720 ° C. in an oxygen atmosphere in a stationary furnace for 5 hours.
  • the powder after the second heat treatment was classified with a sieve having an opening of 300 ⁇ m, and the sieve was collected to obtain a spinel-type lithium manganese-containing composite oxide powder (sample).
  • Example 12 Lithium carbonate having an average particle size (D50) of 7 ⁇ m, nickel hydroxide having an average particle size (D50) of 22 ⁇ m, electrolytic manganese dioxide having an average particle size (D50) of 23 ⁇ m and a specific surface area of 40 m 2 / g, and an average particle size ( D50) 2 ⁇ m of titanium oxide and aluminum hydroxide having an average particle diameter (D50) of 2 ⁇ m were weighed.
  • An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • the added amount of the dispersant was 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, Mn raw material, Ti raw material and Al raw material, and was sufficiently dissolved and mixed in ion-exchanged water.
  • the weighed raw materials only the Ni raw material, the Mn raw material, and the Al raw material were added to the ion-exchanged water in which the dispersant was dissolved in advance, and mixed and stirred to obtain a slurry.
  • the obtained slurry was pulverized with a wet pulverizer at 1300 rpm for 120 minutes.
  • a Li raw material and a Ti raw material were added, mixed and stirred, and a slurry with a solid content concentration of 40 wt% was prepared.
  • the mixture was further pulverized with a wet pulverizer at 1300 rpm for 120 minutes to obtain a pulverized slurry having an average particle diameter (D50) of 0.43 ⁇ m or less.
  • the obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, “RL-10” manufactured by Okawara Chemical Co., Ltd.).
  • a twin jet nozzle was used for spraying, and granulation drying was performed by adjusting the temperature so that the spray pressure was 0.45 MPa, the slurry supply amount was 320 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C. .
  • the obtained granulated powder was baked in an air atmosphere so as to maintain 870 ° C. for 37 hours using a stationary electric furnace, and then pulverized (Orient solid pulverizer, manufactured by Orient Crusher Co., Ltd.). It was crushed. After the crushing, heat treatment (first heat treatment) is carried out using a static electric furnace so that the temperature is maintained at 740 ° C. for 37 hours in an air atmosphere, and a crusher (Orient Solid Crusher, manufactured by Orient Crusher Co., Ltd.) It was crushed at.
  • the mixture was put into a plastic beaker (capacity 5000 mL) containing ion exchange water 2000 mL with a pH of 6 to 7 and a temperature of 25 ° C., and a rotation of 400 to 550 rpm using a stirrer (propeller area 33 cm 2 ) for 20 minutes. Stir. After stirring, stirring was stopped and the stirrer was taken out of the water and allowed to stand for 10 minutes. Then, the supernatant liquid was removed by decantation, and the precipitate was collected from the remainder using a suction filter (filter paper No. 131), and the collected precipitate was dried in a 120 ° C. environment for 12 hours. Then, it dried for 7 hours in the state heated so that product temperature might be 500 degreeC.
  • Example 1 After pulverizing by heat treatment (first heat treatment), pulverization was further performed using a pin mill (Ixed Mill, manufactured by Hadano Sangyo Co., Ltd.), and the obtained powder was pH 6-7, temperature 25 ° C. Was put into a plastic beaker (capacity 5000 mL) containing 2000 mL of ion-exchanged water and stirred for 20 minutes at a rotation of 400 to 550 rpm using a stirrer (propeller area 33 cm 2 ). After stirring, stirring was stopped and the stirrer was taken out of the water and allowed to stand for 10 minutes.
  • a pin mill Ixed Mill, manufactured by Hadano Sangyo Co., Ltd.
  • Example 2 ⁇ Comparative Example 2>
  • the B raw material was not used, the calcination temperature was changed to 740 ° C. and calcination, followed by pulverization with a crusher (Orient solid pulverizer, manufactured by Orient Crusher Co., Ltd.), and a sieve having an opening of 53 ⁇ m.
  • a crusher Orient solid pulverizer, manufactured by Orient Crusher Co., Ltd.
  • a sieve having an opening of 53 ⁇ m To obtain a spinel-type lithium manganese-containing composite oxide powder (sample).
  • the number of times of ultrasonic irradiation was the number of times until the D50 change rate before and after ultrasonic irradiation became 8% or less.
  • the water-soluble solvent used in the measurement was passed through a 60 ⁇ m filter, the solvent refractive index was 1.33, the particle permeability was transmissive, the particle refractive index was 2.46, the shape was non-spherical, and the measurement range was 0.133. ⁇ 704.0 ⁇ m, the measurement time was 30 seconds, and the average value measured twice was defined as each value.
  • the primary particle diameter of the spinel type lithium manganese-containing composite oxide powder (sample) obtained in Examples and Comparative Examples was measured as follows. Using a SEM (scanning electron microscope), the sample (powder) was observed at 1000 times, and particles having a size corresponding to D50 were selected. Next, in accordance with D50, the image was taken with the magnification changed from 2000 to 10,000 times. For example, when the D50 is about 7 ⁇ m, when the D50 is about 10,000 ⁇ m, when the D50 is about 15 ⁇ m, the magnification is 5000 times, and when the D50 is about 22 ⁇ m, the magnification is 2000 times. Can be taken.
  • the primary particle diameter of the selected particles was determined for the photographed image using image analysis software (MAC-VIEW ver. 4 manufactured by Mountec Co., Ltd.). In addition, this primary particle diameter is a cumulative 50% particle diameter (Heywood diameter: equivalent circle diameter) in volume distribution. Moreover, in order to calculate a primary particle diameter, it is preferable to measure 30 or more primary particles. When the number of measurement was insufficient, particles having a size corresponding to D50 were additionally selected and photographed, and measurement was performed so that the total number of primary particles was 30 or more.
  • the XRD measurement was performed under the following measurement condition 1 using an apparatus name “Ultima IV, manufactured by Rigaku Corporation” to obtain an XRD pattern.
  • integrated powder X-ray analysis software PDXL manufactured by Rigaku Corporation
  • crystal phase information was determined for the obtained XRD pattern, refined by WPPF (Whole powder pattern fitting) method, and the lattice constant was obtained. .
  • the crystal phase information is attributed to cubic crystals of the space group Fd-3m (Origin Choice 2), Li at the 8a site, Mn, M1 element, M2 element at the 16d site, and excess Li content, 32e site.
  • the seat occupancy at each site and the atomic displacement parameter B are set to 1, and the calculation was repeated until Rwp and S representing the degree of coincidence between the observed intensity and the calculated intensity converged.
  • the fact that the observed intensity and the calculated intensity are in good agreement means that the obtained sample is not limited to the space group and has a high reliability with a spinel crystal structure.
  • XRD measurement condition 1 Radiation source: CuK ⁇ (line focal point), wavelength: 1.541836 ⁇ Operation axis: 2 ⁇ / ⁇ , Measurement method: Continuous, Count unit: cps Start angle: 15.0 °, end angle: 120.0 °, integration count: 1 sampling width: 0.01 °, scan speed: 1.0 ° / min Voltage: 40 kV, current: 40 mA Divergence slit: 0.2 mm, Divergence length restriction slit: 2 mm Scattering slit: 2 °, light receiving slit: 0.15 mm Offset angle: 0 ° Goniometer radius: 285 mm, optical system: concentrated method attachment: ASC-48 Slit: D / teX Ultra slit detector: D / teX Ultra Incident monochrome: CBO Ni-K ⁇ filter: No rotation speed: 50 rpm
  • the XRD measurement was performed under the following measurement condition 2 using an apparatus name “Ultima IV, manufactured by Rigaku Corporation” to obtain an XRD pattern.
  • XRD measurement condition 2 Radiation source: CuK ⁇ (line focal point), wavelength: 1.541836 ⁇ Operation axis: 2 ⁇ / ⁇ , Measurement method: Continuous, Count unit: cps Start angle: 14.0 °, end angle: 16.5 °, number of integrations: 15 sampling width: 0.01 °, scan speed: 0.1 ° / min Voltage: 40 kV, current: 40 mA Divergence slit: 0.2 mm, Divergence length restriction slit: 2 mm Scattering slit: 2 °, light receiving slit: 0.15 mm Offset angle: 0 ° Goniometer radius: 285 mm, optical system: concentrated method attachment: ASC-48 Slit: D / teX Ultra slit detector: D / teX Ultra Incident monochrome: CBO Ni-K ⁇ filter: No rotation speed: 50 rpm
  • the presence or absence of a peak was determined as follows. First, in the obtained XRD pattern, the average value of cps of 2 ⁇ of 14.0 to 14.5 ° and 16.0 ° to 16.5 ° was set as the intensity A of the background (BG). Next, when the maximum value of cps between 14.5 and 16.0 is the peak intensity B, if the difference between the peak intensity B and the background A (BG) intensity A is 25 cps or more, there is a peak. It was determined that When a peak was present between 14.0 and 16.5 °, “Yes” was indicated in the table, and “None” was indicated when it was not present.
  • the 2 ⁇ of the pattern obtained under XRD measurement condition 2 is 14.4 with respect to the peak intensity of the highest peak among the peaks existing between 18 and 19 ° of the pattern obtained under XRD measurement condition 1.
  • the ratio of the peak intensity of the highest peak among the peaks existing between 0 and 16.5 ° is shown as “P14.0-16.5 ° / P18-19 °”.
  • the crystal structure is attributed to the cubic crystal of the space group Fd-3m (Origin Choice 2), Li is present at the 8a site, Mn, M1 element, M2 element, and excessive Li content a are present at the 16d site.
  • the parameter Beq. Is fixed at 1, and the index indicating the degree of coincidence between the observed intensity and the calculated intensity using the O's fractional coordinates and the seat occupancy at the 32e site as variables.
  • the calculation was repeated until convergence with Rwp ⁇ 10.0 and GOF ⁇ 2.2.
  • the crystallite size and strain were analyzed using a Gaussian function to obtain the crystallite size and strain.
  • XRD measurement condition 3 Radiation source: CuK ⁇ , operation axis: 2 ⁇ / ⁇ , measurement method: continuous, counting unit: cps Start angle: 10 °, end angle: 120 ° Detector: PSD Detector Type: VANTEC-1 High Voltage: 5585V Discr. Lower Level: 0.25V Discr.
  • the specific surface area (SSA) of the spinel-type lithium manganese-containing composite oxide powders (samples) obtained in the examples and comparative examples was measured as follows. First, 2.0 g of a sample (powder) was weighed into a glass cell (standard cell) for a fully automatic specific surface area measuring device Macsorb (manufactured by Mountec Co., Ltd.), and set in an autosampler. After replacing the inside of the glass cell with nitrogen gas, heat treatment was performed at 250 ° C. for 15 minutes in the nitrogen gas atmosphere. Thereafter, cooling was performed for 4 minutes while flowing a mixed gas of nitrogen and helium. After cooling, the sample (powder) was measured by the BET single point method. Note that a mixed gas of 30% nitrogen and 70% helium was used as the adsorption gas during cooling and measurement.
  • the coating machine After coating this positive electrode mixture slurry on an aluminum foil as a current collector at a conveying speed of 20 cm / min using a coating machine, the coating machine is used to hold 70 ° C. for 2 minutes. After heating as described above, drying was performed so as to hold 120 ° C. for 2 minutes to form a positive electrode mixture layer to obtain an aluminum foil with a positive electrode mixture layer.
  • the aluminum foil with the positive electrode mixture layer was punched out to 13 mm ⁇ after punching the electrode into a size of 50 mm ⁇ 100 mm and using a roll press machine to press and dense with a press linear pressure of 3 t / cm. Next, in a vacuum state, the mixture was heated from room temperature to 200 ° C.
  • the negative electrode is a metal Li of ⁇ 14 mm ⁇ thickness 0.6 mm, and a separator (made of a porous polyethylene film) impregnated with an electrolytic solution in which LiPF 6 is dissolved to 1 mol / L in a carbonate-based mixed solvent is placed, A 2032 type coin battery was produced.
  • the coating machine After coating this positive electrode mixture slurry on an aluminum foil as a current collector at a conveying speed of 20 cm / min using a coating machine, the coating machine is used to hold 70 ° C. for 2 minutes. After heating as described above, drying was performed so as to hold 120 ° C. for 2 minutes to form a positive electrode mixture layer to obtain an aluminum foil with a positive electrode mixture layer.
  • the aluminum foil with the positive electrode mixture layer was punched into a size of 50 mm ⁇ 100 mm, and then pressed and dense at a press linear pressure of 3 t / cm using a roll press machine, and then punched into a 40 mm ⁇ 29 mm square. It was. Next, in a vacuum state, the mixture was heated from room temperature to 200 ° C. and dried by heating so as to be held at 200 ° C. for 6 hours to obtain a positive electrode.
  • the positive electrode sheet obtained above and a negative electrode sheet coated with natural spherical graphite (Piotrek Co., Ltd., electrode capacity 1.6 mAh / cm 2 ) were cut into a size of 3.1 cm ⁇ 4.2 cm to form a negative electrode.
  • a separator type battery porous polyethylene film impregnated with an electrolytic solution in which LiPF 6 was dissolved at 1 mol / L in a carbonate-based mixed solvent was placed between the negative electrode and the negative electrode to produce a laminate type battery.
  • a charge / discharge test was conducted by the method described below using the laminate type battery after the initial activation as described above, and the high-temperature cycle life characteristics were evaluated. Place the cell in an environmental testing machine set so that the environmental temperature for charging and discharging the battery is 45 ° C., prepare to charge and discharge, and let it stand for 4 hours so that the cell temperature becomes the environmental temperature, then charge and discharge range was 4.9 V to 2.9 V, charge was performed at a constant current of 0.1 C constant current, and discharge was performed at a constant current of 0.1 C for one cycle, and then charge and discharge cycles were performed 199 times at 1 C. The C rate was calculated based on the discharge capacity at the third cycle at 25 ° C. during initial activation.
  • the percentage (%) of the numerical value obtained by dividing the discharge capacity at the 199th cycle by the discharge capacity at the second cycle was determined as the high temperature cycle life characteristic value.
  • Table 1 shows the high-temperature cycle life characteristic value (“capacity retention ratio”) of each example and comparative example as a relative value when the high-temperature cycle life characteristic value of comparative example 1 is 100.
  • W1 V1 ⁇ I
  • W2 V2 ⁇ I
  • the current value equivalent to 3C is I
  • the natural potential immediately before the start of measurement is V1
  • the potential when the 3C current is applied for 10 seconds is V2
  • W1 is the output value immediately before the start of measurement
  • W2 is the output after the measurement.
  • (W1-W2) indicates a decrease in output, and an increase in the reciprocal thereof reduces the decrease in output. That is, the output characteristics are improved.
  • Table 1 shows the relative values with Comparative Example 1 as 100.
  • Rate characteristics evaluation test Using the 2032 type coin battery produced by the above method, rate characteristics were evaluated by the method described below. The battery after the initial activation was charged at a current value corresponding to 0.1 C, and then discharged at 0.2 C. The discharge rate of this operation was changed to equivalent to 0.33, 0.5, 1, 3, 5C, respectively, and current charging / discharging was performed. A value obtained by dividing the discharge capacity at a current value equivalent to 5 C by the discharge capacity at 0.1 C was used as an indicator of rate characteristics. The larger this value, the better the rate characteristics. In the table, the numerical value of Comparative Example 1 is set to 100, and the values are described as indexes.
  • substitution element species in the following Table 1 means the constituent elements of the spinel type lithium manganese-containing composite oxide other than Li, Mn, Ni and O.
  • the primary particles of the 5V-class spinel are made polycrystalline, and the D50 in the volume particle size distribution measurement is 0.5 to 9 ⁇ m, and the mode diameters, D50 and D10
  • the dispersibility of the primary particles can be improved, and further, the particle size distribution can be made close to the normal distribution and close to the sharpness. It was found that the output characteristics and life characteristics can be improved while suppressing gas generation, and the first problem can be solved.
  • the D50 by volume particle size distribution measurement obtained by measuring by the laser diffraction / scattering particle size distribution measurement method is 0.5 to 9 ⁇ m and is calculated from the mode diameter, D50 and D10 (

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019044733A1 (ja) * 2017-08-28 2019-03-07 三井金属鉱業株式会社 全固体型リチウム二次電池用正極活物質
WO2019044734A1 (ja) * 2017-08-28 2019-03-07 三井金属鉱業株式会社 全固体型リチウム二次電池用正極活物質
JP2020140837A (ja) * 2019-02-27 2020-09-03 三井金属鉱業株式会社 活物質、それを用いた正極合剤及び固体電池
WO2020175506A1 (ja) * 2019-02-27 2020-09-03 三井金属鉱業株式会社 活物質、それを用いた正極合剤及び固体電池
JP2020140839A (ja) * 2019-02-27 2020-09-03 三井金属鉱業株式会社 活物質、それを用いた正極合剤及び固体電池
WO2021225095A1 (ja) * 2020-05-07 2021-11-11 住友化学株式会社 リチウム金属複合酸化物、リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
WO2022054705A1 (ja) 2020-09-11 2022-03-17 三井金属鉱業株式会社 活物質及びその製造方法、電極合剤、並びに電池
JP2022523304A (ja) * 2019-01-25 2022-04-22 セラミック パウダー テクノロジー エーエス セラミック複合酸化物
WO2022259755A1 (ja) 2021-06-10 2022-12-15 三井金属鉱業株式会社 活物質及びその製造方法
CN115916402A (zh) * 2020-06-22 2023-04-04 三井金属矿业株式会社 废气净化用催化剂
US11824188B2 (en) 2017-08-14 2023-11-21 Mitsui Mining & Smelting Co., Ltd. Positive electrode active material for all-solid-state lithium secondary batteries

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6633796B1 (ja) * 2018-12-20 2020-01-22 住友化学株式会社 リチウム金属複合酸化物粉末、リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP6999598B2 (ja) * 2019-03-28 2022-01-18 住友大阪セメント株式会社 リチウムイオン二次電池用正極材料、リチウムイオン二次電池用正極、リチウムイオン二次電池
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AU2024256228A1 (en) * 2023-04-20 2025-09-25 Topsoe Battery Materials A/S Cathode active material having spinel structure
CN116581283B (zh) * 2023-05-17 2024-05-28 巴斯夫杉杉电池材料有限公司 一种低氧空位的高性能锰酸锂正极材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012216548A (ja) * 2011-03-31 2012-11-08 Toda Kogyo Corp 非水電解質二次電池用活物質粉末及び非水電解質二次電池
WO2014185548A1 (ja) * 2013-05-17 2014-11-20 三井金属鉱業株式会社 リチウム二次電池用正極活物質
JP2015140297A (ja) * 2015-04-28 2015-08-03 住友金属鉱山株式会社 マンガンニッケルチタン複合水酸化物粒子とその製造方法、および、非水系電解質二次電池用正極活物質の製造方法
JP2015140292A (ja) * 2014-01-29 2015-08-03 住友金属鉱山株式会社 非水系電解質二次電池用正極活物質、および、非水系電解質二次電池

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3221352B2 (ja) * 1996-06-17 2001-10-22 株式会社村田製作所 スピネル型リチウムマンガン複合酸化物の製造方法
JP3813001B2 (ja) 1997-08-29 2006-08-23 旭化成エレクトロニクス株式会社 非水系二次電池
JP2000012029A (ja) * 1998-06-24 2000-01-14 Shin Kobe Electric Mach Co Ltd 非水電解質二次電池
JP3634694B2 (ja) 1998-12-18 2005-03-30 三洋電機株式会社 リチウム二次電池
JP4325167B2 (ja) 2001-10-18 2009-09-02 日本電気株式会社 非水電解液二次電池用電極材料
KR100562366B1 (ko) * 2002-05-20 2006-03-20 니치아 카가쿠 고교 가부시키가이샤 비수성 전해액 이차전지용 양극활성물질
JP2008147068A (ja) * 2006-12-12 2008-06-26 Ise Chemicals Corp 非水電解液二次電池用リチウム複合酸化物
JP4221448B1 (ja) 2007-07-19 2009-02-12 日鉱金属株式会社 リチウムイオン電池用リチウムマンガン複合酸化物及びその製造方法
WO2010032449A1 (ja) 2008-09-18 2010-03-25 戸田工業株式会社 マンガン酸リチウム粒子粉末の製造方法及び非水電解質二次電池
JP2012089464A (ja) * 2010-03-26 2012-05-10 Sanyo Electric Co Ltd 非水電解質二次電池及び非水電解質二次電池の製造方法
KR20130094286A (ko) * 2010-07-16 2013-08-23 미쓰비시 가가꾸 가부시키가이샤 리튬 2 차 전지용 정극 및 그것을 사용한 리튬 2 차 전지
FR2969595A1 (fr) * 2010-12-23 2012-06-29 Saint Gobain Ct Recherches Procede de fabrication d'un produit lmo.
US20120179323A1 (en) * 2011-01-06 2012-07-12 Ford Global Technologies, Llc Method and Apparatus for Charging Station Guidance
EP2693534B1 (en) * 2011-03-31 2022-06-22 Toda Kogyo Corp. Manganese-nickel composite oxide particle powder, production method therefor, positive-electrode active material particle powder for nonaqueous electrolyte secondary batteries, production method therefor, and nonaqueous electrolyte secondary battery
KR101452029B1 (ko) * 2011-09-20 2014-10-23 주식회사 엘지화학 고용량 양극활물질 및 이를 포함하는 리튬이차전지
ES2915724T3 (es) * 2012-04-05 2022-06-24 Tosoh Corp Partículas combinadas de tetraóxido de trimanganeso que contiene un metal y su proceso de producción
JP5523637B2 (ja) 2012-04-27 2014-06-18 三井金属鉱業株式会社 マンガン系スピネル型リチウム遷移金属酸化物
JP5572268B1 (ja) 2012-08-24 2014-08-13 三井金属鉱業株式会社 スピネル型リチウムマンガンニッケル含有複合酸化物
US9337486B2 (en) * 2012-09-25 2016-05-10 Mitsui Mining & Smelting Co., Ltd. Spinel-type lithium-manganese composite oxide
CN103840147A (zh) * 2012-11-22 2014-06-04 广饶格林新能源有限公司 一种制备锂离子电池正极材料锂锰尖晶石氧化物的方法
US9478808B2 (en) 2012-12-12 2016-10-25 Samsung Sdi Co., Ltd. Positive active material, positive electrode and rechargeable lithium battery including same
JP2014139119A (ja) * 2012-12-20 2014-07-31 Tosoh Corp ニッケル−コバルト−マンガン系複合酸化物及びその製造方法、並びにその用途
GB2528222B (en) * 2013-05-17 2021-11-24 Mitsui Mining & Smelting Co Ltd Positive electrode active material for lithium secondary battery
TWI636613B (zh) * 2013-07-18 2018-09-21 日商東曹股份有限公司 鎳－錳系複合氧氫氧化物及其製造方法、以及其用途
JP6274533B2 (ja) * 2014-07-22 2018-02-07 トヨタ自動車株式会社 リチウム二次電池用正極活物質およびその利用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012216548A (ja) * 2011-03-31 2012-11-08 Toda Kogyo Corp 非水電解質二次電池用活物質粉末及び非水電解質二次電池
WO2014185548A1 (ja) * 2013-05-17 2014-11-20 三井金属鉱業株式会社 リチウム二次電池用正極活物質
JP2015140292A (ja) * 2014-01-29 2015-08-03 住友金属鉱山株式会社 非水系電解質二次電池用正極活物質、および、非水系電解質二次電池
JP2015140297A (ja) * 2015-04-28 2015-08-03 住友金属鉱山株式会社 マンガンニッケルチタン複合水酸化物粒子とその製造方法、および、非水系電解質二次電池用正極活物質の製造方法

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11824188B2 (en) 2017-08-14 2023-11-21 Mitsui Mining & Smelting Co., Ltd. Positive electrode active material for all-solid-state lithium secondary batteries
US12347856B2 (en) 2017-08-28 2025-07-01 Mitsui Mining & Smelting Co., Ltd. Positive electrode active substance for all solid-state lithium secondary battery
WO2019044734A1 (ja) * 2017-08-28 2019-03-07 三井金属鉱業株式会社 全固体型リチウム二次電池用正極活物質
WO2019044733A1 (ja) * 2017-08-28 2019-03-07 三井金属鉱業株式会社 全固体型リチウム二次電池用正極活物質
JP2022523304A (ja) * 2019-01-25 2022-04-22 セラミック パウダー テクノロジー エーエス セラミック複合酸化物
WO2020175506A1 (ja) * 2019-02-27 2020-09-03 三井金属鉱業株式会社 活物質、それを用いた正極合剤及び固体電池
JPWO2020175506A1 (ja) * 2019-02-27 2021-09-13 三井金属鉱業株式会社 活物質、それを用いた正極合剤及び固体電池
JP2020140839A (ja) * 2019-02-27 2020-09-03 三井金属鉱業株式会社 活物質、それを用いた正極合剤及び固体電池
JP2020140837A (ja) * 2019-02-27 2020-09-03 三井金属鉱業株式会社 活物質、それを用いた正極合剤及び固体電池
WO2021225095A1 (ja) * 2020-05-07 2021-11-11 住友化学株式会社 リチウム金属複合酸化物、リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP2021177460A (ja) * 2020-05-07 2021-11-11 住友化学株式会社 リチウム金属複合酸化物、リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP7471903B2 (ja) 2020-05-07 2024-04-22 住友化学株式会社 リチウム金属複合酸化物、リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
CN115516668A (zh) * 2020-05-07 2022-12-23 住友化学株式会社 锂金属复合氧化物、锂二次电池用正极活性物质、锂二次电池用正极及锂二次电池
CN115916402A (zh) * 2020-06-22 2023-04-04 三井金属矿业株式会社 废气净化用催化剂
WO2022054705A1 (ja) 2020-09-11 2022-03-17 三井金属鉱業株式会社 活物質及びその製造方法、電極合剤、並びに電池
WO2022259755A1 (ja) 2021-06-10 2022-12-15 三井金属鉱業株式会社 活物質及びその製造方法

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