WO2016175310A1 - Procédé de production d'oxyde de composite de lithium-manganèse de type spinelle de classe 5v - Google Patents

Procédé de production d'oxyde de composite de lithium-manganèse de type spinelle de classe 5v Download PDF

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Publication number
WO2016175310A1
WO2016175310A1 PCT/JP2016/063450 JP2016063450W WO2016175310A1 WO 2016175310 A1 WO2016175310 A1 WO 2016175310A1 JP 2016063450 W JP2016063450 W JP 2016063450W WO 2016175310 A1 WO2016175310 A1 WO 2016175310A1
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WIPO (PCT)
Prior art keywords
spinel
composite oxide
type lithium
containing composite
lithium manganese
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PCT/JP2016/063450
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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
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三井金属鉱業株式会社
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Application filed by 三井金属鉱業株式会社 filed Critical 三井金属鉱業株式会社
Priority to CN201680002989.7A priority Critical patent/CN106715333B/zh
Priority to JP2017515621A priority patent/JP6649369B2/ja
Publication of WO2016175310A1 publication Critical patent/WO2016175310A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • 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.
  • the present invention relates to an oxide manufacturing method.
  • 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
  • a positive electrode active material for a secondary battery characterized by containing a spinel type lithium manganese composite oxide represented by the following formula: As a manufacturing method thereof, raw materials are weighed and mixed; Positive by firing in air or oxygen at temperatures up to 950 ° C. To obtain an active material 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.
  • Patent Document 6 relates to a method for producing a lithium manganese-containing composite oxide.
  • a method for producing a lithium transition metal oxide the crystallite size can be increased and the crystal structure distortion can be suppressed.
  • a method for producing a lithium transition metal oxide comprising a raw material mixing step, a firing step, and a heat treatment step, after firing at 850 ° C. or higher in an oxygen partial pressure of 0.015 MPa to 0.15 MPa
  • oxygen A method for producing a lithium-manganese-containing composite oxide is disclosed in which heat treatment is performed at a primary oxygen release temperature of ⁇ 50 ° C. in an atmosphere having a partial pressure of 0.03 MPa or more.
  • 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 does not provide a new manufacturing method that can achieve both expansion of the high potential capacity region and suppression of gas generation from the viewpoint of the manufacturing method of the 5V-class spinel type lithium manganese-containing composite oxide. It is what.
  • the present invention relates to a method for producing a spinel-type lithium manganese-containing composite oxide having an operating potential of 4.5 V or more at a metal Li reference potential, and a moisture content in a range of room temperature to 300 ° C. measured by a Karl Fischer moisture measuring device (“The spinel-type lithium manganese-containing composite oxide having a sulfur content of less than 0.34 wt% analyzed by ICP is less than atmospheric pressure.
  • a spinel type comprising a pressure heat treatment step in which heat treatment is performed at a temperature higher than 500 ° C. and lower than 850 ° C. in a treatment atmosphere having a higher pressure and an oxygen partial pressure in the atmosphere higher than the oxygen partial pressure in the atmosphere
  • a method for producing a lithium manganese-containing composite oxide is proposed.
  • the heat treatment is performed in a treatment atmosphere in which the overall pressure of the treatment atmosphere is higher than atmospheric pressure and the oxygen partial pressure in the atmosphere is higher than the oxygen partial pressure in the atmosphere. Accordingly, gas generation can be suppressed, a plateau region near 4.5 V can be expanded, and a high potential capacity region can be expanded, so that the energy density can be improved.
  • the manufacturing method proposed by the present invention it is possible to achieve both expansion of the high potential capacity region and suppression of gas generation.
  • 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
  • This 5V class spinel should just contain Li, Mn, and O and 2 or more types of elements other than these.
  • at least one element of “two or more elements other than these” is an element selected from the group consisting of Ni, Co, and Fe, and the other one element is Mg, Ti, Al, Ba.
  • An element selected from the group consisting of Cr, W, Mo, Y, Zr and Nb is preferred.
  • 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. For example, as 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. can be mentioned as a preferable example, These Mg, Ti, Al , Ba, Cr, W, Mo, Y, Zr, Co, Fe, and Nb may be included, and M2 may include another metal element.
  • “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.
  • the method for producing the present 5V-class spinel may include a 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 further equipped with the washing process can be mentioned.
  • the cleaning steps can be inserted in an appropriate order.
  • other steps can be added.
  • a pulverization / classification step of pulverizing and classifying after each step if necessary.
  • 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 processing object to be subjected to the cleaning process is, for example, each raw material before raw material mixing, raw material mixed powder after raw material mixing, processed powder after pressure heat treatment, processed product obtained in the firing step, and further crushing described later -The processed powder obtained at the classification process may be sufficient. 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 pressure heat treatment is put into the washing solution, stirred, and then allowed to stand to remove the supernatant.
  • 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 pressure heat treatment step has “KF moisture in the range of room temperature to 300 ° C.” measured by a Karl Fischer moisture measuring device (also referred to as “KF moisture measuring device”) of 2% or less, and ICP It is preferable that it is a spinel type lithium manganese containing complex oxide whose sulfur content analyzed by (3) is less than 0.34 wt%. If the KF moisture is greater than 2%, the atmosphere in the pressure furnace contains a large amount of water vapor, and the desired heat treatment atmosphere may not be created. In addition, when heat treatment is performed in a state containing a large amount of moisture, side reactions such as proton exchange between surface moisture and 5 V spinel Li may occur.
  • 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.
  • 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) at 170 ° C. to 300 ° C.”, and the above “KF moisture amount (ppm) at room temperature to 170 ° C.” And the above-mentioned “KF moisture content (170 ° C. to 300 ° C.)”.
  • the total 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. It is preferable to perform the heat treatment at a temperature lower than ° C.
  • oxygen is taken into the structure of the 5V spinel, thereby reducing oxygen deficiency and stabilizing the structure. Since the plateau region in the vicinity of 4.5 V 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 pressure heat treatment step is such that the overall pressure of the treatment atmosphere is a pressure greater than atmospheric pressure (0.1 MPa), for example, greater than 0.19 MPa, especially a pressure in an atmosphere of 0.20 MPa or more. preferable.
  • atmospheric pressure is 1.5 MPa or less, particularly 1.0 MPa or less.
  • Heat treatment is preferred. Thus, by heat-processing in a pressurized state, it becomes easier to take in oxygen and oxygen deficiency can be further suppressed.
  • the treatment atmosphere in the pressure heat treatment step is preferably an oxygen partial pressure higher than the oxygen partial pressure in the atmosphere, for example, an oxygen partial pressure of 0.06 Pma or more, and in particular, an oxygen partial pressure higher than 0.10 MPa.
  • the oxygen partial pressure is more preferably 0.15 MPa or more, particularly preferably higher than 0.19 MPa, and the oxygen partial pressure is more preferably 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 heat treatment temperature in the pressure heat treatment step 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 processing atmosphere is a pressure higher than atmospheric pressure and an oxygen partial pressure higher than 0.19 MPa, and a temperature higher than 500 ° C. and lower than 850 ° C., particularly 600
  • 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.
  • Such pressure heat treatment is performed by using a device such as a pressure furnace (pressurizable pressure 1.0 MPa), so that the overall pressure of the processing atmosphere is higher than atmospheric pressure, and Heating can be performed in a treatment atmosphere in which the oxygen partial pressure in the atmosphere is higher than the oxygen partial pressure in the atmosphere.
  • a device such as a pressure furnace (pressurizable pressure 1.0 MPa), so that the overall pressure of the processing atmosphere is higher than atmospheric pressure, and Heating can be performed in a treatment atmosphere in which the oxygen partial pressure in the atmosphere is higher than the oxygen partial pressure in the atmosphere.
  • a manufacturing method including a raw material mixing step, a granulation step, a firing step, a heat treatment step and a pressure heat treatment step in this order, and further comprising a washing step.
  • the cleaning steps can be inserted in an appropriate order. For example, it is possible to insert before or after one step or two or more steps among the above steps. 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. For example, it is possible to further add a wet pulverization process and other processes. Moreover, it is preferable to carry out a pulverization / classification step of pulverizing and classifying after each step, if necessary.
  • the raw material mixing step, wet pulverization step, granulation step, firing step, pressure heat treatment step and washing 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.
  • the specific surface area of the present 5V-class spinel can be reduced, and when used as a positive electrode active material for a lithium secondary battery, gas generation can be suppressed.
  • the plateau region near 4.5V can be enlarged.
  • This 5V-class spinel can have a specific surface area of 1.5 m 2 / g or less, especially 0.1 m 2 / g or more or 1.0 m 2 / g or less, of which 0.8 m 2 / g or less. It is particularly preferable that Thus, if the specific surface area is relatively small, the reactivity with the electrolytic solution is high, and the amount of gas generated, which is a problem that the 5V class spinel has characteristically, can be suppressed.
  • 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. 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%. Subsequently, the mixture was pulverized at 1300 rpm for 60 minutes with a wet pulverizer to obtain a pulverized slurry having an average particle diameter (D50) of 0.60 ⁇ m or less.
  • D50 average particle diameter
  • 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 is used for spraying, granulation drying is performed by adjusting the temperature so that the spray pressure is 0.33 MPa, the slurry supply amount is 350 ml / min, and the outlet temperature of the drying tower is 100 to 110 ° C. It was.
  • 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 38 hours, and then 750 ° C. in an atmosphere having an oxygen partial pressure of 0.021 MPa.
  • the calcined mass obtained by heat treatment was put in a mortar and crushed with a pestle, 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.
  • the collected sediment was dried at 120 ° C. for 10 hours. Then, it dried for 7 hours in the state heated so that product temperature might be 500 degreeC. After drying, it 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).
  • this spinel type lithium manganese-containing composite oxide powder (KF moisture content: 144 ppm, sulfur content: 0.02%) was subjected to pressure heat treatment using a pressure furnace (manufactured by Hiroki Co., Ltd.). That is, 200 g of a sample 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 1.5 ° C./min. Heat to 740 ° 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 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 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.
  • 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 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.).
  • a twin jet nozzle is used for spraying, granulation drying is performed by adjusting the temperature so that the spray pressure is 0.15 MPa, the slurry supply amount is 400 ml / min, and the outlet temperature of the drying tower is 100 to 110 ° C. It was.
  • 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 36 hours, and then 750 ° C. in an atmosphere having an oxygen partial pressure of 0.021 MPa. Was heat treated to hold for 37 hours.
  • the calcined mass obtained by heat treatment was put in a mortar and crushed with a pestle, 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.
  • the collected sediment was dried at 120 ° C. for 10 hours. Then, it dried for 7 hours in the state heated so that product temperature might be 500 degreeC. After drying, it 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).
  • this spinel type lithium manganese-containing composite oxide powder (KF moisture content: 130 ppm, sulfur content: 0.03%) was subjected to pressure heat treatment using a pressure furnace (manufactured by Hiroki Co., Ltd.). That is, 200 g of a sample 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 1.5 ° C./min. Heat to 720 ° C.
  • a pressure furnace manufactured by Hiroki Co., Ltd.
  • 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) 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.
  • 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 is used for spraying, granulation drying is performed by adjusting the temperature so that the spray pressure is 0.15 MPa, the slurry supply amount is 400 ml / min, and the outlet temperature of the drying tower is 100 to 110 ° C. It was.
  • 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. Was heat treated to hold for 37 hours.
  • the calcined mass obtained by heat treatment was put in a mortar and crushed with a pestle, 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.
  • the collected sediment was dried at 120 ° C. for 10 hours. Then, it dried for 7 hours in the state heated so that product temperature might be 500 degreeC. After drying, it 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).
  • this spinel type lithium manganese-containing composite oxide powder (KF moisture content: 100 ppm, sulfur content: 0.04%) was subjected to pressure heat treatment using a pressure furnace (manufactured by Hiroki Co., Ltd.). That is, 200 g of a sample 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 1.5 ° C./min. Heat to 730 ° C.
  • a pressure furnace manufactured by Hiroki Co., Ltd.
  • 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) 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 is used for spraying, granulation drying is performed by adjusting the temperature so that the spray pressure is 0.16 MPa, the slurry supply amount is 390 ml / min, and the outlet temperature of the drying tower is 100 to 110 ° C. It was.
  • 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 37 hours, and then the obtained baked lump was put in a mortar and a pestle And then 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.
  • this spinel type lithium manganese-containing composite oxide powder (KF moisture content: 277 ppm, sulfur content: 0.27%) was subjected to pressure heat treatment using a pressure furnace (manufactured by Hiroki Co., Ltd.). That is, 200 g of a sample 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. at a temperature rate and hold for 15 hours, then cool down to room temperature at a rate of 0.3 ° C./min while continuing oxygen inflow and spinel lithium manganese-containing composite oxide powder (sample) Got.
  • a pressure furnace manufactured by Hiroki Co., Ltd.
  • the obtained spinel-type lithium manganese-containing composite oxide powder (sample) was classified with a sieve having an opening of 53 ⁇ m. Thereafter, 1 kg of the sample was put into a plastic beaker (capacity 5000 mL) containing 2000 mL of ion-exchanged water having a pH of 6 to 7 and a temperature of 25 ° C., and was rotated at 400 to 550 rpm using a stirrer (propeller area 33 cm 2 ). Stir for minutes. After stirring, stirring was stopped and the stirrer was taken out of the water and allowed to stand for 10 minutes. And the supernatant liquid was removed by decantation, the remaining slurry was filtered with the suction filter (filter paper No.
  • Example 5 In Example 3, the raw material weighing value was changed, the spraying pressure during granulation was changed to 0.19 MPa, the slurry supply amount was 350 ml / min, the pressure treatment conditions were oxygen partial pressure 0.89 MPa, and the entire treatment atmosphere A spinel-type lithium manganese-containing composite oxide powder (sample) was obtained in the same manner as in Example 3 except that the pressure was changed to 0.90 MPa.
  • the chemical analysis of the sample was carried out, they were Li: 4.0 wt%, Ni: 15.5 wt%, Mn: 39.3 wt%, Ti: 5.1%, and B: 0.1%.
  • Example 6 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) 1 ⁇ m of titanium oxide and zirconium oxide having an average particle diameter (D50) of 31 ⁇ 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.
  • 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 Zr 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, and granulation drying was performed by adjusting the temperature so that the spray pressure was 0.51 MPa, the slurry supply amount was 313 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.
  • Example 7 In Example 6, 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 and titanium oxide having an average particle diameter (D50) of 1 ⁇ m, changing the weighing value of the raw material, changing the spraying pressure during granulation drying to 0.47 MPa, setting the slurry supply amount to 336 ml / min, 850 A spinel-type lithium manganese-containing composite oxide powder (sample) was obtained in the same manner as in Example 6 except that firing was performed so that the temperature was maintained for 37 hours.
  • 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: 15.1 wt%, Mn: 42.5 wt%, Ti: It was 2.7 wt%.
  • Example 8 In Example 6, 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 and titanium oxide having an average particle diameter (D50) of 1 ⁇ m, changing the weighing value of the raw material, changing the spraying pressure during granulation drying to 0.48 MPa, and setting the slurry supply amount to 316 ml / min, 850 A spinel-type lithium manganese-containing composite oxide powder (sample) was obtained in the same manner as in Example 6 except that the temperature was kept at 37 ° C.
  • Example 8 Li: 4.1 wt%, Ni: 14.7 wt%, Mn: 41.4 wt%, Ti: It was 4.0 wt%.
  • Example 9 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) 1 ⁇ 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.
  • 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, 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.
  • Li raw material and Ti raw material were added to the slurry, 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 is used for spraying, granulation drying is performed by adjusting the temperature so that the spray pressure is 0.14 MPa, the slurry supply rate is 400 ml / min, and the outlet temperature of the drying tower is 100 to 110 ° C. It was.
  • 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 940 ° C. for 37 hours, and then 740 ° C. in an atmosphere having an oxygen partial pressure of 0.021 MPa. Was heat treated to hold for 37 hours.
  • the calcined mass obtained by heat treatment was put in a mortar and crushed with a pestle, 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.
  • the collected sediment was dried at 120 ° C. for 10 hours. Then, it dried for 7 hours in the state heated so that product temperature might be 500 degreeC. After drying, it 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).
  • this spinel type lithium manganese-containing composite oxide powder (KF moisture content: 100 ppm, sulfur content: 0.04%) was subjected to pressure heat treatment using a pressure furnace (manufactured by Hiroki Co., Ltd.). That is, 200 g of a sample 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 pressurizing furnace, the oxygen partial pressure was adjusted to 0.20 MPa, and the overall pressure of the processing atmosphere was adjusted to 0.22 MPa. Heat to 730 ° C.
  • a pressure furnace manufactured by Hiroki Co., Ltd.
  • Example 10 In Example 9, 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, aluminum hydroxide with an average particle diameter (D50) of 2 ⁇ m, and lithium tetraborate with an average particle diameter (D50) of 60 ⁇ m, the raw material weighed The B raw material was added to the slurry at the same timing as the Li raw material and the Ti raw material, mixed and stirred, the spray pressure during granulation drying was changed to 0.14 MPa, the slurry supply rate was 421 ml / min, and the oxygen-containing atmosphere
  • the spinel type lithium matrix was the same as in Example 9 except that the temperature of the pressure heat treatment was 720 ° C.
  • Example 10 a cancer-containing composite oxide powder (sample).
  • 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 is used for spraying, granulation drying is performed by adjusting the temperature so that the spray pressure is 0.19 MPa, the slurry supply amount is 350 ml / min, and the outlet temperature of the drying tower is 100 to 110 ° C. It was.
  • 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.
  • they 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 is used for spraying, granulation drying is performed by adjusting the temperature so that the spray pressure is 0.33 MPa, the slurry supply amount is 350 ml / min, and the outlet temperature of the drying tower is 100 to 110 ° C. It was.
  • 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. Was heat treated to hold for 37 hours.
  • 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 is used for spraying, granulation drying is performed by adjusting the temperature so that the spray pressure is 0.46 MPa, the slurry supply rate is 250 ml / min, and the outlet temperature of the drying tower is 100 to 110 ° C. It was.
  • 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).
  • Sample When the chemical analysis of the sample was conducted, they were Li: 4.0 wt%, Ni: 15.2 wt%, Mn: 39.7 wt%, and Ti: 5.0%.
  • 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 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 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 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.
  • Crystal phase information was determined for the obtained XRD pattern using integrated powder X-ray analysis software PDXL (manufactured by Rigaku Co., Ltd.), and refined by a WPPF (Whole powder pattern fitting) method.
  • 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.
  • Rwp is more preferably less than 8, more preferably less than 6, and S is more preferably less than 2.3, and even more preferably less than 2.1.
  • 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. That is, the average value of cps with 2 ⁇ of 14.0-14.5 ° and 16.0 ° to 16.5 ° is the background (BG) intensity A, and the maximum value of cps of 14.5 to 16.0 If the difference (B ⁇ A) is 25 cps or more when the peak intensity B is, a peak is present. 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.
  • 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 in the following Table 1 means a constituent element of the spinel-type lithium manganese-containing composite oxide other than Li, Mn, and O.
  • the lithium manganese-containing composite oxide obtained after the firing and the finally obtained lithium manganese-containing composite oxide were measured in the space group Fd-3m (Origin Choice 2) by XRD measurement in any of Examples 1 to 10. Fitting with a cubic crystal structure model, it was confirmed that 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. Further, it was confirmed to be a spinel-type lithium manganese-containing composite oxide having a peak in an XRD pattern (2 ⁇ is 14.5 to 16.0 °). Also, from the results of the battery performance evaluation test, in any of Examples 1 to 10, the finally obtained lithium manganese-containing composite oxide had an operating potential of 4.5 V or more at the metal Li reference potential. It was confirmed that there was.
  • the overall pressure of the processing atmosphere is higher than atmospheric pressure after firing in the manufacturing process of the 5V-class spinel type lithium manganese-containing composite oxide.
  • a spinel-type lithium manganese-containing composite oxide heated to a temperature higher than 500 ° C. and lower than 850 ° C. in a treatment atmosphere having a pressure and an oxygen partial pressure in the atmosphere higher than the oxygen partial pressure in the atmosphere,
  • oxygen is taken into the structure and a stable crystal structure can be obtained.

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  • 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 procédé de production d'un nouvel oxyde de composite de lithium-manganèse de type spinelle de classe 5V qui rend possible l'extension d'une région de capacité à potentiel élevé et de réduire au minimum la génération de gaz. Le procédé permet de produire un oxyde de composite de lithium-manganèse de type spinelle présentant un potentiel de fonctionnement de 4,5 V ou plus à l'aide de Li métallique en tant que potentiel de référence. Le procédé de production d'un oxyde de composite de lithium-manganèse de type spinelle comprend une étape de mise sous pression/traitement thermique au cours de laquelle un oxyde de composite de lithium-manganèse de type spinelle ayant un taux d'humidité KF de 2 % ou moins et une teneur en soufre inférieure à 0,34 % en poids, tel qu'analysé par ICP, est soumis à un traitement thermique à une température supérieure à 500 °C mais inférieure à 850 °C dans une atmosphère de traitement où la pression totale de ladite atmosphère de traitement est supérieure à la pression atmosphérique, et la pression partielle d'oxygène dans l'atmosphère de traitement est supérieure à la pression partielle d'oxygène dans l'atmosphère.
PCT/JP2016/063450 2015-04-30 2016-04-28 Procédé de production d'oxyde de composite de lithium-manganèse de type spinelle de classe 5v WO2016175310A1 (fr)

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CN107808952B (zh) * 2017-10-13 2021-03-30 湖南力合厚浦科技有限公司 一种高振实密度高容量复合镍钴锰氧化物三元锂离子电池正极材料的制备方法

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