WO2018096999A1 - Oxyde complexe de lithium-manganèse et son procédé de production - Google Patents

Oxyde complexe de lithium-manganèse et son procédé de production Download PDF

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WO2018096999A1
WO2018096999A1 PCT/JP2017/041059 JP2017041059W WO2018096999A1 WO 2018096999 A1 WO2018096999 A1 WO 2018096999A1 JP 2017041059 W JP2017041059 W JP 2017041059W WO 2018096999 A1 WO2018096999 A1 WO 2018096999A1
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charge
crystal phase
lithium
layered rock
composite oxide
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English (en)
Japanese (ja)
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田渕　光春
敏勝 小島
京介 堂前
英香 渋谷
田村　宜之
亮太 弓削
薫 成田
直樹 河野
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国立研究開発法人産業技術総合研究所
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium manganese composite oxide and a method for producing the same.
  • Lithium ion secondary batteries are now being put into practical use as electric vehicles, plug-in hybrid vehicles, and other large-scale batteries for power load leveling systems such as solar cells and wind power generation. Increasingly.
  • positive electrode active materials include lithium-containing transition metal oxides such as lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ), and negative electrodes
  • lithium-containing transition metal oxides such as lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ), and negative electrodes
  • the active material graphite, lithium titanate, silicon oxide or the like is used.
  • the positive electrode active material functions as the only lithium ion supply source, and the amount of lithium ions that can be reversibly taken in and out of the positive electrode active material becomes a capacity that can be used as a battery.
  • the voltage of the hour becomes the maximum voltage as a battery. Therefore, it is no exaggeration to say that what kind of positive electrode active material is selected determines the battery performance.
  • the crystal structure of this material is a layered rock-salt structure, but it is known that it gradually changes to a crystalline phase of a lithium manganese spinel structure represented by LiMn 2 O 4 as the cycle progresses (for example, Non-Patent Document 2).
  • LiFe 1/2 Ni 1/2 O 2 —Li 2 MnO 3 positive electrode active material is also known (for example, Patent Document 1, Non-Patent Document 3).
  • the present invention has been made in view of the current state of the prior art described above, and an object of the present invention is to provide a lithium manganese composite oxide positive electrode material excellent in cycle characteristics, in particular, similarity in charge / discharge curve shape. .
  • the present invention includes the following configurations. Item 1.
  • Item 2. The lithium manganese composite oxide according to Item 1, wherein m1 and m2 are 0 in the general formula (1).
  • Item 3. The lithium manganese composite oxide according to Item 1 or 2, comprising a mixed phase of the crystal phase of the spinel structure and the crystal phase of a layered rock salt structure.
  • Item 4. Item 4.
  • Item 5. The method for producing a lithium manganese composite oxide according to any one of Items 1 to 4, Using lithium manganese based composite oxide containing a layered rock salt type crystal phase as a positive electrode active material, after performing an activation treatment of performing multiple charge / discharge cycles while gradually increasing the charge capacity or charge potential, A manufacturing method provided with the process of performing a charging / discharging cycle.
  • Item 6. Item 6. The manufacturing method according to Item 5, wherein the maximum potential in the charge / discharge cycle of the activation treatment is 4.55 V or more.
  • Item 7. Item 7.
  • Item 5 The manufacturing method according to Item 5 or 6, wherein a maximum potential in a charge / discharge cycle performed after the activation treatment is less than 4.70V.
  • Item 8. Item 5.
  • Item 9. Item 9.
  • a method for suppressing a change in a charge / discharge curve when a charge / discharge cycle of a lithium ion secondary battery is performed Using lithium manganese based composite oxide containing a layered rock salt type crystal phase as a positive electrode active material, after performing an activation treatment of performing multiple charge / discharge cycles while gradually increasing the charge capacity or charge potential, A method comprising performing a charge / discharge cycle such that a maximum potential is lower than a maximum potential in the activation treatment.
  • the present invention it is possible to provide a lithium-manganese composite oxide having a spinel structure crystal phase that can suppress adverse effects on charge / discharge characteristics by charging / discharging under specific charge / discharge test conditions. Therefore, it is possible to provide a lithium manganese composite oxide positive electrode material excellent in cycle characteristics, in particular, similarity of charge / discharge curve shapes.
  • Example 2 shows a charge / discharge curve measured in order to obtain the sample of Example 1.
  • FIG. A curve rising to the right corresponds to charging, and a curve falling to the right corresponds to discharging.
  • the numbers correspond to the number of cycles, the suffix c corresponds to charging, and the suffix d corresponds to discharging.
  • the measured (+) and calculated (solid line) X-ray diffraction patterns of the sample obtained in Example 2 are shown.
  • FIG. 2 shows a charge / discharge curve measured in order to obtain a sample of Example 2.
  • FIG. A curve rising to the right corresponds to charging, and a curve falling to the right corresponds to discharging.
  • the numbers correspond to the number of cycles, the suffix c corresponds to charging, and the suffix d corresponds to discharging.
  • the measured (+) and calculated (solid line) X-ray diffraction patterns of the sample obtained in Example 3 are shown.
  • the upper part is the crystal phase of the hexagonal layered rock salt structure, and the lower part is the crystal phase of the spinel structure of the present invention.
  • 2 shows a charge / discharge curve measured to obtain a sample of Example 3.
  • FIG. A curve rising to the right corresponds to charging, and a curve falling to the right corresponds to discharging.
  • the numbers correspond to the number of cycles, the suffix c corresponds to charging, and the suffix d corresponds to discharging.
  • the measured (+) and calculated (solid line) X-ray diffraction patterns of the sample obtained in Comparative Example 1 are shown.
  • the upper part is the crystal phase of the hexagonal layered rock salt structure, and the lower part is the crystal phase of the spinel structure of the present invention.
  • 2 shows a charge / discharge curve measured to obtain a sample of Comparative Example 1. A curve rising to the right corresponds to charging, and a curve falling to the right corresponds to discharging. The numbers correspond to the number of cycles, the suffix c corresponds to charging, and the suffix d corresponds to discharging. The measured (+) and calculated (solid line) X-ray diffraction patterns of the sample obtained in Comparative Example 2 are shown.
  • the upper part is the crystal phase of the hexagonal layered rock salt structure, and the lower part is the crystal phase of the spinel structure of the present invention.
  • 2 shows a charge / discharge curve measured to obtain a sample of Comparative Example 2. A curve rising to the right corresponds to charging, and a curve falling to the right corresponds to discharging. The numbers correspond to the number of cycles, the suffix c corresponds to charging, and the suffix d corresponds to discharging. The measured (+) and calculated (solid line) X-ray diffraction patterns of the sample obtained in Reference Example 1 are shown.
  • the upper part is the crystal phase of the hexagonal layered rock salt structure, and the lower part is the crystal phase of the spinel structure of the present invention.
  • the contribution of the PTFE peak (around 18 °) and the acetylene black peak (around 25 °) has been removed.
  • the measured (+) and calculated (solid line) X-ray diffraction patterns of the sample obtained in Reference Example 2 are shown.
  • the upper part is the crystal phase of the hexagonal layered rock salt structure, and the lower part is the crystal phase of the spinel structure of the present invention.
  • the contribution of the PTFE peak (around 18 °) and the acetylene black peak (around 25 °) has been removed.
  • the measured (+) and calculated (solid line) X-ray diffraction patterns of the sample obtained in Reference Example 3 are shown.
  • the upper part is the crystal phase of the hexagonal layered rock salt structure, and the lower part is the crystal phase of the spinel structure of the present invention.
  • the contribution of the PTFE peak (around 18 °) and the acetylene black peak (around 25 °) has been removed.
  • Lithium manganese complex oxide The lithium manganese complex oxide of the present invention has the general formula (1): ⁇ Li 1-xa (Mn 1-n1-m1 M 1 n1 Ti m1 ) x ⁇ 8a [(Mn 1-n2-m2 M 2 n2 Ti m2 ) y Li 2-yb ] 16d O 4 (1) [Wherein, M 1 and M 2 are the same or different and represent at least one selected from the group consisting of Fe, Co and Ni.
  • x, y, n1, n2, m1, m2, a and b are 0 ⁇ x ⁇ 0.50, 0 ⁇ y ⁇ 1.60, 0 ⁇ n1 ⁇ 0.50, 0 ⁇ n2 ⁇ 0.50, 0 ⁇ m1 ⁇ 0.20, 0 ⁇ m2. ⁇ 0.20, 0 ⁇ a ⁇ 1-x, 0 ⁇ b ⁇ 2-y.
  • the inside of ⁇ shows the oxygen 4 coordination position (8a position) in the structure, and the [] shows the oxygen 6 coordination position (16d position) in the structure.
  • the oxygen occupancy position transition metal occupancy is 80 atomic% or less and includes a crystal phase of a spinel structure (particularly a crystal phase of a cubic spinel structure).
  • LiMn 2 O 4 called positive spinel (all transition metal ions are present at the 16d position) from the viewpoint of the similarity of the charge / discharge curve shape. It is preferable that the crystal phase has a LiMn 2 O 4 type spinel structure composed of only a crystal phase having a unit cell similar to the above.
  • the crystal phase of the spinel structure will be described by taking LiMn 2 O 4 as an example.
  • the crystal structure of LiMn 2 O 4 drawn by the crystal structure drawing software VESTA K. Momma and F. Izumi, J. Appl. Cryst., 44, 1272-1276 (2011).
  • VESTA crystal structure drawing software
  • Mn occupies 100 atomic% of oxygen 6-coordinated position called 16d position (corresponding to 2.0 per composition formula), and Li is oxygen 4-coordinated called 8a position. Present at the position.
  • Li 4 Mn 5 O 12 which is a known substance with the lowest 16d-position Mn content
  • the composition formula when the composition formula is considered as Li 4/3 Mn 5/3 O 4 , ⁇ Li ⁇ 8a [Li 1/3 Mn 5 / 3 ] 16dO 4, and the 16d position Mn occupancy is 5/6 (83 atomic%, 5/3 per composition formula).
  • the lithium manganese-based composite oxide of the present invention has an oxygen 6-coordinated transition metal occupancy rate of 80 atomic% or less, and is characterized by being lower than any of known materials. The reason why the lithium manganese composite oxide of the present invention shows such a unique transition metal ion distribution is considered to be derived from the similarity to the layered rock salt type crystal structure which is the parent structure.
  • Fig. 1 shows the ion distribution in the crystal phase of the spinel structure and the crystal phase of the layered rock salt structure (space group monoclinic C2 / m or hexagonal crystal).
  • the spinel structure belongs to the same cubic close-packed rock salt structure as the layered rock salt structure, and has an alternate layered structure of Mn single layers and Li-Mn mixed layers.
  • the monoclinic Li 2 MnO 3 type layered rock salt structure (C2 / m) is used as the parent structure, so there is no Mn single layer, and a certain amount of Li (maximum 33 Therefore, it is an Mn-Li mixed layer.
  • the activation process by the step charging method disturbs the transition metal distribution, and some Mn moves to the Li-Mn mixed layer and the crystal structure is hexagonal.
  • the staged charging method is a charge / discharge cycle by capacity or potential regulated charging, and after that, the charge capacity is gradually increased (or the charge potential is gradually increased) and divided into several times, and finally the target charge is achieved. It means a method of cycling in the potential range.
  • the spinel structure crystalline phase of the lithium manganese composite oxide of the present invention has the same transition metal ion distribution as the layered rock salt structure crystalline phase, and therefore has the same charge / discharge characteristics. It can be interpreted that it is an oxygen-rich spinel phase because the transition metal occupancy at the 16d position is low and the O / Mn ratio is large.
  • the x value (corresponding to the ratio of transition metal ions present at the 8a position) is 0.50 (50 atomic%) or less.
  • the position 8a is a Li ion diffusion path at the time of charge / discharge, and if there are a large amount of transition metal ions there, it is preferable that the high-speed ion diffusion is hindered, resulting in deterioration of charge / discharge characteristics. From this point of view, the 8a position occupancy x is 0 to 0.50, preferably 0 to 0.20.
  • the y value (corresponding to the ratio of transition metal ions per composition formula existing at the 16d position) is 1.60 (80 atomic%) or less.
  • the 16d position is one of the oxygen six-coordinate position lattice positions in the spinel phase, and 0 ⁇ y ⁇ 1.60, preferably 0.10 from the viewpoint of maintaining an oxygen-rich spinel composition having good charge / discharge characteristics. ⁇ 1.00.
  • the a value and the b value can vary depending on the charge / discharge depth.
  • the a value and b value are small at the end of discharge and large during charging. Specifically, the value a is 0 when fully discharged and 1f-x when fully charged.
  • the b value is 0 when fully discharged and 2-y when fully charged.
  • the lithium manganese composite oxide of the present invention contains at least one selected from the group consisting of a specific amount of Fe, Co and Ni in addition to Mn.
  • Fe ions, Co ions, and Ni ions are effective in improving the reversibility of the charge / discharge curve and reducing hysteresis.
  • the content of Fe, Co, and Ni ions with respect to the amount of transition metal present at the 8a position and the amount of transition metal present at the 16d position is 50 atomic% or less (corresponding to 0 ⁇ n1 ⁇ 0.50, 0 ⁇ n2 ⁇ 0.50) , Preferably 5 to 50 atomic% (corresponding to 0.05 ⁇ n1 ⁇ 0.50, 0.05 ⁇ n2 ⁇ 0.50), more preferably 15 to 40 atomic% (corresponding to 0.15 ⁇ n1 ⁇ 0.40, 0.15 ⁇ n2 ⁇ 0.40) is there. Further, as described in the literature, a part of Mn can be substituted with Ti for the purpose of further improving the cycle characteristics (M.
  • the content of Ti ions with respect to the amount of transition metal present at the 8a position and the amount of transition metal present at the 16d position is 20 atomic% or less (corresponding to 0 ⁇ m1 ⁇ 0.20, 0 ⁇ m2 ⁇ 0.20) , Preferably 2 to 20 atomic% (corresponding to 0.02 ⁇ m1 ⁇ 0.20, 0.02 ⁇ m2 ⁇ 0.20), more preferably 5 to 10 atomic% (corresponding to 0.05 ⁇ m1 ⁇ 0.10, 0.05 ⁇ m2 ⁇ 0.10) is there.
  • the crystal phase of the spinel structure possessed by the lithium manganese composite oxide of the present invention is an oxygen-rich spinel phase as described above.
  • the oxygen-rich spinel phase is generated by a specific charge / discharge cycle from the crystal phase of the layered rock salt type structure, which is the parent structure, and therefore may be mixed with the crystal phase of the layered rock salt type structure.
  • the lithium manganese composite oxide of the present invention may be a single phase of a spinel type crystal phase or a mixed phase of a spinel type crystal phase and a layered rock salt type crystal phase. Good.
  • the crystalline phase of the spinel structure of the lithium manganese composite oxide of the present invention is an oxygen-rich spinel phase and a crystalline phase with a low transition metal occupancy at the 16d position, which adversely affects charge / discharge characteristics. Since it does not give, it is preferable that there are many this oxygen rich spinel phases. Therefore, the transition metal occupancy in the transition metal layer (oxygen 6 coordination position; 16d position) is 80 atomic% or less, preferably 30 to 60 atoms so that an oxygen-rich spinel phase can be obtained by a specific charge / discharge cycle. %. For the same reason, the transition metal occupancy at the oxygen 4 coordination position (position 8a) is 30 atomic% or less, preferably 1 to 20 atomic%.
  • the mixing ratio of the crystal phase of the layered rock salt structure and the spinel structure is preferably 90: 10 to 10: 90, more preferably 70: 30 to 30: 70 in terms of mass ratio. Further, up to 50 mass% of the cubic rock salt type crystal phase may be mixed with the layered rock salt type crystal phase in addition to the parent structure within a range that does not greatly affect the charge / discharge characteristics.
  • the lithium manganese based composite oxide of the present invention is a lithium hydroxide, lithium carbonate, iron compound, nickel compound, manganese compound, cobalt compound, titanium compound, and these compounds in a range that does not significantly affect the charge / discharge characteristics.
  • an impurity phase such as a composite metal compound containing two or more of lithium, iron, cobalt, titanium and nickel.
  • the amount of the impurity phase can be within a range that does not impair the effects of the present invention. For example, 0 to 10 wt% is preferable in the lithium manganese composite oxide of the present invention, and 1 to 5 wt% is more preferable. .
  • the crystal phase of the spinel structure possessed by the lithium manganese composite oxide of the present invention is generated by performing a specific charge / discharge cycle from the crystal phase of the layered rock salt structure which is the parent structure. To do.
  • the crystal phase of the spinel structure possessed by the lithium manganese composite oxide of the present invention is generated, for example, by the following process.
  • the crystalline phase of the layered rock-salt structure that is the activated phase by charging from the crystalline phase of the layered rock-salt structure that is the parent phase (especially the crystalline phase of the monoclinic layered rock-salt structure) Crystal phase) and oxygen-rich spinel phase (corresponding to the Li-free crystal phase of the present invention), and then the crystal phase of the layered rock salt structure that is the activation phase (especially the crystal phase of the hexagonal layered rock salt structure)
  • a crystal phase having a layered rock salt structure in particular, a crystal phase having a hexagonal layered rock salt structure
  • a crystal phase having a spinel structure of the present invention are generated.
  • the lithium manganese composite oxide of the present invention can be interpreted as the oxygen-rich spinel phase generated after charging remaining after discharging. Therefore, in order to produce the lithium manganese composite oxide of the present invention, (1) a step of producing a crystal phase of a layered rock salt type structure (particularly a crystal phase of a monoclinic layered rock salt type structure); There are three processes: a process for producing a crystalline phase with a layered rock salt structure (particularly a crystalline phase with a hexagonal layered rock salt structure), and (3) a process for obtaining a crystalline phase with a spinel structure according to the present invention. preferable.
  • step (1) First, step (1) will be described.
  • any of the conventionally known methods can be adopted, such as coprecipitation-firing method, coprecipitation-hydrothermal-firing method.
  • Any solid phase reaction method can be used and is not particularly limited.
  • coprecipitation can easily produce a complex oxide having excellent charge and discharge characteristics by uniformly distributing a desired transition metal in the structure with a minimum process. It is preferable to use a firing method.
  • An example of a production method using a coprecipitation-firing method is as follows: i) First, a manganese compound, at least one selected from the group consisting of an iron compound, a cobalt compound, and a nickel compound, and, if necessary, a titanium compound. A coprecipitate is formed by gradually adding an aqueous solution containing the mixture to the alkaline solution, and then the precipitate is aged by wet oxidation. ii) Next, by heating (especially firing) in the presence of a lithium compound, a crystal phase having a layered rock salt structure (particularly a crystal phase having a monoclinic layered rock salt structure) can be obtained. This manufacturing method will be specifically described below.
  • the process i) will be described.
  • a component capable of forming a mixed aqueous solution containing these compounds is preferable.
  • a water-soluble compound e.g., water-soluble salts such as manganese, iron, cobalt, nickel, or titanium chloride, nitrate, sulfate, oxalate, and acetate; Can be mentioned.
  • permanganates such as potassium permanganate can also achieve uniform distribution of metals other than lithium ions, and charge / discharge characteristics can be further improved.
  • water-soluble compounds can employ both anhydrides and hydrates. Further, even water-insoluble compounds such as oxides of manganese, iron, cobalt, nickel, or titanium can be dissolved in an acid such as hydrochloric acid or nitric acid and used as an aqueous solution. Moreover, the raw material compound which has several metal seed
  • the mixing ratio of the manganese compound, the iron compound, the cobalt compound, the nickel compound, and, if necessary, the titanium compound can be the same element ratio as each element ratio in the target lithium manganese composite oxide of the present invention.
  • the concentration of each compound is not particularly limited, and can be determined as appropriate so that a uniform mixed aqueous solution can be formed and a coprecipitate can be smoothly formed.
  • the total concentration of the manganese compound, iron compound, cobalt compound and nickel compound and, if necessary, the titanium compound is preferably 0.01 to 5 mol / L, particularly preferably 0.1 to 2 mol / L.
  • water can be used alone, or a water-alcohol mixed solvent containing a water-soluble alcohol such as methanol or ethanol can be used.
  • a water-alcohol mixed solvent containing a water-soluble alcohol such as methanol or ethanol
  • the water-soluble alcohol acts as an antifreeze and precipitates can be formed at temperatures below 0 ° C.
  • impurities such as lithium ferrite and manganese ferrite, which are likely to occur during precipitation formation when Fe is contained, can be further suppressed, and as a result, uniform precipitation can be obtained.
  • a manganese source such as potassium permanganate, which is difficult to form a precipitate only with water, can be used, the range of raw material selection is further expanded.
  • the amount of alcohol used can be appropriately determined according to the target precipitation temperature, the concentration when potassium permanganate is used, and is usually 50 parts by mass or less (for example, 10 parts by mass with respect to 100 parts by mass of water). It is preferable that the amount used is about 50 parts by mass).
  • a precipitate can be generated by making the mixed aqueous solution alkaline.
  • Conditions for forming a good precipitate cannot be defined unconditionally because it varies depending on the type, concentration, etc. of each compound contained in the mixed aqueous solution.
  • pH 8 or higher for example, pH 8 to 14
  • pH 11 or higher for example, More preferred is pH 11-14.
  • the method of making the mixed aqueous solution alkaline is not particularly limited, and it is usually preferable to add the mixed aqueous solution to an aqueous solution containing an alkali in order to form a uniform precipitate.
  • a precipitate (coprecipitate) can also be formed by a method of adding an alkali or an aqueous solution containing an alkali to the mixed aqueous solution.
  • alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide, ammonia and the like can be used.
  • these alkalis can be used as an aqueous solution having a concentration of 0.1 to 20 mol / L, particularly 0.3 to 10 mol / L.
  • the alkali can be dissolved in a water-alcohol mixed solvent containing water and a water-soluble alcohol, as well as in the case of using only water as a solvent, as in the mixed aqueous solution of the metal compound described above.
  • the temperature of the mixed aqueous solution is usually -50 to 50 ° C, particularly -20 to 30 ° C, so that when Fe is contained, the spinel ferrite accompanying the generation of neutralization heat during the reaction occurs. Since the formation is further suppressed and a fine and homogeneous precipitate (coprecipitate) is easily formed, the reactivity with the lithium compound described later is further increased, and the lithium manganese composite oxide of the present invention is synthesized. It becomes easy. Further, in order to form a precipitate (coprecipitate) satisfactorily in this step, at least the mixture (particularly the mixed aqueous solution) is used with respect to an aqueous solution containing alkali in order to further suppress generation of heat of neutralization. A method of gradually dropping over several hours is preferable. In this case, the longer the reaction time, the better. However, in practice, 1 hour to 1 day, particularly 2 to 12 hours are preferable.
  • the obtained precipitate is aged by wet oxidation.
  • the crystal phase of the layered rock salt structure (particularly, the crystal phase of the monoclinic layered rock salt structure) can be more easily obtained.
  • the aqueous solution containing the precipitate obtained above is preferably subjected to wet oxidation treatment and ripened. More specifically, aging can be performed by bubbling a gas containing oxygen with a compressor, an oxygen gas generator, or the like, into the alkaline aqueous solution containing the precipitate formed by the above process.
  • the gas to be blown preferably contains a certain amount of oxygen. Specifically, it is preferable to contain 10 to 100% by volume of oxygen of the gas to be blown. Examples of such a gas to be blown include air and oxygen, and oxygen is preferable.
  • the aging temperature is not particularly limited, and a temperature at which wet oxidation treatment of the precipitate (coprecipitate) can be performed is preferable. Usually, 0 to 150 ° C. is preferable, and 10 to 100 ° C. is more preferable.
  • the aging time is not particularly limited, and a time during which the wet oxidation treatment of the precipitate (coprecipitate) can be performed is preferable. The longer the aging time is, the better. However, in practice, 1 hour to 7 days is preferable, and 12 hours to 4 days is more preferable.
  • the aged product obtained in step i) is heated (particularly calcined) in the presence of a raw material compound containing a lithium compound.
  • the aged product obtained in step i) and a lithium compound are mixed, and an aqueous solution containing the raw material compound thus obtained is heated after forming a slurry as necessary ( In particular, firing is preferable.
  • firing is preferable.
  • the content of the aged product obtained in the step i) is usually preferably 100 to 3000 g, more preferably 500 to 2000 g per liter of water.
  • lithium compound examples include water-soluble lithium salts such as lithium chloride, lithium iodide, lithium nitrate, lithium acetate, and lithium hydroxide; lithium carbonate and the like. These lithium compounds can be used alone or in combination of two or more. Moreover, as a lithium compound, both an anhydride and a hydrate can be employ
  • the concentration of the lithium compound in the aqueous solution is usually preferably from 0.1 to 10.0 mol / L, more preferably from 1.0 to 8.0 mol / L.
  • the mixing method of the aged product obtained in step i) and the lithium compound is not particularly limited.
  • Stirring can be carried out by a usual method, for example, it is preferable to stir with a known mixer such as a mixer, a V-type mixer, a W-type mixer, or a ribbon mixer.
  • a known mixer such as a mixer, a V-type mixer, a W-type mixer, or a ribbon mixer.
  • the drying conditions are not particularly limited.
  • the drying temperature is preferably 20 to 100 ° C., more preferably 30 to 80 ° C.
  • the drying time is preferably, for example, 1 hour to 5 days, and more preferably 12 hours to 3 days.
  • pulverization In order to improve the reactivity during the subsequent heat treatment, it is preferable to grind. Regarding the degree of pulverization, it is preferable that coarse particles are not included and the mixture has a uniform color tone.
  • pulverizing a normal method can be adopted, and for example, pulverization can be performed by a vibration mill, a ball mill, a jet mill or the like. Further, the grinding can be repeated twice or more.
  • the heat treatment (particularly baking treatment) is usually preferably performed in a closed container (electric furnace or the like).
  • the heating conditions are not particularly limited, but the final heating temperature is preferably 750 ° C. or higher in order to further stabilize the charge / discharge cycle characteristics.
  • the heating temperature is preferably 1000 ° C. or lower so that lithium is less likely to volatilize.
  • the final heating temperature is particularly preferably 800 to 950 ° C. By heating (especially firing) within this range, it has a higher charge / discharge capacity, better charge / discharge cycle characteristics, and higher discharge capacity at a high current density (more improved rate characteristics). .
  • the heating atmosphere is not particularly limited.
  • the final heating atmosphere is an inert atmosphere such as nitrogen or argon, or a reducing atmosphere using a reducing agent such as polyethylene glycol (PEG), lithium acetate (LiOAc), sucrose, glucose, starch, or lithium stearate.
  • a reducing agent such as polyethylene glycol (PEG), lithium acetate (LiOAc), sucrose, glucose, starch, or lithium stearate.
  • the heating time is not particularly limited. More specifically, the holding time at the final heating temperature is preferably 10 minutes to 24 hours, more preferably 30 minutes to 12 hours. In addition, when performing two-stage heat treatment, the holding time at the first stage heating temperature is preferably 10 minutes to 24 hours (particularly 30 minutes to 12 hours), and the holding time at the second stage final heating temperature is 10 minutes. ⁇ 24 hours (especially 30 minutes to 12 hours) is preferred.
  • the resulting mixture may be subjected to a water washing treatment, a solvent washing treatment, etc. in order to remove an excess lithium compound. it can. Thereafter, filtration is performed, and for example, heat drying can be performed at 80 ° C. or higher, preferably 100 ° C. or higher. Thereby, a crystal phase of a layered rock salt type structure (particularly, a crystal phase of a monoclinic layered rock salt type structure) is obtained.
  • the lithium-manganese composite oxide of the present invention needs to be charged and discharged because the oxygen-rich spinel phase generated after charging remains after discharging. That is, it is necessary to perform charge / discharge using the lithium manganese composite oxide obtained in the step (1) as the positive electrode active material. Therefore, first, a lithium ion secondary battery is produced using the lithium manganese composite oxide obtained in step (1) as a positive electrode active material.
  • the lithium ion secondary battery can be manufactured by a known method.
  • the lithium-manganese composite oxide obtained in step (1) is used as the positive electrode material, and the known metal lithium, carbon-based material (activated carbon, graphite, etc.), silicon, silicon oxide, Si— Use a SiO-based material, lithium titanium oxide, etc., and dissolve lithium salt such as lithium perchlorate and LiPF 6 in a solvent consisting of one or more of known ethylene carbonate, dimethyl carbonate, diethyl carbonate, etc. as the electrolyte.
  • the lithium ion secondary battery can be assembled according to a conventional method.
  • a layered rock salt structure crystal phase (especially a monoclinic layered rock salt structure crystal phase) is used as the positive electrode active material, and the charge capacity or charge potential is gradually increased and charged multiple times.
  • An activation process for performing a discharge cycle is performed.
  • the activation process by the step charge method disturbs the transition metal distribution, and some Mn moves to the Li-Mn mixed layer and the crystal structure changes to the hexagonal R-3m phase, but the Mn-Li mixed layer is maintained. Is done.
  • the staged charging method is a charge / discharge cycle by capacity or potential regulated charge, and thereafter, the charge capacity is gradually increased (or the charge potential is gradually increased), and is cycled in several times, and finally It means a method of cycling in the target potential range.
  • the maximum potential in the charge / discharge cycle of the activation treatment is preferably 4.55 V or more, more preferably 4.70 to 5.00 V.
  • the number of cycles is preferably 3 to 10 times, more preferably 4 to 7 times.
  • charging capacity regulation when the activation treatment is performed in a potential range of 2.00-4.80 V, for example, with a half-cell whose negative electrode is metallic lithium, the charging capacity is limited to, for example, 80 mAh / g with a constant current.
  • a crystal phase of a layered rock salt structure activated by post-discharge (particularly a crystal phase of a hexagonal layered rock salt structure) can be obtained.
  • the charge capacity regulation method may be capacity regulation or upper limit potential regulation. Also, the charging current can be appropriately changed at each charge / discharge.
  • the crystalline phase of the layered rock salt structure accompanying charging (especially the monoclinic layered rock salt structure) Of the crystal phase) is greatly suppressed, and as a result, an activated phase having excellent charge / discharge cycle characteristics can be obtained.
  • the mixed phase containing the crystal phase of the spinel structure of the present invention is obtained from the crystal phase of the layered rock salt structure (particularly the crystal phase of the hexagonal layered rock salt structure) obtained in the step (2).
  • the process will be described.
  • the crystal phase of the spinel structure of the present invention undergoes a gradual crystal structure transition from the activated phase by subjecting the activated phase obtained in step (2) to a charge / discharge cycle.
  • the charge / discharge cycle at this time is preferably adjusted so that the maximum potential is lower than the maximum potential in the activation process.
  • the maximum potential in the charge / discharge cycle is preferably less than 4.70 V, more preferably 4.50 to 4.65 V.
  • the number of cycles is preferably 1 to 100 times, more preferably 5 to 50 times.
  • An example of the charge / discharge cycle is a half-cell in which the negative electrode is metallic lithium.
  • the crystalline phase of the spinel structure of the present invention and the activated phase A mixed phase containing a crystal phase of a certain layered rock salt structure (particularly a crystal phase of a hexagonal layered rock salt structure) can be obtained.
  • the charge / discharge cycle is performed so that the maximum potential of the activation phase obtained in step (2) is equal to or higher than the maximum potential in the activation treatment.
  • the total amount of Fe, Co, and Ni is less than 30 mol% with respect to the total amount of transition metals, for example, as described later in Examples (Comparative Examples 1 and 2), 2.00-4.80 V
  • the charge / discharge cycle is performed, oxygen is deprived (reduced) from the positive electrode by the reaction between the positive electrode and the electrolyte at the charge upper limit voltage, and a known LiMn 2 O 4 or Li 4 Mn 5 O 12 is produced, resulting in a charge / discharge curve. Since the similarity is lost, the charge / discharge cycle characteristics deteriorate.
  • the spinel structure crystalline phase of the present invention When determining whether or not the spinel structure crystalline phase of the present invention is generated, first, after disassembling the lithium ion secondary battery produced in step (2), take out the positive electrode, After washing with diethyl carbonate, dimethyl carbonate, etc., X-ray diffraction measurement is performed. After that, X-ray Rietveld analysis is performed, and fitting is performed with a two-phase structure model of a crystal phase of a layered rock salt structure (particularly a crystal phase of a hexagonal rock salt structure) and a crystal phase of a cubic spinel structure. In particular, in the structure model on the crystal phase side of the spinel structure, it is necessary to construct a model so that the transition metal ion occupancy can be evaluated at the 8a position and the 16d position.
  • Lithium Ion Secondary Battery A lithium ion secondary battery using the lithium manganese composite oxide of the present invention can be produced by a known method.
  • the lithium manganese composite oxide of the present invention is used as a positive electrode material, and known metal lithium, carbon-based materials (activated carbon, graphite, etc.), silicon, silicon oxide, Si—SiO based materials, lithium as negative electrode materials
  • a solution in which lithium salt such as lithium perchlorate or LiPF 6 is dissolved in a solvent composed of one or more of known ethylene carbonate, dimethyl carbonate, diethyl carbonate, etc., using titanium oxide, etc.
  • the “lithium ion secondary battery” is a concept including a “lithium secondary battery” using metallic lithium as a negative electrode material.
  • the term “lithium ion secondary battery” refers to both a “nonaqueous lithium ion secondary battery” using a nonaqueous electrolyte and an “all solid lithium ion secondary battery” using a solid electrolyte. It is a concept to include.
  • Example 1 Sample synthesis and structure evaluation 10.10 g of iron (III) nitrate nonahydrate, 7.27 g of nickel (II) nitrate hexahydrate, 39.58 g of manganese (II) chloride tetrahydrate (total amount 0.25 mol, Fe: Ni: Mn Molar ratio 1: 1: 8) was added to 500 mL of distilled water and completely dissolved to obtain an aqueous metal salt solution. In another beaker, 50 g of lithium hydroxide monohydrate was weighed, 500 mL of distilled water was added and dissolved while stirring, and then 150 mL of ethanol was added to produce an antifreeze lithium hydroxide solution.
  • This lithium hydroxide aqueous solution was put into a titanium beaker and allowed to stand in a thermostatic bath maintained at ⁇ 10 ° C. Next, the metal salt aqueous solution was gradually added dropwise to the lithium hydroxide solution over about 3 hours to form an Fe—Ni—Mn precipitate (coprecipitate). After confirming that the reaction solution was completely alkaline, oxygen was blown into the reaction solution containing the coprecipitate with stirring at room temperature for 2 days to ripen the precipitate.
  • the obtained precipitate was washed with distilled water, filtered, and mixed with 20.98 g of 0.50 mol lithium hydroxide monohydrate dissolved in 200 mL of distilled water to form a uniform slurry.
  • the slurry was transferred to a tetrafluoroethylene petri dish, dried at 50 ° C. for 2 days, and then pulverized to prepare a firing raw material.
  • the obtained powder was heated to 850 ° C. over 1 hour under an air stream, held at that temperature for 5 hours, and then cooled to near room temperature in a furnace.
  • the fired product is taken out from the electric furnace, washed with distilled water, filtered, dried, subjected to XRD evaluation and chemical analysis (ICP emission analysis), and a lithium-manganese complex oxide that matches the prepared transition metal ratio ( The monoclinic layered rock salt structure crystal phase) was obtained as a powdery product in a single phase.
  • a tablet positive electrode 20 mg was mixed with 5 mg of acetylene black (AB) and then bound with 0.5 mg of polytetrafluoroethylene (PTFE) to obtain a tablet positive electrode.
  • the tablet positive electrode was vacuum-dried overnight at 120 ° C. and then introduced into a glove box (GB).
  • Metal lithium was used for the negative electrode, and a mixed solution of ethylene carbonate and dimethyl carbonate in which 1M LiPF 6 was dissolved was used for the electrolyte.
  • the coin battery was activated by the above-described step charging method.
  • charge capacity is limited to 80mAh / g with constant current (positive electrode powder weight 40mA / g), discharge to 2.00V, then gradually increase charge capacity in increments of 40mAh / g and repeat charge / discharge 200mAh in the 4th cycle Discharge after charging to / g, and activated after charging to 4.8V without any capacity regulation in the 5th cycle to obtain a crystalline phase of hexagonal layered rock salt structure.
  • the electric potential range was limited to 2.00-4.60V and charge / discharged for 29 cycles.
  • the battery was disassembled in GB, the tablet positive electrode was taken out, washed with diethyl carbonate and left in GB to dry, then air The sample was mounted in a non-exposed sample holder, removed from the GB, and evaluated for powder X-ray diffraction using an X-ray diffractometer.
  • the abundance ratio of the crystal phase of the layered rock salt type structure and the crystal phase of the spinel type structure was 55:45 by mass ratio.
  • the crystal phase of the hexagonal layered rock-salt structure has lattice positions that can be occupied by three kinds of transition metals as shown below, but the 3a position (0 0 0), 3b position (0 0 0.5), 6c position ( 0 0 z) (z is a value close to 3/8), and it was found that each of them has an irregular arrangement structure in which transition metals exist.
  • Table 1 shows the lattice constant and ion distribution of the crystal phase of the spinel structure (space group Fd3m). From Table 1, it is clear that the 16d position occupancy is 80 atomic% or less, and the target oxygen-rich spinel phase was obtained. Also, the 8a position transition metal occupancy is low, and it can be predicted that the influence on the charge / discharge characteristics is low.
  • Example 2 A sample of a crystal phase having a monoclinic layered rock salt structure was prepared in the same manner as in Example 1 except that the final firing condition was maintained at 850 ° C. for 5 hours in a nitrogen stream. XRD evaluation and chemical analysis (ICP emission analysis) are performed on the product, and lithium manganese composite oxide (crystalline phase of monoclinic layered rock-salt structure) that matches the charged transition metal ratio is used as a powdery single phase It was confirmed that In the same manner as in Example 1, positive electrode and battery preparation, charge / discharge characteristic evaluation, and battery disassembly were performed. After washing with a solvent, the positive electrode mixture was taken out and subjected to XRD evaluation.
  • ICP emission analysis ICP emission analysis
  • the XRD pattern is shown in FIG. As in Example 1, it was a mixed phase of a crystal phase having a hexagonal layered rock salt structure and a crystal phase having a cubic spinel structure.
  • the mass ratio between the crystal phase of the layered rock salt structure and the crystal phase of the spinel structure was 63:37.
  • the transition metal distribution in the crystal phase of the layered rock salt structure was not much different from the sample of Example 1.
  • Table 1 shows the lattice constant and transition metal ion distribution of the crystal phase of the spinel structure. From Table 1, it is clear that the 16d position occupancy is 80 atomic% or less, and the target oxygen-rich spinel phase was obtained. Also, the 8a position transition metal occupancy is low, and it can be predicted that the influence on the charge / discharge characteristics is low.
  • Example 3 Using 25.25 g of iron (III) nitrate and 37.11 g of manganese chloride tetrahydrate (total amount 0.25 mol, Fe: Mn molar ratio 1: 3) as starting materials, amount of lithium hydroxide monohydrate added before firing
  • the crystal phase of the monoclinic layered rock salt structure was prepared in the same manner as in Example 1 except that 0.375 mol (15.74 g) was used and the final firing condition was maintained at 850 ° C. for 1 hour.
  • XRD evaluation and chemical analysis are performed on the product, and lithium manganese composite oxide (crystalline phase of monoclinic layered rock-salt structure) that matches the charged transition metal ratio is used as a powdery single phase It was confirmed that In the same manner as in Example 1, positive electrode and battery preparation, charge / discharge characteristic evaluation, and battery disassembly were performed. After washing with a solvent, the positive electrode mixture was taken out and subjected to XRD evaluation.
  • the XRD pattern is shown in FIG. As in Example 1, it was a mixed phase of a crystal phase having a hexagonal layered rock salt structure and a crystal phase having a cubic spinel structure.
  • the mass ratio of the crystal phase of the layered rock-salt structure to the crystal phase of the spinel structure was 71:29.
  • the transition metal distribution in the crystal phase of the layered rock salt structure was not much different from the sample of Example 1.
  • Table 1 shows the lattice constant and transition metal ion distribution of the crystal phase of the spinel structure. From Table 1, it is clear that the 16d position occupancy is 80 atomic% or less, and the target oxygen-rich spinel phase was obtained. Also, the 8a position transition metal occupancy is low, and it can be predicted that the influence on the charge / discharge characteristics is low.
  • Example 1 Sample preparation as in Example 1, except that the monoclinic layered rock salt structure crystal phase was prepared and activated by step charging, and then the potential range was changed to 2.0-4.8V and 29 cycles charge / discharge cycles were performed. Went. Chemical analysis confirmed that the transition metal composition was maintained in the monoclinic layered rock-salt structure in the crystalline ratio. XRD evaluation showed that the desired crystal phase was obtained as a single phase.
  • the XRD pattern is shown in FIG. As in Example 1, it was a mixed phase of a crystal phase having a hexagonal layered rock salt structure and a crystal phase having a cubic spinel structure.
  • the mass ratio between the crystal phase of the layered rock salt structure and the crystal phase of the spinel structure was 79:21.
  • the transition metal distribution in the crystal phase of the layered rock salt structure was not much different from the sample of Example 1.
  • Table 1 shows the lattice constant and transition metal ion distribution of the crystal phase of the spinel structure. From Table 1, it is clear that the 16d position occupancy is 100 atomic%, and a phase close to the crystal phase of the known LiMn 2 O 4 spinel structure is obtained.
  • FIG. 9 shows a charge / discharge curve measured to obtain the sample of Comparative Example 1. Looking at the discharge curve, the similarity is maintained until the 24th cycle, but in the discharge curve at the 34th cycle, a sudden drop in potential is seen from around 3.7V, and the typical LiMn 2 O 4 spinel 4V And it is close to the two-stage plateau curve consisting of 3V. Therefore, when a crystal phase having a known spinel structure different from the crystal phase having the spinel structure of the present invention is mixed, it is clear that the similarity of the practically important discharge curve cannot be maintained and the charge / discharge cycle characteristics are inferior.
  • the XRD pattern is shown in FIG. As in Example 1, it was a mixed phase of a crystal phase having a hexagonal layered rock salt structure and a crystal phase having a cubic spinel structure.
  • the mass ratio between the crystal phase of the layered rock salt structure and the crystal phase of the spinel structure was 74:26.
  • the transition metal distribution in the crystal phase of the layered rock salt structure was not much different from the sample of Example 1.
  • Table 1 shows the lattice constant and transition metal ion distribution of the crystal phase of the spinel structure. From Table 1, it is clear that the 16d position occupancy was 86 atomic%, and a phase close to the crystal phase of the known Li 4 Mn 5 O 12 spinel structure was obtained.
  • the XRD pattern of the obtained sample is shown in FIG. 12, and the crystal phase parameters of the spinel structure are shown in Table 1.
  • Table 1 the crystal phase parameters of the spinel structure are shown in Table 1.
  • the key to material development is how to reduce the abundance of the spinel-type crystal phase generated during charging. Considering the principle of charge neutralization of this oxygen-rich spinel phase, a large amount of peroxide ions (O 2 2 ⁇ ) or superoxide ions (O 2 ⁇ ⁇ ) are contained in the lithium manganese composite oxide of the present invention.
  • Example 1 a positive electrode and a coin battery were produced.
  • the coin battery was activated by the step charging method.
  • the charge capacity was limited to 80mAh / g with constant current (positive electrode powder weight 40mA / g) and discharged to 2.0V, then gradually increased the charge capacity in increments of 40mAh / g and repeated charge / discharge 200mAh in the 4th cycle
  • a sample was obtained that was discharged after charging to 4.8 g and charged to 4.8 V without capacity regulation in the fifth cycle.
  • the target sample was obtained by washing with dimethyl carbonate.
  • the XRD pattern of the obtained sample is shown in FIG. 13 and the parameters of the crystal phase of the spinel structure are shown in Table 1. Although the Li content is different, it is clear that the same spinel-type crystal phase of the present invention as in the Examples was obtained.
  • Example 3 A crystal phase having a monoclinic layered rock salt structure was prepared in the same manner as in Example 3, and a positive electrode and a coin battery were prepared in the same manner as in Example 1.
  • the coin battery was activated by the step charging method.
  • the charge capacity was limited to 80mAh / g with constant current (positive electrode powder weight 40mA / g) and discharged to 2.0V, then gradually increased the charge capacity in increments of 40mAh / g and repeated charge / discharge 200mAh in the 4th cycle
  • a sample was obtained that was discharged after charging to 4.8 g and charged to 4.8 V without capacity regulation in the fifth cycle. After the battery was disassembled, the target sample was obtained by washing with dimethyl carbonate.
  • Fig. 14 shows the XRD pattern of the obtained sample
  • Table 1 shows the parameters of the spinel phase. Although the amount of Li is different, it is apparent that the same crystal phase of the spinel structure of the present invention as in the examples is obtained.
  • the lithium manganese composite oxide having the oxygen-rich spinel structure of the present invention coexists with the crystal phase of the hexagonal layered rock salt structure including the charged state. It is possible to maintain the similarity of the charge / discharge curve even if the charge / discharge cycle is repeated, and thus it is clear that the charge / discharge characteristics are different from those of various known spinel phases.
  • the lithium manganese based composite oxide of the present invention can be used as a positive electrode material for lithium ion secondary batteries, for example, for small consumer use, in-vehicle use, and stationary use.

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Abstract

La présente invention concerne un oxyde complexe de lithium-manganèse qui, est représenté par la formule générale suivante (1) {Li1-x-a(Mn1-n1-m1M1 n1Tim1)x}8a[(Mn1-n2-m2M2 n2Tim2)yLi2-y-b]16dO4 (où M1 et M2 sont identiques ou différents l'un de l'autre et représentent au moins un type sélectionné dans le groupe constitué de Fe, Co et Ni ; x, y, n1, n2, m1, m2, a et b représentent 0 ≤ x ≤ 0,50, 0 < y ≤ 1,60, 0 < n1 ≤ 0,50, 0 < n2 ≤ 0,50, 0 ≤ m1 ≤ 0,20, 0 ≤ m2 ≤ 0,20, 0 ≤ a ≤ 1-x et 0 ≤ b ≤ 2-y ; la partie à l'intérieur des accolades représente une position de coordonnée (4) d'oxygène (position 8a) dans la structure ; et la partie à l'intérieur des crochets représente une position de coordonnée (6) d'oxygène (position 16d) dans la structure) ; présente un taux d'occupation de métal de transition en position de coordonnée (6) de l'oxygène de 80 % atm. ou moins ; et comprend une phase cristalline présentant une structure en spinelles. Cet oxyde complexe de lithium-manganèse est un matériau d'électrode positive d'oxyde complexe de lithium-manganèse présentant d'excellentes caractéristiques de cycle, et particulièrement, une excellente similitude entre les formes des courbes de charge/décharge.
PCT/JP2017/041059 2016-11-28 2017-11-15 Oxyde complexe de lithium-manganèse et son procédé de production WO2018096999A1 (fr)

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