[go: up one dir, main page]

WO2016175312A1 - Oxyde composite de lithium-manganèse de type spinelle de classe 5v - Google Patents

Oxyde composite de lithium-manganèse de type spinelle de classe 5v Download PDF

Info

Publication number
WO2016175312A1
WO2016175312A1 PCT/JP2016/063454 JP2016063454W WO2016175312A1 WO 2016175312 A1 WO2016175312 A1 WO 2016175312A1 JP 2016063454 W JP2016063454 W JP 2016063454W WO 2016175312 A1 WO2016175312 A1 WO 2016175312A1
Authority
WO
WIPO (PCT)
Prior art keywords
spinel
composite oxide
type lithium
lithium manganese
containing composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/063454
Other languages
English (en)
Japanese (ja)
Inventor
徹也 光本
恭平 山口
松山　敏和
松嶋　英明
蔭井　慎也
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Kinzoku Co Ltd
Original Assignee
Mitsui Mining and Smelting Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Mining and Smelting Co Ltd filed Critical Mitsui Mining and Smelting Co Ltd
Priority to JP2017515623A priority Critical patent/JP6630724B2/ja
Publication of WO2016175312A1 publication Critical patent/WO2016175312A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a 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 overcharging, so that it can be used in electric vehicles (EV) and hybrid electric vehicles (HEV). 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.
  • the 5V-class spinel type lithium manganese-containing composite oxide having an operating potential of 4.5V or more is a problem that hardly occurs in the 4V class spinel-type lithium manganese-containing composite oxide, that is, generation of gas generated by reaction with the electrolyte. I had a characteristic problem of a large amount.
  • the plateau region around 4.5V can be expanded, the high potential capacity region can be expanded, the energy density can be increased, and the amount of gas generated can be reduced. It has been found to increase. For this reason, it has been difficult for the 5V-class spinel type lithium manganese-containing composite oxide 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 intended to provide a new 5V-class spinel type lithium manganese-containing composite oxide that can achieve both expansion of the high potential capacity region and suppression of gas generation.
  • the present invention relates to a spinel-type lithium manganese-containing composite oxide containing Li, Mn, and O and two or more elements other than these and having a working potential of 4.5 V or more at a metal Li reference potential,
  • a spinel type lithium manganese-containing oxide characterized by the presence of three absorbance ABS peaks in the region of 435 to 525 cm ⁇ 1 is proposed.
  • 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 can suppress gas generation and has a plateau region around 4.5 V. Since it can be enlarged and the high potential capacity region can be enlarged, the energy density can be improved. Therefore, according to the spinel type lithium manganese containing composite oxide which this invention proposes, expansion of a high potential capacity area and suppression of gas generation can be made compatible. Furthermore, by including Li, Mn, and O and two or more elements other than these, the crystal structure can be stabilized, and the cycle characteristics can be improved.
  • Example 3 is a spectrum obtained by FT-IR of a spinel type lithium manganese-containing composite oxide powder (sample) obtained in Example 1.
  • 4 is a spectrum obtained by FT-IR of a spinel type lithium manganese-containing composite oxide powder (sample) obtained in Comparative Example 3.
  • the wave number interval ⁇ X (1.9285 cm ⁇ 1 ) of the data and the amount of change ⁇ Y in the infrared absorptance ABS are calculated, and the X axis is the Wave Number and the Y axis. This is an approximate curve created from a drawn curve with ⁇ Y / ⁇ X as.
  • the wave number interval ⁇ X (1.9285 cm ⁇ 1 ) of the data and the amount of change ⁇ Y in the infrared absorptance ABS are calculated, the X axis is the Wave Number, and the Y axis is This is an approximate curve created from a drawn curve with ⁇ Y / ⁇ X as.
  • 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.
  • 5V class spinel having a working potential of 4.5 V or more at a metal Li reference potential, wherein Rwp and S representing the degree of coincidence of strength and calculated intensity are Rwp ⁇ 10 or S ⁇ 2.5.
  • Type lithium manganese-containing composite oxide is
  • “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.
  • This 5V class spinel is a spinel-type lithium manganese-containing composite oxide containing Li, Mn, and O and two or more elements other than these.
  • at least one element of the “two or more elements other than these” may be an element M1 selected from the group consisting of Ni, Co, and Fe, and the other one element may be Mg, Ti.
  • Any element M2 selected from the group consisting of Al, Ba, Cr, W, Mo, Y, Zr and Nb may be used.
  • 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 mainly contributes to stabilizing the crystal structure and improving the characteristics.
  • a substitution element that contributes to an improvement in capacity retention rate for example, Mg, Ti, Al, Ba, Cr, W , Mo, Y, Zr, and Nb. It suffices to contain at least one of these Mg, Ti, Al, Ba, Cr, W, Mo, Y, Zr and Nb, and M2 may contain other metal elements.
  • a compound containing a spinel type lithium manganese containing composite oxide represented by the formula (1): Li [Li a Mn 2 -abc M1 b M2 c ] O 4 - ⁇ .
  • M1 and M2 in the formula (1) are as described above.
  • “a” may be 0.00 to 0.20, particularly 0.01 or more and 0.10 or less, and more preferably 0.02 or more and 0.08 or less. Even more preferred. “B” indicating the content of M1 may be 0.20 to 1.20, more preferably 0.30 or more and 1.10 or less, and more preferably 0.35 or more and 1.05 or less. Even more preferred. “C” 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, by setting it to 0.10 or more, the amount of gas generated can be more effectively suppressed. Note that “4- ⁇ ” in each of the above formulas indicates that oxygen deficiency may be included, and a part of oxygen may be substituted with fluorine.
  • this 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.
  • a compound containing a spinel-type lithium manganese-containing composite oxide represented by the formula (2): Li [Li a Mn 2 -abc Ni b M 2 c ] O 4- ⁇ can be cited. it can.
  • “a”, “b”, “c”, and “4- ⁇ ” are the same as those in the above formula (1).
  • M2 in Formula (2) Mg, Ti, Al, Ba, Cr, W, Mo, Y, Zr, Co, Fe, Nb etc.
  • Mg Ti, Al , Ba, Cr, W, Mo, Y, Zr, Co, Fe, and Nb
  • M2 may include another metal element.
  • M2 it is more preferable that M2 contains Ti or Al or these two elements.
  • “a” may be 0.00 to 0.20, more preferably 0.01 or more and 0.10 or less, and more preferably 0.02 or more and 0.08 or less. Even more preferred.
  • “B” indicating the content of M1 may be 0.20 to 0.70, particularly 0.30 or more and 0.60 or less, particularly 0.35 or more and 0.55 or less, and more preferably 0. More preferably, it is .49 or less. In particular, by setting it to 0.49 or less, the cycle characteristics in the high potential range can be improved more effectively.
  • “C” 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 0.300 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.
  • 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.
  • this 5V-class spinel is a cubic crystal structure model of space group Fd-3m (Origin Choice 2) in an X-ray diffraction pattern measured by a powder X-ray diffractometer (XRD) using CuK ⁇ 1 rays.
  • Rwp and S representing the degree of coincidence between the observed intensity and the calculated intensity are 5V class spinels with Rwp ⁇ 10 or S ⁇ 2.5.
  • Rwp is more preferably less than 8, particularly preferably less than 6, and S is more than 1.0 or more preferably less than 2.3, and more preferably less than 2.1.
  • This 5V-class spinel is also characterized by the presence of three absorbance ABS peaks in the 435 to 525 cm ⁇ 1 section in the spectrum determined by FT-IR.
  • 5V class spinel containing Li, Mn, and O and two or more other elements there are three absorbance ABS peaks in the section of 435 to 525 cm ⁇ 1.
  • the shoulder near 4 V disappeared and the plateau region near 4.5 expanded, the high potential capacity region expanded, and the energy density increased compared to the case where three peaks did not exist. It was also found that gas generation can be suppressed.
  • a 5V spinel-type lithium manganese-containing composite oxide is used as an object to be processed. It is preferable to perform an oxygen-containing atmosphere pressure heat treatment.
  • the tap density of the 5V-class spinel is preferably 1.2 g / cm 3 or more, especially 1.3 g / cm 3 or more, or 3.0 g / cm 3 or less, and more preferably 1.5 g / cm 3 or more. It is particularly preferably 8 g / cm 3 or less.
  • the electrode density can be increased, so that the volume energy density can be increased.
  • this 5V-class spinel To increase the tap density of this 5V-class spinel to 1.2 g / cm 3 or more, add a substance that enhances the reactivity during firing, such as firing at a high temperature of 800 ° C. or higher, or a boron compound or a fluorine compound. It is preferable to produce the 5V-class spinel by firing and using dense raw materials. However, it is not limited to this method.
  • the average primary particle size of the present 5V class spinel is preferably larger than 0.5 ⁇ m, more preferably 1.0 ⁇ m or more or 20 ⁇ m or less, and more preferably 2.0 ⁇ m or more or 15 ⁇ m or less. Furthermore, it is further more preferable that it exceeds 6.0 micrometers among them, and it is especially preferable that it is 8.5 micrometers or more especially among them. Thus, if the average primary particle size of this 5V class spinel is larger than 0.5 micrometer, a contact area with electrolyte solution can be reduced and the amount of gas generation can be reduced.
  • the average primary particle size of the 5V class spinel In order to make the average primary particle size of the 5V class spinel larger than 0.5 ⁇ m, it is necessary to calcinate at a high temperature of 800 ° C. or higher, or to add a substance that enhances the reactivity during calcination such as a boron compound or a fluorine compound.
  • the 5V-class spinel is preferably manufactured by firing. However, it is not limited to this method.
  • primary particles mean the smallest unit particles surrounded by grain boundaries when observed with a SEM (scanning electron microscope, for example, 500 to 5000 times).
  • the “present spinel particles” mean primary particles unless otherwise specified.
  • the average diameter of the primary particles is observed with an SEM (scanning electron microscope, for example, 500 to 5000 times), 50 primary particles are arbitrarily selected, and the selected primary particle is selected using image analysis software.
  • the average particle diameter of the particles can be calculated, and the 50 primary particle diameters can be averaged to obtain the “average diameter of primary particles”.
  • the “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. is there.
  • standard particle size distribution obtained by measuring by the laser diffraction scattering type particle size distribution measuring method has a meaning as an alternative value of the average diameter of the particle
  • the specific surface area (SSA) of the present 5V class spinel is preferably 1.5 m 2 / g or less, especially 0.1 m 2 / g or more or 1.0 m 2 / g or less, and more preferably 0.1 m 2 / g or more. Or it is especially preferable that it is 0.8 m ⁇ 2 > / g or less.
  • SSA specific surface area
  • the present 5V class spinel preferably has a crystallite size of 100 nm or more. If the crystallite size is 100 nm or more, the ion conductivity 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. From this point of view, the crystallite size of the 5V class spinel is preferably 100 nm or more, more preferably 110 nm or more or 300 nm or less, particularly 120 nm or more or 250 nm or less, and more preferably 130 nm or more or 200 nm or less. Even more preferred.
  • crystallite means the largest group that can be regarded as a single crystal, and can be obtained by XRD measurement and Rietveld analysis.
  • the firing temperature, firing time, auxiliary agent for enhancing reactivity, firing atmosphere, raw material type, and the like it is preferable to adjust the firing temperature, firing time, auxiliary agent for enhancing reactivity, firing atmosphere, raw material type, and the like.
  • the manufacturing method of the present 5V-class spinel may include an oxygen-containing atmospheric pressure heat treatment step using a spinel-type lithium manganese-containing composite oxide, preferably a 5V spinel-type lithium manganese-containing composite oxide as an object to be processed.
  • the spinel-type lithium manganese-containing composite oxide as the object to be processed may be manufactured from raw materials as described later, or a product manufactured separately from the manufacturing method of the present 5V class spinel is obtained and You may use as a to-be-processed object.
  • the manufacturing method provided with the raw material mixing process, the baking process, and the oxygen containing atmosphere pressurization heat treatment process in this order, and also the washing process can be mentioned.
  • the cleaning steps can be inserted in an appropriate order. For example, it can be inserted before the raw material mixing step, after the raw material mixing step, before the firing step, after the firing step, before the oxygen-containing atmosphere pressure heat treatment step, or after the firing step.
  • other steps can be added. For example, it is possible to further add a wet grinding process, a granulation process, a heat treatment process, and other processes.
  • Formula (1) Li [Li a Mn 2 -abc M1 b M2 c ] O 4- ⁇ or Formula (2): Spinel type represented by Li [Li a Mn 2 -abc Ni b M2 c ] O 4- ⁇
  • Examples of raw materials for producing the lithium manganese-containing composite oxide include lithium raw materials, manganese raw materials, M1 metal raw materials, M2 metal raw materials, and other examples such as boron raw materials.
  • lithium raw material examples include lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ), lithium nitrate (LiNO 3 ), LiOH ⁇ H 2 O, lithium oxide (Li 2 O), other fatty acid lithium and lithium halide.
  • the manganese raw material examples 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.
  • M1 metal raw material and the M2 metal raw material examples include carbonates, nitrates, chlorides, oxyhydroxides and hydroxides of M1 or M2 metals.
  • 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 object to be processed for the cleaning step is, for example, each raw material before raw material mixing, raw material mixed powder after raw material mixing, processed powder after oxygen-containing atmosphere pressure heat treatment, processed product obtained in the firing step, and further described below.
  • the processed powder obtained in the crushing / classifying step may be used. One or more of these may be washed.
  • the object to be processed is washed with a polar solvent so as to release impurities contained in the powder.
  • a polar solvent for example, it may be mixed with a polar solvent and stirred to form a slurry, and the obtained slurry may be solid-liquid separated by filtration or the like to remove impurities.
  • 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 liquid temperature at the time of washing it has been confirmed that 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. 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 workpiece (powder) is preferably 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 content it is more preferable to adjust the content to be 20 wt% or more or 60 wt% or less, and more preferably 30 wt% or more or 50 wt% or less. If 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.
  • each raw material or raw material mixed powder is put into the cleaning liquid, stirred, and then allowed to stand to remove the supernatant liquid. This method may be adopted.
  • the supernatant when washing the processed product obtained in the firing step, that is, the spinel-type lithium manganese-containing composite oxide, the supernatant may be removed by adding it to the washing solution 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.
  • the spinel-type lithium manganese-containing composite oxide obtained by the oxygen-containing atmosphere pressure heat treatment is added to the cleaning liquid, stirred, and then allowed to stand.
  • the supernatant liquid may be removed.
  • 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.
  • 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 it is preferable to employ wet mixing.
  • Examples of the dry mixing 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.
  • a nickel compound and a nickel compound and a manganese compound are pulverized and classified as necessary 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.
  • 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 formed so as to contain agglomerated particles (secondary particles) formed by agglomeration. Forms can be prepared.
  • firing is preferably performed in an atmosphere having an oxygen partial pressure of 0.015 MPa to 0.15 MPa, for example, in an air atmosphere. If the oxygen partial pressure is higher than 0.15 MPa, crystal growth cannot be promoted and the crystallite size cannot be increased. In addition, as will be described later, in order to promote crystal growth by firing, it is preferable that the oxygen partial pressure in the atmosphere is low. However, if the oxygen partial pressure during firing is too low, oxygen deficiency will increase and heat treatment will also occur. Since the strain cannot be recovered, baking is preferably performed at an oxygen partial pressure of 0.015 MPa or more.
  • the oxygen partial pressure during firing is more preferably 0.015 MPa to 0.13 MPa, particularly 0.015 MPa to 0.12 MPa, particularly 0.015 MPa or more, or less than 0.08 MPa, and especially 0. More preferably, it is at least .015 MPa or less than 0.061 MPa.
  • firing is preferably performed at a temperature higher than 770 ° C., particularly 800 ° C. or higher, particularly 850 ° C. or higher.
  • 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 kind of baking furnace is not specifically 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 770 ° C., more preferably 800 ° C. or higher, and particularly preferably 850 ° C. or higher.
  • firing is preferably performed at 980 ° C. or lower, and particularly at 960 ° C. or lower. Is more preferable.
  • baking is preferably performed at a temperature higher than 800 ° C., more preferably 840 ° C. or higher, and particularly preferably 880 ° C. or higher.
  • firing temperature is preferably performed at 1000 ° C. or lower, and particularly at 980 ° C. or lower. Is more preferable.
  • the workpiece to be subjected to the oxygen-containing atmosphere pressure heat treatment step is measured with a Karl Fischer moisture measuring device (also referred to as “KF moisture measuring device”) “KF moisture content in the range of room temperature to 300 ° C. (referred to as“ KF moisture ”). ) "Is 2% or less, and the sulfur content analyzed by ICP is preferably a spinel-type lithium manganese-containing composite oxide of less than 0.34 wt%. If the KF moisture is more than 2%, the atmosphere in the oxygen-containing atmosphere pressurizing furnace contains a large amount of water vapor, and the desired heat treatment atmosphere may not be created.
  • the KF moisture is preferably 1% or less, particularly less than 5000 ppm, particularly 2000 ppm, and more preferably 1000 ppm or less.
  • the sulfur content is 0.34 wt% or more, a large amount of sulfate such as Na 2 SO 4 or Li 2 SO 4 exists on the surface, which may hinder the heat treatment effect. From this viewpoint, the sulfur content is preferably less than 0.34 wt%, and particularly preferably less than 0.28 wt%.
  • Such a spinel-type lithium manganese-containing composite oxide having KF moisture and sulfur content can be obtained, for example, by adjusting the conditions of the firing step and the cleaning step. For example, by firing the raw material before mixing at a high temperature of 600 ° C. or higher, washing the raw material before mixing, or washing the processed product obtained in the firing step, that is, the spinel-type lithium manganese-containing composite oxide,
  • the sulfur content can be less than 0.34 wt%.
  • the KF moisture content can be reduced to 2% or less by baking at a high temperature of 800 ° C. or higher in the baking step.
  • the “KF moisture in the range of room temperature to 300 ° C.” measured by the KF moisture measuring device means that the measurement chamber of the KF moisture measuring device is heated to 170 ° C. with a nitrogen atmosphere, and then a sample is put in the measuring chamber. The amount of water released when the sample was allowed to stand at 170 ° C. for 45 minutes was measured to obtain “KF moisture (ppm) from room temperature to 170 ° C.”, and then the temperature was raised to 300 ° C. The amount of water released when left at 300 ° C. for 45 minutes was measured to obtain “KF moisture (ppm) from 170 ° C. to 300 ° C.”. ) ”And the above-mentioned“ KF moisture content (170 ° C. to 300 ° C.) (ppm) ”.
  • the overall pressure of the processing atmosphere is higher than atmospheric pressure, and the oxygen partial pressure in the atmosphere is higher than the oxygen partial pressure in the atmosphere, and is 500 ° C.
  • Heat treatment is preferably performed at a temperature higher than 850 ° C.
  • the oxygen-containing atmosphere pressure heat treatment allows oxygen to be incorporated into the 5V spinel structure, thereby reducing oxygen deficiency and stabilizing the structure.
  • the plateau region near 4.5V can be expanded and the high potential capacity region can be expanded, it can be considered that the energy density 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 treatment atmosphere in the oxygen-containing atmosphere pressure heat treatment step is a pressure in which the total pressure of the treatment atmosphere is greater than atmospheric pressure (0.1 MPa), for example, greater than 0.19 MPa, and in particular an atmosphere of 0.20 MPa or more. Is particularly preferred.
  • 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 treatment atmosphere in the pressurized atmosphere is preferably an oxygen partial pressure higher than, for example, 0.19 MPa, and particularly preferably an oxygen partial pressure of 0.20 MPa or more.
  • 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 during the oxygen-containing atmosphere pressure heat treatment is greater than 0.19 MPa and is preferably controlled to 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 pressure heat treatment step that is, the holding temperature
  • 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.
  • 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.
  • 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 total pressure of the treatment atmosphere is a pressure higher than atmospheric pressure, an oxygen partial pressure higher than 0.19 MPa, and a temperature higher than 500 ° C. and lower than 850 ° C.
  • oxygen-containing atmosphere pressure heat treatment is performed at a temperature of 600 ° C. or higher or lower than 850 ° C., of which higher than 700 ° C. or 800 ° C.
  • 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.
  • heating is performed using an apparatus such as a pressure furnace (pressurizable pressure: 1.0 MPa), so that the overall pressure of the treatment atmosphere is higher than atmospheric pressure. And it can heat in the process atmosphere whose oxygen partial pressure in this atmosphere is higher than the oxygen partial pressure in air
  • a pressure furnace pressurizable pressure: 1.0 MPa
  • a manufacturing method including a raw material mixing step, a granulating step, a firing step, a heat treatment step, and an oxygen-containing atmosphere pressure heat treatment step in this order, and further including a cleaning step.
  • the cleaning steps can be inserted in an appropriate order.
  • Any one of the granulation step, the heat treatment step and the washing step, or two or more steps can be omitted, and other steps can be added.
  • the raw material mixing step, wet pulverization step, granulation step, firing step, oxygen-containing atmosphere pressure heat treatment step and cleaning step may be carried out in the same manner as described above.
  • the heat treatment step is preferably performed in an atmosphere of 500 to 850 ° C., preferably 600 ° C. or higher or 800 ° C. or lower for 0.5 to 300 hours in an air atmosphere to facilitate oxygen uptake.
  • 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 (LiPF6) is used for the non-aqueous electrolyte.
  • LiPF6 lithium hexafluorophosphate
  • a lithium battery can be formed using a material 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.
  • the Ni raw material and the Mn 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.
  • Li raw material, Ti raw material and B raw material were added, mixed and stirred, and a slurry having 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 0.60 ⁇ 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 0.15 MPa, the slurry supply amount was 375 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C. .
  • the obtained granulated powder was baked by using a static electric furnace in an atmosphere having an oxygen partial pressure of 0.021 MPa so as to maintain 950 ° C. for 40 hours, and then 750 ° C. in an atmosphere having an oxygen partial pressure of 0.021 MPa.
  • the fired powder obtained by the heat treatment was put in a mortar and crushed with a pestle, classified with a sieve having an opening of 53 ⁇ m, and the sieve was collected to obtain a spinel type lithium manganese-containing composite oxide powder.
  • this spinel type lithium manganese-containing composite oxide powder was subjected to an oxygen-containing atmosphere pressure heat treatment using a pressure furnace (manufactured by Hiroki Co., Ltd.). That is, 200 g of spinel-type lithium manganese-containing composite oxide powder was filled in a magnetic crucible, and this magnetic crucible was placed in a pressure furnace. Thereafter, oxygen gas (oxygen concentration 99%) was introduced into the pressure furnace, the oxygen partial pressure was adjusted to 0.20 MPa, and the overall pressure of the processing atmosphere was adjusted to 0.21 MPa, and the temperature was increased by 1.7 ° C./min. Heat to 730 ° C.
  • a pressure furnace manufactured by Hiroki Co., Ltd.
  • the oxygen concentration was measured using an oxygen concentration meter (XPO-318 (New Cosmos Electric Co., Ltd.)). The same applies to Examples and Comparative Examples described later.
  • the temperature at the time of the said baking and the heat processing is the product temperature of the processed material measured by making the thermocouple contact the processed material in a furnace. The same applies to Examples and Comparative Examples described later.
  • Example 2 the spinel-type lithium manganese-containing composite oxide powder (sample) was prepared in the same manner as in Example 1 except that the weighing value of the raw material was changed, the firing temperature was changed to 940 ° C., and the firing time was changed to 37 hours. Obtained.
  • the chemical analysis of the spinel-type lithium manganese-containing composite oxide powder (sample) obtained in Example 2 was performed, Li: 4.1 wt%, Ni: 15.6 wt%, Mn: 39.9 wt%, Ti: It was 5.0 wt% and B: 0.1 wt%.
  • Example 3 In Example 2, as raw materials, lithium carbonate having an average particle diameter (D50) of 7 ⁇ m, electrolytic manganese dioxide having an average particle diameter (D50) of 23 ⁇ m and a specific surface area of 40 m 2 / g, and an average particle diameter (D50) of 22 ⁇ m as raw materials Of nickel hydroxide, titanium oxide having an average particle diameter (D50) of 2 ⁇ m, aluminum hydroxide having an average particle diameter (D50) of 2 ⁇ m, and lithium tetraborate having an average particle diameter (D50) of 60 ⁇ m are weighed.
  • nickel hydroxide titanium oxide having an average particle diameter (D50) of 2 ⁇ m
  • aluminum hydroxide having an average particle diameter (D50) of 2 ⁇ m
  • lithium tetraborate having an average particle diameter (D50) of 60 ⁇ m
  • the spinel-type lithium manganese-containing composite oxidation was carried out in the same manner as in Example 2 except that the Al raw material was added to ion-exchanged water in which the dispersant was dissolved in advance at the same time as the Mn raw material and Ni raw material, and mixed and stirred.
  • a product powder (sample) was obtained.
  • Example 4 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) Each 1 ⁇ m of titanium oxide was 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, and Ti raw material, and was sufficiently dissolved and mixed in ion-exchanged water.
  • the above-mentioned raw materials weighed 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 60 minutes to obtain a pulverized slurry having an average particle size (D50) of 0.60 ⁇ 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.). 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 316 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 by using a static electric furnace in an atmosphere having an oxygen partial pressure of 0.021 MPa so as to maintain 880 ° C. for 22 hours, and then 740 ° C. in an atmosphere having an oxygen partial pressure of 0.021 MPa.
  • the fired powder obtained by the heat treatment was put in a mortar and crushed with a pestle, classified with a sieve having an opening of 53 ⁇ m, and the sieve was collected to obtain a spinel type lithium manganese-containing composite oxide powder.
  • this spinel type lithium manganese-containing composite oxide powder was subjected to an oxygen-containing atmosphere pressure heat treatment using a pressure furnace (manufactured by Hiroki Co., Ltd.). That is, 200 g of spinel-type lithium manganese-containing composite oxide powder was filled in a magnetic crucible, and this magnetic crucible was placed in a pressure furnace. Thereafter, oxygen gas (oxygen concentration 99%) was introduced into the pressure furnace, the oxygen partial pressure was adjusted to 0.20 MPa, and the overall pressure of the processing atmosphere was adjusted to 0.21 MPa, and the temperature was increased by 1.7 ° C./min. Heat to 730 ° C.
  • a pressure furnace manufactured by Hiroki Co., Ltd.
  • spinel lithium manganese-containing composite oxide powder (sample) Got.
  • the chemical analysis of the spinel type lithium manganese containing complex oxide powder (sample) was carried out, it was Li: 4.1 wt%, Ni: 14.7 wt%, Mn: 41.4 wt%, Ti: 4.0 wt% .
  • Example 5 In Example 4, as raw materials, 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, and water having an average particle size (D50) of 22 ⁇ m Using nickel oxide, titanium oxide with an average particle diameter (D50) of 1 ⁇ m, and cerium oxide with an average particle diameter (D50) of 19 ⁇ m, changing the raw material weighing value, and spraying pressure during granulation drying to 0.48 MPa Except for the changed points, a spinel-type lithium manganese-containing composite oxide powder (sample) was obtained in the same manner as in Example 4.
  • Example 5 When the chemical analysis of the spinel-type lithium manganese-containing composite oxide powder (sample) obtained in Example 5 was performed, Li: 4.1 wt%, Ni: 14.2 wt%, Mn: 40.0 wt%, Ti: It was 5.3 wt% and Ce: 0.8 wt%.
  • Example 6 In Example 4, as raw materials, 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, and water having an average particle size (D50) of 22 ⁇ m Using nickel oxide, titanium oxide with an average particle diameter (D50) of 1 ⁇ m, and yttrium oxide with an average particle diameter (D50) of 7 ⁇ m, changing the weighing value of the raw material, the spray pressure during granulation drying to 0.5 MPa Except for the changed points, a spinel-type lithium manganese-containing composite oxide powder (sample) was obtained in the same manner as in Example 4.
  • Example 6 When the chemical analysis of the spinel-type lithium manganese-containing composite oxide powder (sample) obtained in Example 6 was performed, Li: 4.1 wt%, Ni: 14.2 wt%, Mn: 40.1 wt%, Ti: It was 5.3 wt%, Y: 0.5 wt%.
  • Example 7 In Example 4, as raw materials, 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, and water having an average particle size (D50) of 22 ⁇ m Using nickel oxide, titanium oxide with an average particle diameter (D50) of 1 ⁇ m, and niobium oxide with an average particle diameter (D50) of 70 ⁇ m, changing the weighing value of the raw material, and spraying pressure during granulation drying to 0.5 MPa Except for the changed points, a spinel-type lithium manganese-containing composite oxide powder (sample) was obtained in the same manner as in Example 4.
  • Example 7 When the chemical analysis of the spinel-type lithium manganese-containing composite oxide powder (sample) obtained in Example 7 was performed, Li: 4.1 wt%, Ni: 14.1 wt%, Mn: 40.2 wt%, Ti: It was 5.3 wt% and Nb: 0.5 wt%.
  • Example 8 In Example 4, as raw materials, 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, and water having an average particle size (D50) of 22 ⁇ m Using nickel oxide, titanium oxide with an average particle diameter (D50) of 1 ⁇ m, and tungsten oxide with an average particle diameter (D50) of 62 ⁇ m, changing the weighing value of the raw material, and spraying pressure during granulation drying to 0.5 MPa A spinel-type lithium manganese-containing composite oxide powder (sample) was obtained in the same manner as in Example 4 except that the slurry supply rate was changed to 313 ml / min.
  • Example 8 When the chemical analysis of the spinel-type lithium manganese-containing composite oxide powder (sample) obtained in Example 8 was performed, Li: 4.0 wt%, Ni: 14.0 wt%, Mn: 39.9 wt%, Ti: It was 5.3 wt% and W: 1.0 wt%.
  • Example 9 In Example 3, as raw materials, lithium carbonate having an average particle diameter (D50) of 7 ⁇ m, electrolytic manganese dioxide having an average particle diameter (D50) of 23 ⁇ m and a specific surface area of 40 m 2 / g, and water having an average particle diameter (D50) of 22 ⁇ m Using nickel oxide, titanium oxide with an average particle diameter (D50) of 1 ⁇ m, and aluminum hydroxide with an average particle diameter (D50) of 2 ⁇ m, changing the weighing value of the raw material, the spray pressure during granulation drying is 0.14 MPa A spinel type lithium manganese-containing composite oxide powder (sample) was obtained in the same manner as in Example 3 except that the slurry supply amount was changed to 465 ml / min.
  • Example 9 When the chemical analysis of the spinel-type lithium manganese-containing composite oxide powder (sample) obtained in Example 9 was performed, Li: 4.0 wt%, Ni: 15.7 wt%, Mn: 39.3 wt%, Ti: It was 5.2 wt% and Al: 0.15 wt%.
  • SN Dispersant 5468 manufactured by San Nopco Co., Ltd.
  • the addition amount of the dispersant was 6 wt% with respect to the total of the above-mentioned Li raw material, Ni raw material, and Mn raw material, and was sufficiently dissolved and mixed in ion-exchanged water.
  • the weighed raw material was 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 average particle size (D50) was adjusted to 0.60 ⁇ m or less by pulverizing at 1300 rpm for 120 minutes with a wet pulverizer.
  • 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 0.19 MPa, the slurry supply amount was 350 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 by using a stationary electric furnace in an atmosphere having an oxygen partial pressure of 0.021 MPa so as to maintain 950 ° C. for 37 hours, and then 750 ° C. in an atmosphere having an oxygen partial pressure of 0.021 MPa.
  • the fired powder obtained by the heat treatment was classified with a sieve having an opening of 53 ⁇ m, and the powder under the sieve was collected to obtain a spinel type lithium manganese-containing composite oxide powder (sample).
  • the spinel-type lithium manganese-containing composite oxide powder (sample) thus obtained was subjected to chemical analysis.
  • the results were Li: 3.9 wt%, Ni: 16.0 wt%, and Mn: 43.0 wt%. .
  • 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.
  • the weighed raw material was 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%. Subsequently, the mixture was further pulverized with a wet pulverizer at 1300 rpm for 60 minutes to obtain a pulverized slurry having an average particle size (D50) of 0.60 ⁇ m or less.
  • D50 average particle size
  • 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 0.33 MPa, the slurry supply amount was 350 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 fired so as to maintain 880 ° C. for 37 hours in an atmosphere having an oxygen partial pressure of 0.021 MPa using a stationary electric furnace, and then 750 ° C. in an atmosphere having an oxygen partial pressure of 0.021 MPa.
  • the fired powder obtained by heat treatment was crushed with a pestle and classified with a sieve having an opening of 53 ⁇ m to obtain a spinel-type lithium manganese-containing composite oxide powder.
  • ⁇ Comparative Example 3 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) Each 2 ⁇ m of titanium oxide was 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 addition 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 and Ti raw material, and was sufficiently dissolved and mixed in ion-exchanged water.
  • the weighed raw material was 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 mixture was pulverized with a wet pulverizer at 1300 rpm for 60 minutes to obtain a pulverized slurry having an average particle size (D50) of 0.60 ⁇ 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.). 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 0.46 MPa, the slurry supply amount was 250 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 fired by using a static electric furnace in an atmosphere having an oxygen partial pressure of 0.021 MPa so as to maintain 750 ° C. for 37 hours.
  • the obtained fired powder was crushed with a pestle and classified with a sieve having an opening of 53 ⁇ m to obtain a spinel-type lithium manganese-containing composite oxide powder (sample).
  • the amount of water released into the tube is “170 ° C. to 300 ° C. KF moisture (ppm)”, the “room temperature to 170 ° C. KF moisture amount (ppm)” and the “170 ° C. to 300 ° C. KF moisture amount (ppm) ) ”Was defined as“ KF water content (ppm) ”.
  • 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 D50.
  • the average primary particle size (primary particle average diameter) of the spinel-type lithium manganese nickel-containing composite oxide powder (sample) obtained in Examples and Comparative Examples obtained in Examples and Comparative Examples was measured as follows. did. 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.
  • the D50 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 it is about 22 ⁇ m, the magnification is 2000 times, which is suitable for obtaining the average primary particle size in the image analysis software described later. Images can be taken.
  • the average primary particle size of the selected particles was determined from the captured images using image analysis software (MAC-VIEW ver. 4 manufactured by Mountec Co., Ltd.).
  • the average primary particle size is a cumulative 50% particle size (Heywood diameter: equivalent circle diameter) in volume distribution.
  • 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, 0.5 g of a sample (powder) is weighed in a glass cell for a flow method gas adsorption specific surface area measuring device MONOSORB LOOP (“Product Name MS-18” manufactured by Yuasa Ionics Co., Ltd.), and the MONOSORB LOOP pretreatment is performed. In the apparatus, the inside of the glass cell was replaced with nitrogen gas for 5 minutes at a gas amount of 30 mL / min, and then heat treatment was performed at 250 ° C. for 10 minutes in the nitrogen gas atmosphere. Then, the sample (powder) was measured by the BET single point method using the MONOSORB LOOP. The adsorbed gas at the time of measurement was a mixed gas of 30% nitrogen: 70% helium.
  • 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.
  • the crystal phase information was determined for the obtained XRD pattern, refined by the 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 at the 16d site, M1 element, M2 element, and the excess Li component at the 32e site.
  • the seat occupancy at each site and the atomic displacement parameter B were set to 1, and 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
  • Fd-3m Ole Choice 2
  • 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.
  • XRD measurement condition 2 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 absorbance ABS obtained above was confirmed, and the sample and KBr were adjusted so that the maximum value of the absorbance ABS appearing in the section where Wave Number was 400-700 cm ⁇ 1 was in the range of 0.5 to 1.0.
  • the ratio of tablets, pellet thickness, etc. were adjusted as appropriate, and re-measurement was performed. Further, when comparing between samples, the comparison was performed after normalization (normalization) so that the maximum absorbance of the obtained spectrum was 1.
  • the wave number interval ⁇ X (1.9285 cm ⁇ 1 ) of the data and the amount of change ⁇ Y in the infrared absorptance ABS are calculated.
  • Number, Y-axis was ⁇ Y / ⁇ X, and a curve was drawn.
  • An approximate curve was created from the drawn curve.
  • the approximate curve was a moving average of 5 sections.
  • the number of peaks was confirmed from the obtained approximate curve.
  • the peak refers to a maximum value, and refers to a portion that protrudes upward in the approximate curve.
  • the portion indicated by the downward arrow is a peak.
  • 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.
  • a positive electrode for a coin battery was prepared in the same manner as described above.
  • a negative electrode sheet coated with natural spherical graphite (Piotrek Co., Ltd., electrode capacity 1.6 mAh / cm 2 ) was used and punched out to a size of ⁇ 14 mm.
  • a separator (made of a porous polyethylene film) impregnated with an electrolytic solution in which LiPF 6 was dissolved at 1 mol / L was placed in a carbonate-based mixed solvent to prepare a 2032 type coin battery.
  • initial activation was performed by the method described below.
  • the battery was charged at a constant current and a constant potential to 4.9 V at 0.1 C at 25 ° C., and then discharged at a constant current to 2.9 V at 0.1 C. This was repeated for 3 cycles.
  • the actually set current value was calculated from the content of the positive electrode active material in the positive electrode.
  • a charge / discharge test was performed by the method described below using the coin battery after 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 200 times at 1 C. The C rate was calculated based on the discharge capacity at the third cycle at 25 ° C. during initial activation.
  • Table 1 shows the high temperature cycle life characteristic values of the examples and the comparative examples as relative values when the high temperature cycle life characteristic value of the comparative example 2 is 100.
  • 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 is punched into a size of 50 mm ⁇ 100 mm, and then pressed and dense at a press line 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.
  • the M element species in the following Table 1 means the constituent elements of the spinel-type lithium manganese-containing composite oxide other than Li, Mn, and O.
  • the obtained lithium manganese-containing composite oxide was fitted with a cubic crystal structure model of space group Fd-3m (Origin Choice 2) by XRD measurement, and observed intensity and calculated intensity. It was confirmed that Rwp and S representing the degree of coincidence are 5V-class spinels with Rwp ⁇ 10 or S ⁇ 2.5. Further, in the spectrum obtained by FT-IR, it was confirmed to be a spinel-type lithium manganese-containing composite oxide having three absorbance ABS peaks in the region of 435 to 525 cm ⁇ 1 . In addition, from the results of the battery performance evaluation test, it was confirmed that the metal Li reference potential had an operating potential of 4.5 V or higher.

Landscapes

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

Abstract

L'invention concerne un nouvel oxyde composite de lithium-manganèse de type spinelle de classe 5V qui rend possible l'extension d'une région de capacité à potentiel élevé et la réduction au minimum de la génération de gaz. L'oxyde composite de lithium-manganèse de type spinelle comprend du Li, du Mn, de l'O, et deux autres éléments ou plus et présente un potentiel de fonctionnement de 4,5 V ou plus en utilisant le Li métallique comme potentiel de référence. L'oxyde composite de lithium-manganèse de type spinelle est caractérisé en ce que trois pics pour l'absorbance ABS sont présents dans le segment de 432 à 525 cm-1 dans un spectre déterminé par FT-IR.
PCT/JP2016/063454 2015-04-30 2016-04-28 Oxyde composite de lithium-manganèse de type spinelle de classe 5v Ceased WO2016175312A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017515623A JP6630724B2 (ja) 2015-04-30 2016-04-28 ５ｖ級スピネル型リチウムマンガン含有複合酸化物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015093289 2015-04-30
JP2015-093289 2015-04-30

Publications (1)

Publication Number Publication Date
WO2016175312A1 true WO2016175312A1 (fr) 2016-11-03

Family

ID=57199203

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/063454 Ceased WO2016175312A1 (fr) 2015-04-30 2016-04-28 Oxyde composite de lithium-manganèse de type spinelle de classe 5v

Country Status (2)

Country Link
JP (1) JP6630724B2 (fr)
WO (1) WO2016175312A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106861776A (zh) * 2017-01-04 2017-06-20 潍坊学院 一种铁基锂离子提取材料的制备方法
WO2023205993A1 (fr) * 2022-04-25 2023-11-02 宁德时代新能源科技股份有限公司 Matériau oxyde de lithium-nickel-manganèse spinelle et son procédé de préparation
WO2024099774A1 (fr) * 2022-11-07 2024-05-16 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Méthode de production d'oxyde de métal de transition mixte au lithium de type spinelle

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003075376A1 (fr) * 2002-03-01 2003-09-12 Matsushita Electric Industrial Co., Ltd. Matiere active d'anode, procede de fabrication associe, et batterie secondaire d'electrolyte non aqueuse
JP2004119333A (ja) * 2002-09-30 2004-04-15 Ngk Insulators Ltd リチウムマンガン複合酸化物及びそれを正極活物質として用いたリチウム二次電池
JP2011089969A (ja) * 2009-10-26 2011-05-06 Toyota Central R&D Labs Inc 定量方法、プログラム及び定量装置
WO2012132155A1 (fr) * 2011-03-31 2012-10-04 戸田工業株式会社 Poudre de particules d'oxyde composite à base de manganèse-nickel, procédé de production associé, poudre de particules de matériau actif d'électrode positive destinée à des batteries secondaires à électrolyte non aqueux, procédé de production associé, et batterie secondaire à électrolyte non aqueux
WO2014030764A1 (fr) * 2012-08-24 2014-02-27 三井金属鉱業株式会社 Oxyde composite contenant du lithium, du manganèse et du nickel de spinelle
WO2014185343A1 (fr) * 2013-05-13 2014-11-20 日産自動車株式会社 Matière active d'électrode positive contenant une matière active en solution solide, électrode positive contenant ladite matière active d'électrode positive, batterie secondaire à électrolyte non aqueux utilisant ladite électrode positive
JP2014238976A (ja) * 2013-06-07 2014-12-18 住友金属鉱山株式会社 リチウム二次電池正極活物質と該正極活物質を用いたリチウム二次電池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003075376A1 (fr) * 2002-03-01 2003-09-12 Matsushita Electric Industrial Co., Ltd. Matiere active d'anode, procede de fabrication associe, et batterie secondaire d'electrolyte non aqueuse
JP2004119333A (ja) * 2002-09-30 2004-04-15 Ngk Insulators Ltd リチウムマンガン複合酸化物及びそれを正極活物質として用いたリチウム二次電池
JP2011089969A (ja) * 2009-10-26 2011-05-06 Toyota Central R&D Labs Inc 定量方法、プログラム及び定量装置
WO2012132155A1 (fr) * 2011-03-31 2012-10-04 戸田工業株式会社 Poudre de particules d'oxyde composite à base de manganèse-nickel, procédé de production associé, poudre de particules de matériau actif d'électrode positive destinée à des batteries secondaires à électrolyte non aqueux, procédé de production associé, et batterie secondaire à électrolyte non aqueux
WO2014030764A1 (fr) * 2012-08-24 2014-02-27 三井金属鉱業株式会社 Oxyde composite contenant du lithium, du manganèse et du nickel de spinelle
WO2014185343A1 (fr) * 2013-05-13 2014-11-20 日産自動車株式会社 Matière active d'électrode positive contenant une matière active en solution solide, électrode positive contenant ladite matière active d'électrode positive, batterie secondaire à électrolyte non aqueux utilisant ladite électrode positive
JP2014238976A (ja) * 2013-06-07 2014-12-18 住友金属鉱山株式会社 リチウム二次電池正極活物質と該正極活物質を用いたリチウム二次電池

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106861776A (zh) * 2017-01-04 2017-06-20 潍坊学院 一种铁基锂离子提取材料的制备方法
WO2023205993A1 (fr) * 2022-04-25 2023-11-02 宁德时代新能源科技股份有限公司 Matériau oxyde de lithium-nickel-manganèse spinelle et son procédé de préparation
WO2024099774A1 (fr) * 2022-11-07 2024-05-16 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Méthode de production d'oxyde de métal de transition mixte au lithium de type spinelle

Also Published As

Publication number Publication date
JP6630724B2 (ja) 2020-01-15
JPWO2016175312A1 (ja) 2018-02-22

Similar Documents

Publication Publication Date Title
JP6391857B2 (ja) スピネル型リチウムマンガン含有複合酸化物
JP6849812B2 (ja) 全固体型リチウム二次電池用正極活物質
JP6864104B2 (ja) 全固体型リチウム二次電池用正極活物質
JP6655070B2 (ja) ５ｖ級スピネル型リチウムマンガン含有複合酸化物
US9240595B2 (en) Spinel type lithium-manganese-nickel-containing composite oxide
EP3351510B1 (fr) Oxyde composite contenant du lithium nickel manganèse de type spinelle
CN110402239B (zh) 尖晶石型含锂镍锰复合氧化物
JP6630725B2 (ja) ５ｖ級スピネル型リチウムマンガン含有複合酸化物
JP6630724B2 (ja) ５ｖ級スピネル型リチウムマンガン含有複合酸化物
JP6649369B2 (ja) ５ｖ級スピネル型リチウムマンガン含有複合酸化物の製造方法
GB2529106A (en) Positive electrode active material for lithium secondary battery

Legal Events

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

Ref document number: 16786588

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017515623

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16786588

Country of ref document: EP

Kind code of ref document: A1