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WO2018181967A1 - Oxyde de manganèse, son procédé de production et batterie rechargeable au lithium - Google Patents

Oxyde de manganèse, son procédé de production et batterie rechargeable au lithium Download PDF

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Publication number
WO2018181967A1
WO2018181967A1 PCT/JP2018/013796 JP2018013796W WO2018181967A1 WO 2018181967 A1 WO2018181967 A1 WO 2018181967A1 JP 2018013796 W JP2018013796 W JP 2018013796W WO 2018181967 A1 WO2018181967 A1 WO 2018181967A1
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manganese oxide
lithium
molar ratio
containing manganese
charge
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Japanese (ja)
Inventor
昌樹 岡田
雄哉 阪口
秋本　順二
早川　博
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National Institute of Advanced Industrial Science and Technology AIST
Tosoh Corp
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National Institute of Advanced Industrial Science and Technology AIST
Tosoh Corp
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    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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 manganese oxide, a method for producing the same, and a lithium secondary battery using the same.
  • Lithium secondary batteries are widely used as storage batteries for mobile terminals because they have a higher energy density than other storage batteries. Recently, application to a large-sized application requiring a large capacity such as a stationary one and an in-vehicle one has been promoted.
  • NCM material (patent document 1) consisting of lithium (Li), nickel (Ni), cobalt (Co), manganese (Mn), and oxygen
  • Li NCA material (Patent Document 2) made of Ni, aluminum (Al), Co, and oxygen is used. All of these materials belong to R3-m having a layered structure in which a layer occupied by Li and a layer occupied by a metal element other than Li are alternately stacked with a layer occupied by oxygen interposed therebetween. It is a layered rock salt crystal compound.
  • the electrochemical capacity is at most about 80% of the electrochemical capacity calculated from the Li content, and the discharge capacity of 200 to 220 mAh / g is the upper limit for practical use.
  • Li 2 MnO 3 has a Li-excess composition compared to NCA and NCM, a high capacity is expected.
  • Li 2 MnO 3 in the Li-rich Mn oxide is labeled Li [Li 1/3 Mn 2/3 ] O 2 and is an orthorhombic system in the space group C2 / m of the layered rock-salt crystal with Li-rich composition. Belonging to.
  • the composition of Li is excessive, the symmetry of the crystal is lower than that of the layered rock salt type crystal, and in addition to the diffraction peak of the layered rock salt type crystal, a diffraction pattern corresponding to the lowering of the symmetry is characteristic.
  • a unique diffraction pattern is shown in a region where the diffraction angle 2 ⁇ is 20 ° to 35 °.
  • Li 2 MnO 3 has a Li-excess composition compared to NCA and NCM, a high capacity is expected. However, in reality, a high discharge capacity of 250 mAh / g can be obtained in the initial stage, but it has been reported that a rapid capacity drop occurs as the charge / discharge cycle proceeds. It is thought that the cause of the large decrease in capacity with respect to the cycle is related to the transition of the crystal phase to the cubic spinel phase (Fd3-m) due to the release of oxygen generated during charging and the accompanying movement of the transition metal element in the crystal structure. (Non-Patent Document 1).
  • Li 2 MnO 3 The valence of Mn contained in Li 2 MnO 3 is +4, and in the charge / discharge reaction of Li 2 MnO 3 , oxygen ions compensate for the charge.
  • the oxygen ion O 2 ⁇ is known to be oxidized to the O 2 state via the peroxidized state O 2 2 ⁇ , and therefore the ideal charge / discharge reaction of Li 2 MnO 3 is as follows: Can be considered. Li 2 Mn 4+ O 3 ⁇ Mn 4+ O 2 + 2Li + + 2e ⁇ + 1 / 2O 2 (Formula 1)
  • Li 2 MnO 3 belongs to the same layered rock salt type crystal system except that it has a Li-excess composition
  • Ni excess composition Ni, Co which can be regarded as a solid solution with lithium nickel manganese oxide (LiNi 1/2 Mn 1/2 O 2 ) of NCM or layered rock salt type crystal system
  • Ni, Mn oxide or Li excess composition, Mn oxide has been studied.
  • the valences of Ni and Co in the solid solution are theoretically +2 and +3, respectively, and Mn has the same +4 valence as Mn in Li 2 MnO 3 and maintains a high capacity property.
  • Patent Document 3 A method has been proposed in which calcium (Ca) and magnesium (Mg), which are highly covalently bound to oxygen, are introduced into the structure of Ni and Mn oxides with an excess of Li to suppress the release of oxygen during charging.
  • Patent Document 3 It is known that the oxygen desorption reaction forms a potential flat at about 4.5 V with respect to lithium at the time of initial charge, but Ni in the Li-rich composition and part of Li in the Mn oxide are replaced with Ca or Mg. Then, a potential flat portion of 4.5 V is not recognized, and it is shown that the detachment of oxygen can be suppressed. As a result, even when charging and discharging are repeated, the space structure C2 / m is maintained in the crystal structure, and a charging / discharging capacity of 250 to 300 mAh / g is stably obtained.
  • Patent Document 3 is a proposal that shows that a high capacity can be stably expressed if the release of oxygen can be suppressed.
  • an element having a large ion radius such as Ca is introduced into the Li layer, the charge / discharge Li
  • the diffusion in the solid phase may be inhibited, and there is a concern that the capacity may decrease due to a decrease in the amount of Li due to substitution.
  • An object of the present invention is to provide a manganese oxide having a Li-excess composition that stably expresses a high capacity without substitution with a different element such as Ca and Mg, and a method for producing the same.
  • the present invention provides a lithium secondary battery having a high energy density in which is used for a positive electrode.
  • a lithium secondary battery comprising a positive electrode containing the manganese oxide described in any one of (1) to (3) above.
  • the manganese oxide of the present invention When the manganese oxide of the present invention is used as a positive electrode material for a lithium secondary battery, it can be charged / discharged with an extremely high capacity compared to the conventional lithium secondary battery having a high energy density. Provision becomes possible.
  • the method for producing manganese oxide of the present invention can efficiently produce the above-mentioned book by electrochemically oxidizing and reducing the raw material lithium manganese oxide, preferably through charge / discharge in a lithium battery using this as a positive electrode. Enables the production of the manganese oxides of the invention.
  • FIG. 2 is a powder X-ray diffraction pattern of the lithium-containing manganese oxide obtained in Example 1.
  • 3 is a powder X-ray diffraction pattern of each lithium-containing manganese oxide obtained in Examples 2 to 4.
  • FIG. It is a powder X-ray-diffraction pattern in the discharge state after repeating the charge / discharge cycle of the coin cell in Example 2 25 times.
  • the manganese oxide of the present invention is represented by the general formula Li 4 / 3-XY M 2/3 + X O 2 .
  • 0 ⁇ X ⁇ 1/3 preferably 1/20 ⁇ X ⁇ 2/15, and particularly preferably 1/20 ⁇ X ⁇ 1/8.
  • 0 ⁇ Y ⁇ 4/3 and preferably 0.7 ⁇ Y ⁇ 1.0.
  • M is only Mn and Ni and satisfies 0 ⁇ Ni / Mn molar ratio ⁇ 2/5.
  • the value of the Ni / Mn molar ratio in the general formula Li 4 / 3-XY M 2/3 + X O 2 which is the manganese oxide of the present invention is a raw material used in the method for producing a manganese oxide of the present invention. It can be determined from a composition analysis of the general formula Li (4 / 3-X) M (2/3 + X) O 2 which is a lithium-containing manganese oxide. Examples of the method include dielectric coupling plasma emission analysis and atomic absorption analysis.
  • the value of Y in the general formula Li 4 / 3-XY M 2/3 + X O 2 corresponds to the amount of Li desorption by electrochemical oxidation / reduction. It can be calculated by using Coulomb's law from the quantity of electricity at the time of selective oxidation / reduction.
  • the crystal structure of the general formula Li 4 / 3-XY M 2/3 + X O 2 which is the manganese oxide of the present invention can be identified by powder X-ray diffraction measurement.
  • the manganese oxide of the present invention has a crystal structure belonging to a monoclinic crystal (space group C2 / m).
  • the mechanism is unknown, but this monoclinic crystal structure of the manganese oxide of the present invention reversibly reduces the electrostatic repulsion of oxygen when lithium is desorbed in large quantities and suppresses structural changes. Therefore, it is considered that a large amount of Li can be stably inserted and removed.
  • the manganese oxide of the present invention preferably contains two phases having different lattice constants.
  • the mechanism is unknown, but the presence of two phases with different lattice constants relieves or cancels Li insertion / desorption with respect to charging / discharging and the expansion / contraction of crystals associated with redox of Ni, Mn, and oxygen. It is considered that stability is improved.
  • M is only Ni and Mn, and it is necessary to satisfy 0 ⁇ Ni / Mn molar ratio ⁇ 2/5.
  • Ni / Mn molar ratio exceeds 2/5, the crystal structure of Ni becomes difficult to maintain a monoclinic crystal, and the upper limit of the Ni / Mn molar ratio is 2/5.
  • the Ni / Mn molar ratio is preferably 1/3 or less, particularly preferably 1/4 or less.
  • the Ni / Mn molar ratio is preferably 1/8 or more, and particularly preferably 1/5 or more, in order to suppress the decrease in capacity due to the transition of the Ni valence to a +3 highly oxidized state.
  • the manganese oxide of the present invention has a BET specific surface area of 0.5 m 2 / g or less and a primary particle diameter of 0.5 ⁇ m or more, and has the general formula Li (4 / 3-X) M (2/3 + X) O 2 (where 0 ⁇ X ⁇ 1/3, M is only Mn and Ni, and 0 ⁇ Ni / Mn molar ratio ⁇ 2/5 is satisfied), and the crystal structure is monoclinic (space It is obtained by electrochemically repeating oxidation / reduction of lithium-containing manganese oxide belonging to group C2 / m).
  • 1/20 ⁇ X ⁇ 2/15 particularly preferably 1/20 ⁇ X ⁇ 1/8.
  • the BET specific surface area of the lithium-containing manganese oxide is 0.5 m 2 / g or less and the primary particle diameter is 0.5 ⁇ m or more, the detachment of oxygen that is likely to occur at the time of charging is suppressed, which is inherently high.
  • the capacity property can be stably expressed.
  • the BET specific surface area of the lithium-containing manganese oxide is preferably 0.1 to 0.4 m 2 / g, and the primary particle diameter is preferably 0.5 to 1.0 ⁇ m.
  • a method for electrochemically oxidizing / reducing the lithium-containing manganese oxide preferably, a method in which a battery is produced and charging and discharging are repeated in the battery is exemplified.
  • oxidation and reduction may be performed outside the battery.
  • a method of producing a battery and charging / discharging the battery a lithium battery is produced using the lithium-containing manganese oxide as a positive electrode material, and charging / discharging is performed in the battery.
  • a configuration that can be used as it is as a lithium secondary battery is preferable. Since it can be used as a battery as it is, a method of electrochemically oxidizing / reducing is preferably a method of producing a battery and repeating charging and discharging in the battery.
  • the monoclinic manganese oxide of the present invention can be obtained by electrochemically repeating oxidation and reduction of monoclinic lithium-containing manganese oxide.
  • composition of the lithium-containing manganese oxide used in the production of the manganese oxide of the present invention can be determined from composition analysis.
  • Examples of the method obtained from the composition analysis include dielectric coupling plasma emission analysis and atomic absorption analysis.
  • the BET specific surface area of the lithium-containing manganese oxide used in the production of the manganese oxide of the present invention is obtained by converting the adsorption isotherm obtained from physical gas adsorption into a BET plot, and based on the BET isotherm, the gas adsorption of the monolayer
  • the amount Vm can be obtained and can be obtained by the so-called BET method in which the specific surface area is calculated based on the molecular size of the gas used for physical adsorption.
  • the primary particle diameter of the lithium-containing manganese oxide used in the production of the manganese oxide of the present invention can be determined from direct observation with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the primary particle diameter refers to particles in which crystallites are densely aggregated to form one particle.
  • the lithium-containing manganese oxide used in the manufacture of the manganese oxide of the present invention has a molar ratio of (Mn raw material + Ni raw material) to Li raw material] of 0 ⁇ [Li / (Mn + Ni) ratio] ⁇ 2, and the Mn raw material and Ni
  • the raw material molar ratio] is set to 0 ⁇ [Ni / Mn molar ratio] ⁇ 2/5, and a mixture of Mn raw material, Ni raw material, and Li raw material in a solid phase, a liquid phase, or a combination of both is fired.
  • Examples of the firing include a method in which the firing is performed in the air, preferably at 400 to 1000 ° C., preferably for 6 to 24 hours, but is not particularly limited as long as a monoclinic crystal structure can be obtained.
  • Examples of the temperature increase and temperature decrease conditions during firing include temperature increase and decrease at a constant rate, and stepwise temperature increase and decrease, but are not limited thereto.
  • Mn raw material used by manufacture of lithium containing manganese oxide there is no restriction
  • Ni raw material used in the production of lithium-containing manganese oxide there is no particular limitation on the Ni raw material used in the production of lithium-containing manganese oxide.
  • nickel sulfate, nickel carbonate, nickel nitrate, nickel chloride, nickel hydroxide, nickel oxide and the like are exemplified, but not limited thereto.
  • the lithium-containing manganese oxide it is possible to use an oxide prepared in advance so that Mn and Ni have the Ni / Mn molar ratio of the present invention.
  • hydroxide [(Mn ⁇ Ni) (OH) 2 ] oxyhydroxide [(Mn ⁇ Ni) OOH] prepared beforehand so that Mn and Ni have the Ni / Mn molar ratio of the present invention
  • oxidation Examples include [[Mn ⁇ Ni) O, (Mn ⁇ Ni) O 2 , (Mn ⁇ Ni) 2 O 3 , (Mn ⁇ Ni) 3 O 4 ], but are not limited thereto.
  • the Li raw material used in the production of the lithium-containing manganese oxide is not particularly limited, and examples include lithium carbonate, lithium hydroxide, lithium nitrate, lithium chloride, lithium iodide, lithium oxalate, lithium sulfate, and lithium oxide. However, it is not limited to these.
  • the manganese oxide of the present invention for the positive electrode of a lithium secondary battery, it becomes possible to constitute a high-capacity lithium secondary battery that could not be obtained conventionally.
  • the configuration of the lithium secondary battery other than the positive electrode is not particularly limited, but the negative electrode is a material that occludes and releases Li, for example, a carbon-based material, a tin oxide-based material, Li 4 Ti 5 O 12 , SiO, Li, and the like.
  • the material etc. which form an alloy are illustrated.
  • Examples of the material that forms an alloy with Li include silicon-based materials and aluminum-based materials.
  • Examples of the electrolyte include an organic electrolytic solution in which a Li salt and various additives are dissolved in an organic solvent, a Li ion conductive solid electrolyte, and a combination thereof.
  • composition analysis> The composition of the prepared lithium-containing manganese oxide was analyzed with a dielectric coupled plasma emission spectrometer (trade name: ICP-AES, manufactured by PerkinElmer Japan).
  • the BET specific surface area is measured by a one-point method using a mixed gas of 30% nitrogen and 70% helium as an adsorbed gas using a BET measuring device (trade name: MiCROMERITIC DeSorbIII, manufactured by Shimadzu Corporation). did.
  • Measurement wavelength 0.78 mm ⁇ Measurement resolution: 0.01 deg Measurement method: Debye-Scherrer method Capillary material: Lindeman glass Using the obtained measurement data, Rietveld method crystal structure analysis was performed to determine the crystal structure.
  • Example of raw material production Nickel sulfate and manganese sulfate were dissolved in pure water to obtain an aqueous solution containing 0.5 mol / L (liter) of nickel sulfate and 1.5 mol / L of manganese sulfate. .
  • the total concentration of all metals in the metal aqueous solution was 2.0 mol / L.
  • 200 g of pure water was put into a reaction vessel having an internal volume of 1 L, and then this was heated to 80 ° C. and maintained.
  • the metal salt aqueous solution was added to the reaction vessel at a supply rate of 0.28 g / min. Further, air was bubbled into the reaction vessel at a supply rate of 1 L / min as an oxidant.
  • a 2 mol / L sodium hydroxide aqueous solution (caustic soda aqueous solution) was intermittently added so that the pH was 10 when supplying the metal salt aqueous solution and air to obtain a mixed aqueous solution.
  • nickel-manganese composite oxyhydroxide was precipitated to obtain a slurry. The obtained slurry was filtered and washed, and then the wet cake after washing was air-dried in the air for 1 week, and then dried at 115 ° C. for 5 hours, thereby obtaining an oxyhydroxide containing Mn and Ni (Ni 0.245). Mn 0.755 OOH, Mn: 45.3 wt%, Ni: 14.7 wt%).
  • Example 1 1.80 g of oxyhydroxide containing Mn and Ni obtained in the above raw material production example and 1.21 g of commercially available lithium carbonate (manufactured by Rare Metallics) were dry-mixed for 15 minutes using a mortar. To the resulting mixture, 2 mL of ethanol (special grade reagent, manufactured by Kishida Chemical Co., Ltd.) was added and mixed for 60 minutes. 1.00 g of the obtained mixed powder was put in a baking dish, subjected to heat treatment at 900 ° C. for 12 hours in a box furnace, cooled to room temperature, and a sample was taken out. The temperature increase rate and temperature decrease rate were 300 ° C./hr. When the temperature was lowered, the furnace was cooled at 300 ° C. or lower.
  • ethanol special grade reagent, manufactured by Kishida Chemical Co., Ltd.
  • the obtained crystal belongs to monoclinic C2 / m, the Ni / Mn molar ratio is 0.304, and the Li / (Mn + Ni) molar ratio. Was 1.50. From these values, X was 0.13, and a lithium-containing manganese oxide of Li 1.20 M 0.80 O 2 (Li 1.20 Mn 0.61 Ni 0.19 O 2 ) was obtained. I understood.
  • the lithium-containing manganese oxide had a BET specific surface area of 0.4 m 2 / g and a primary particle size of 1 ⁇ m. The powder X-ray diffraction pattern of this lithium-containing manganese oxide is shown in FIG.
  • a coin cell using the obtained lithium-containing manganese oxide as a positive electrode was produced, and a charge / discharge cycle test was performed. It was found that no potential flat portion was observed around 4.5 V during charging, and no oxygen was released.
  • the cycle in which the maximum discharge capacity was obtained was the 11th cycle, and the maximum discharge capacity value was 277 mAh / g.
  • the value of Y calculated from this discharge capacity value of 277 mAh / g is 0.88, which is Li 0.32 M 0.80 O 2 (Li 0.32 Mn 0.61 Ni 0.19 O 2 ). It was.
  • the X-ray diffraction pattern after repeating the charge / discharge cycle belonged to the same monoclinic crystal structure as that of the lithium-containing manganese oxide.
  • Example 2 2.00 g of oxyhydroxide containing Mn and Ni obtained in Production Example and 1.39 g of commercially available lithium carbonate (made by Rare Metallics) were dry-mixed for 15 minutes using a mortar, and then ethanol (reagent) 2 mL of special grade, manufactured by Kishida Chemical Co., Ltd. was added and mixed for 60 minutes. 1.00 g of the obtained mixed powder was put in a baking dish, subjected to heat treatment at 900 ° C. for 12 hours in a box furnace, cooled to room temperature, and a sample was taken out. The temperature increase rate and temperature decrease rate were 300 ° C./hr. When the temperature was lowered, the furnace was cooled at 300 ° C. or lower.
  • the obtained lithium-containing manganese oxide belongs to monoclinic crystals, the Ni / Mn molar ratio is 0.333, and the Li / (Mn + Ni) molar ratio is 1.63. Met. From this value, it was confirmed that X was 0.09, and a lithium-containing manganese oxide of Li 1.24 M 0.76 O 2 (Li 1.24 Mn 0.57 Ni 0.19 O 2 ) was obtained. I understood.
  • the lithium-containing manganese oxide had a BET specific surface area of 0.2 m 2 / g and a primary particle size of 1 ⁇ m.
  • a coin cell using the obtained lithium-containing manganese oxide as a positive electrode was produced, and a charge / discharge cycle test was performed. It was found that no potential flat portion was observed around 4.5 V during charging, and no oxygen was released.
  • the cycle in which the maximum discharge capacity was obtained was the 25th cycle, and the maximum discharge capacity value was 250 mAh / g.
  • the value of Y calculated from this discharge capacity value 250 mAh / g was 0.62, and was Li 0.62 M 0.76 O 2 (Li 0.62 Mn 0.57 Ni 0.19 O 2 ). .
  • the powder X-ray diffraction pattern of this lithium-containing manganese oxide is shown in FIG.
  • Example 3 A lithium-containing manganese oxide was prepared in the same manner as in Example 2 except that 1.43 g of lithium carbonate was used. From the evaluation of crystallinity and composition analysis of the prepared sample, it was attributed to monoclinic crystal, the Ni / Mn molar ratio was 0.315, and the Li / (Mn + Ni) molar ratio was 1.67. It was. From these values, it was found that X was 0.08, and it was a lithium-containing manganese oxide of Li 1.25 M 0.75 O 2 (Li 1.25 Mn 0.57 Ni 0.18 O 2 ). It was. The lithium-containing manganese oxide had a BET specific surface area of 0.2 m 2 / g and a primary particle size of 1 ⁇ m. The powder X-ray diffraction pattern of this lithium-containing manganese oxide is shown in FIG.
  • a coin cell using the obtained lithium-containing manganese oxide as a positive electrode was produced, and a charge / discharge cycle test was performed. It was found that no potential flat portion was observed around 4.5 V during charging, and no oxygen was released.
  • the cycle in which the maximum discharge capacity was obtained was the 25th cycle, and the maximum discharge capacity value was 270 mAh / g.
  • the value of Y calculated from this discharge capacity value 270 mAh / g was 0.66 and was Li 0.59 Mn 0.75 O 2 (Li 0.59 Mn 0.57 Ni 0.18 O 2 ). .
  • the X-ray diffraction pattern after repeating the charge / discharge cycle belonged to the same monoclinic crystal structure as that of the lithium-containing manganese oxide.
  • FIG. 4 shows a charge / discharge profile after the charge / discharge cycle is repeated 25 times.
  • Example 4 A lithium-containing manganese oxide was prepared in the same manner as in Example 2 except that 1.47 g of lithium carbonate was used. From the evaluation of crystallinity and composition analysis of the prepared samples, the obtained crystals belonged to monoclinic crystals, and the Ni / Mn molar ratio was 0.321 and the Li / (Mn + Ni) molar ratio was 1.70. From these values, it was found that X was 0.07, and it was a lithium-containing manganese oxide of Li 1.26 Mn 0.74 O 2 (Li 1.26 Mn 0.56 Ni 0.18 O 2 ). It was. The lithium-containing manganese oxide had a BET specific surface area of 0.1 m 2 / g and a primary particle size of 1 ⁇ m. The powder X-ray diffraction pattern of this lithium-containing manganese oxide is shown in FIG.
  • a coin cell using the obtained lithium-containing manganese oxide as a positive electrode was produced, and a charge / discharge cycle test was performed. It was found that no potential flat portion was observed around 4.5 V during charging, and no oxygen was released.
  • the cycle in which the maximum discharge capacity was obtained was the 25th cycle, and the maximum discharge capacity value was 250 mAh / g.
  • the value of Y calculated from this discharge capacity ratio value of 250 mAh / g is 0.61 and is Li 0.65 M 0.74 O 2 (Li 0.65 Mn 0.56 Ni 0.18 O 2 ). It was.
  • the X-ray diffraction pattern after repeating the charge / discharge cycle belonged to the same monoclinic crystal structure as that of the lithium-containing manganese oxide.
  • Example 5 A coin cell using a lithium-containing manganese oxide synthesized in the same manner as in Example 2 as a positive electrode was prepared, and a charge / discharge cycle test was performed. It was found that no potential flat portion was observed around 4.5 V during charging, and no oxygen was released. The cycle in which the maximum discharge capacity was obtained was the 25th cycle, and the maximum discharge capacity value was 250 mAh / g. The value of Y calculated from this discharge capacity value 250 mAh / g was 0.62, and was Li 0.62 M 0.76 O 2 (Li 0.62 Mn 0.57 Ni 0.19 O 2 ). . When the powder X-ray diffraction pattern measurement was performed in the discharge state after repeating 50 cycles of charge / discharge, it was found that the crystal structure was a manganese oxide belonging to a monoclinic crystal.
  • Example 6 A coin cell using the lithium-containing manganese oxide obtained in Example 1 as a positive electrode was prepared, a charge / discharge cycle test was performed, and a manganese oxide in a discharged state after repeating the charge / discharge cycle 20 times was obtained. It was.
  • FIG. 6 shows the synchrotron radiation X-ray measurement result and Rietveld analysis result of the manganese oxide in the discharge state after repeating the charge / discharge cycle 20 times.
  • the existence ratio of the two phases was determined to be 41% and 59%.
  • the interatomic distance from the six oxygen atoms around the four kinds of metal seats is 1.92 (9) ⁇ to 2.05 (5) ⁇ for the M1 seat, and 2 for the M2 seat. .06 (5) ⁇ -2.13 (9) ⁇ , M3 seats are 2.08 (3) ⁇ -2.22 (6) ⁇ , M4 seats are 2.00 (1) ⁇ -2.04 (0 )
  • the interatomic distance showed a significant variation beyond the error range, it was found that the monoclinic system is appropriate.
  • the interatomic distance from the six oxygen atoms around the four metal seats is 1.85 (6) ⁇ to 1.89 (3) ⁇ for the M1 seat and 2 for the M2 seat. .12 (1) ⁇ -2.24 (8) ⁇ , M3 seats are 1.83 (0) ⁇ -2.43 (9) ⁇ , M4 seats are 2.00 (6) ⁇ -2.10 (5) )
  • the interatomic distance showed a significant variation beyond the error range, it was found that the monoclinic system is appropriate.
  • Example 7 A coin cell using the lithium-containing manganese oxide obtained in Example 1 as a positive electrode was prepared, a charge / discharge cycle test was performed, and a manganese oxide in a discharged state after repeating the charge / discharge cycle 30 times was obtained. It was.
  • FIG. 7 shows the synchrotron radiation X-ray measurement result and Rietveld analysis result of the manganese oxide in the discharge state after repeating the charge / discharge cycle 30 times.
  • the interatomic distance was obtained from the Rietveld analysis result.
  • the distance between the six oxygen atoms around the four metal seats is 1.98 (1) ⁇ to 1.98 (9) ⁇ for the M1 seat and 2 for the M2 seat. .11 (2) ⁇ -2.14 (0) ⁇ , M3 seats are 1.95 (3) ⁇ -2.34 (0) ⁇ , M4 seats are 2.00 (1) ⁇ -2.08 (5) )
  • the interatomic distance showed a significant variation beyond the error range, it was found that the monoclinic system is appropriate.
  • the interatomic distance from the six oxygen atoms around the four metal seats is 1.85 (6) ⁇ to 1.89 (3) ⁇ for the M1 seat and 2 for the M2 seat. .12 (1) ⁇ -2.24 (8) ⁇ , M3 seats are 1.83 (0) ⁇ -2.43 (9) ⁇ , M4 seats are 2.00 (6) ⁇ -2.10 (5) )
  • the interatomic distances at each site showed significant variation beyond the error range, indicating that the monoclinic system was appropriate.
  • FIG. 4 shows a charge / discharge profile after 25 cycles of the charge / discharge cycle.
  • the manganese oxide of the present invention can be used in various fields including positive electrode materials for lithium secondary batteries. It should be noted that the entire content of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2017-72111 filed on March 31, 2017 is cited here as the disclosure of the specification of the present invention. Incorporate.

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Abstract

L'invention concerne un nouvel oxyde de manganèse approprié pour un matériau d'électrode positive dans une batterie rechargeable au lithium à haute densité d'énergie, un procédé de production dudit oxyde de manganèse, et une batterie rechargeable au lithium à haute densité d'énergie. Cet oxyde de manganèse est représenté par la formule générale Li(4/3-X-Y)M(2/3+X)O2 (0≤X≤1/3, 0<Y≤4/3, M représente uniquement Mn et Ni, et 0<rapport molaire Ni/Mn≤2/5), et présente une structure cristalline appartenant au système cristallin monoclinique (groupe spatial : C2/m). Ce procédé de production d'oxyde de manganèse comprend l'oxydation électrochimique et la réduction d'un oxyde de manganèse contenant du lithium qui est représenté par la formule générale Li(4/3-X)M(2/3+X)O2 (0≤X≤1/3, M représente uniquement Mn et Ni, et 0<rapport molaire Ni/Mn≤2/5), qui présente une surface spécifique BET inférieure ou égale à 0,5 m2/g et une taille de particule primaire supérieure ou égale à 0,5 µm, et qui présente une structure cristalline appartenant au système cristallin monoclinique (groupe spatial : C2/m). Cette batterie rechargeable au lithium comporte une électrode positive contenant ledit oxyde de manganèse.
PCT/JP2018/013796 2017-03-31 2018-03-30 Oxyde de manganèse, son procédé de production et batterie rechargeable au lithium Ceased WO2018181967A1 (fr)

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JP2021017397A (ja) * 2019-07-23 2021-02-15 国立研究開発法人産業技術総合研究所 単斜晶系リチウムニッケルマンガン系複合酸化物及びその製造方法
WO2021193467A1 (fr) * 2020-03-25 2021-09-30 国立研究開発法人理化学研究所 Oxyde complexe de manganèse-iridium pour catalyseur de décomposition d'eau, matériau d'électrode d'oxyde complexe de manganèse-iridium et procédés de production associés
JP2023544339A (ja) * 2020-12-04 2023-10-23 エコプロ ビーエム カンパニー リミテッド 正極活物質およびこれを含むリチウム二次電池

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JP2021017397A (ja) * 2019-07-23 2021-02-15 国立研究開発法人産業技術総合研究所 単斜晶系リチウムニッケルマンガン系複合酸化物及びその製造方法
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WO2021193467A1 (fr) * 2020-03-25 2021-09-30 国立研究開発法人理化学研究所 Oxyde complexe de manganèse-iridium pour catalyseur de décomposition d'eau, matériau d'électrode d'oxyde complexe de manganèse-iridium et procédés de production associés
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JP2025015605A (ja) * 2020-12-04 2025-01-30 エコプロ ビーエム カンパニー リミテッド 正極活物質およびこれを含むリチウム二次電池

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