Classifications

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  • 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
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  • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
  • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
  • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/04—Hybrid capacitors
  • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
• • H—ELECTRICITY
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  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/46—Metal oxides
• • H—ELECTRICITY
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  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/66—Current collectors
  • H01G11/68—Current collectors characterised by their material
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  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
  • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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  • 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
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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  • 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
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • H—ELECTRICITY
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  • 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
  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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  • C01P2006/40—Electric properties
• • H—ELECTRICITY
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  • 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
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/028—Positive electrodes
• • 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
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  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a lithium cobalt composite oxide and a method for producing the same, and an electrochemical device and a lithium ion secondary battery using the lithium cobalt composite oxide. About.
• This secondary battery is not limited to a small electronic device, but is also considered to be applied to a large-sized electronic device represented by an automobile or the like, or an electric power storage system represented by a house.
• lithium ion secondary batteries are easily expected to be smaller and have higher capacity. This is because an energy density higher than that of a lead battery or a nickel cadmium battery can be obtained.
• This lithium ion secondary battery includes an electrolyte solution together with a positive electrode, a negative electrode, and a separator.
• the positive electrode and the negative electrode include a positive electrode active material and a negative electrode active material related to the charge / discharge reaction.
• a lithium cobalt composite oxide having a hexagonal layered rock salt structure belonging to the space group R-3m and containing a transition metal which is a rare metal such as cobalt or nickel is used as a positive electrode active material.
• a water electrolyte secondary battery has been proposed. In recent years, a higher capacity is required for such a non-aqueous electrolyte secondary battery, and a cycle life with respect to a higher potential is also required. However, there is still a high demand for improvement in terms of cycle life, and various attempts have been made to improve it (see, for example, Patent Documents 1-6).
• the present invention has been made in view of the above problems, and when used as a positive electrode active material for an electrochemical device, a lithium cobalt composite oxide capable of obtaining high cycle characteristics along with a high charge / discharge capacity, and the production thereof It aims to provide a method.
• the present invention provides a lithium cobalt composite oxide used as an active material for a positive electrode of an electrochemical device, wherein the lithium cobalt composite oxide is dispersed in ultrapure water.
• Fluorine ions eluted into the lithium cobalt-based composite oxide in a mass ratio of 500 ppm to 15000 ppm, and the composition is the following general formula (1): Li 1 ⁇ x Co 1 ⁇ z M z O 2 ⁇ a F a ( ⁇ 0.1 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ a ⁇ 2) (1)
• M represents one or more metal elements selected from the group consisting of Mn, Ni, Fe, V, Cr, Al, Nb, Ti, Cu, and Zn).
• a composite oxide is provided.
• lithium ions can be stably and appropriately supplied by facilitating desorption / insertion of lithium ions, so when used as a positive electrode active material for an electrochemical device High cycle characteristics can be obtained with a high charge / discharge capacity.
• the lithium ions eluted in the eluate in which the lithium cobalt composite oxide is dispersed with ultrapure water is 500 ppm or more and 20000 ppm or less in a mass ratio with respect to the lithium cobalt composite oxide.
• the charge / discharge capacity is used when used as the positive electrode active material for electrochemical devices. And the cycle characteristics can be improved more effectively.
• the mass ratio (the mass of fluorine ions / the mass of lithium ions) of lithium ions and fluorine ions eluted in the eluate in which the lithium cobalt composite oxide is dispersed with ultrapure water is 0.1 or more and 5 The following is preferable.
• the mass ratio of the eluted lithium ions to fluorine ions (the mass of fluorine ions / the mass of lithium ions) is within the above range, the charge / discharge capacity and cycle characteristics when used as the active material for the positive electrode of an electrochemical device Can be increased more reliably.
• the average particle size is preferably 0.5 ⁇ m or more and 30.0 ⁇ m or less.
• the charge / discharge capacity and cycle characteristics can be increased more effectively when used as the active material of the positive electrode of the electrochemical device.
• it preferably has a BET specific surface area of less 0.10 m 2 / g or more 2.00 m 2 / g.
• the charge / discharge capacity and cycle characteristics can be increased more effectively when used as the active material of the positive electrode of the electrochemical device.
• the composition of the present invention has the following general formula (1): Li 1 ⁇ x Co 1 ⁇ z M z O 2 ⁇ a F a ( ⁇ 0.1 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ a ⁇ 2) (1) (Wherein, M represents one or more metal elements selected from the group consisting of Mn, Ni, Fe, V, Cr, Al, Nb, Ti, Cu, and Zn).
• Lithium cobalt composite oxide having a mass ratio of 500 ppm to 15000 ppm with respect to the lithium cobalt composite oxide is a fluorine ion eluted in the eluate when the lithium cobalt composite oxide is dispersed with ultrapure water.
• a method for producing a cobalt-based composite oxide is provided.
• the manufactured lithium cobalt composite oxide can provide high cycle characteristics with a high charge / discharge capacity when used as an active material for the positive electrode of an electrochemical device.
• the active material it is possible to produce a lithium-cobalt composite oxide that can provide high cycle characteristics with high charge / discharge capacity at low cost.
• lithium is extracted electrochemically from the lithium cobalt based composite oxide precursor.
• Such a method can be suitably used as a method for extracting lithium.
• lithium is extracted electrochemically after the lithium cobalt complex oxide precursor is molded with a thickness of 1.0 mm or more.
• Such a method can also be suitably used as a method for extracting lithium.
• the lithium compound preferably contains lithium hexafluorophosphate (LiPF 6 ).
• Fluorine can be added to the lithium cobalt complex oxide by using a lithium compound containing lithium hexafluorophosphate as the lithium compound to be reacted with the lithium cobalt complex oxide precursor.
• the lithium compound preferably contains lithium tetrafluoroborate (LiBF 4 ).
• Fluorine can be added to the lithium cobalt complex oxide by using a lithium compound containing lithium tetrafluoroborate as the lithium compound to be reacted with the lithium cobalt complex oxide precursor.
• the step of reacting includes a step of firing, and in the step of firing, the firing temperature is preferably 600 ° C. or higher and 1100 ° C. or lower.
• a method for reacting the lithium cobalt complex oxide precursor and the lithium compound a method of performing firing in the above temperature range can be suitably used.
• the reacting step includes a firing step, and the firing is performed in an air atmosphere in the firing step.
• firing is preferably performed in an air atmosphere containing oxygen.
• adjustment of the firing atmosphere becomes unnecessary, so that manufacturing costs can be reduced.
• the present invention provides a negative electrode comprising a negative electrode active material layer containing negative electrode active material particles having a charge / discharge efficiency of 80% or less when used as a negative electrode active material in an electrochemical device, and the negative electrode current collector,
• an electrochemical device having a positive electrode active material layer containing a lithium cobalt-based composite oxide and a positive electrode comprising a positive electrode current collector.
• Such an electrochemical device can have high cycle characteristics as well as high charge / discharge capacity.
• the present invention also includes a negative electrode active material layer containing negative electrode active material particles containing silicon oxide represented by a composition formula of SiO x (0.5 ⁇ x ⁇ 1.6) and a negative electrode current collector.
• a negative electrode active material layer containing negative electrode active material particles containing silicon oxide represented by a composition formula of SiO x (0.5 ⁇ x ⁇ 1.6) and a negative electrode current collector.
• an electrochemical device comprising a negative electrode, and a positive electrode comprising a positive electrode active material layer containing the lithium cobalt-based composite oxide and a positive electrode current collector.
• Such an electrochemical device can have high cycle characteristics as well as high charge / discharge capacity.
• the present invention also provides a negative electrode comprising a negative electrode active material layer containing negative electrode active material particles having a charge / discharge efficiency of 80% or less when used as a negative electrode active material of a lithium ion secondary battery, and a negative electrode current collector.
• a lithium ion secondary battery comprising a positive electrode active material layer containing the lithium cobalt-based composite oxide and a positive electrode comprising a positive electrode current collector.
• Such a lithium ion secondary battery can have high cycle characteristics as well as high charge / discharge capacity.
• the present invention also includes a negative electrode active material layer containing negative electrode active material particles containing silicon oxide represented by a composition formula of SiO x (0.5 ⁇ x ⁇ 1.6) and a negative electrode current collector.
• a lithium ion secondary battery comprising a negative electrode, a positive electrode comprising a positive electrode active material layer containing the lithium cobalt-based composite oxide, and a positive electrode current collector.
• Such a lithium ion secondary battery can have high cycle characteristics as well as high charge / discharge capacity.
• lithium cobalt based composite oxide of the present invention when used as an active material for a positive electrode of an electrochemical device, lithium ions can be smoothly inserted and removed, thereby stabilizing lithium ions. Since it can supply suitably, cycling characteristics can be made high with charge / discharge capacity.
• the method for producing a lithium cobalt composite oxide of the present invention is used, even a lithium cobalt composite oxide regenerated from a used positive electrode is high when used as an active material for a positive electrode of an electrochemical device.
• lithium cobalt-based composite oxides that can provide high cycle characteristics together with high charge / discharge capacity when used as an active material for the positive electrode of an electrochemical device are manufactured at low cost. be able to. Furthermore, if it is the electrochemical device of this invention, it can have a high cycle characteristic with a high charging / discharging capacity
• a non-aqueous electrolyte secondary battery using lithium cobalt composite oxide as a positive electrode active material has been proposed.
• a cycle for higher capacity and higher potential is proposed. Life expectancy is required.
• the cycle life there is still a high demand for improvement, and various attempts for improvement have been made, but a satisfactory cycle life has not yet been achieved.
• the present inventors have made extensive studies on a lithium cobalt-based composite oxide that, when used as a positive electrode active material for an electrochemical device, can provide high cycle characteristics with a high charge / discharge capacity.
• the lithium cobalt composite oxide in which the fluorine ions eluted in the eluate in which the lithium cobalt composite oxide is dispersed with ultrapure water is in a mass ratio of 500 ppm to 15000 ppm with respect to the lithium cobalt composite oxide If it exists, when it used as a positive electrode active material of an electrochemical device, it discovered that a high cycle characteristic was acquired with a high charging / discharging capacity
• the lithium cobalt-based composite oxide of the present invention is a lithium cobalt-based composite oxide used as an active material for a positive electrode of an electrochemical device, wherein the lithium cobalt-based composite oxide is dispersed in ultrapure water.
• Fluorine ions to be eluted are 500 ppm to 15000 ppm, more preferably 1000 ppm to 15000 ppm, more preferably 1500 ppm to 15000 ppm in mass ratio to the lithium cobalt composite oxide, and the composition is represented by the following general formula (1): Li 1 ⁇ x Co 1 ⁇ z M z O 2 ⁇ a F a ( ⁇ 0.1 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ a ⁇ 2) (1) (Wherein M represents one or more metal elements selected from the group consisting of Mn, Ni, Fe, V, Cr, Al, Nb, Ti, Cu and Zn).
• x is more preferably 0 ⁇ x ⁇ 0.5, and further preferably 0 ⁇ x ⁇ 0.3.
• z is more preferably 0 ⁇ z ⁇ 0.7, and further preferably 0 ⁇ z ⁇ 0.4. That is, it is preferable that the content of cobalt in the lithium cobalt composite oxide precursor is large. This is because if the cobalt content is high, high cycle characteristics are easily obtained along with a high charge / discharge capacity.
• lithium ions can be stably and appropriately supplied by facilitating lithium ion desorption / insertion.
• high cycle characteristics can be obtained with a high charge / discharge capacity.
• the eluted fluorine ions are considered to be contained in the form of LiF on the composite surface.
• Fluorine may be dissolved in the base material.
• the lithium ions eluted in the eluate dispersed with ultrapure water are preferably 500 ppm or more and 20000 ppm or less in a mass ratio with respect to the lithium cobalt complex oxide, and 500 ppm or more and 15000 ppm or less. More preferably, it is 500 ppm or more and 10000 ppm or less.
• the charge / discharge capacity is used when used as the positive electrode active material for electrochemical devices. And the cycle characteristics can be improved more effectively.
• the mass ratio of the lithium ions eluted in the eluate dispersed with ultrapure water and the fluorine ions is 0.1 or more and 5 or less. It is preferable that it is 0.3 or more and 4.5 or less, and it is more preferable that it is 0.5 or more and 4.5 or less.
• the mass ratio of the eluted lithium ions to fluorine ions (the mass of fluorine ions / the mass of lithium ions) is within the above range, the charge / discharge capacity and cycle characteristics when used as the active material for the positive electrode of an electrochemical device Can be increased more reliably.
• the average particle diameter (median diameter) of the lithium cobalt composite oxide is preferably 0.5 ⁇ m or more and 30 ⁇ m or less, and more preferably 1 ⁇ m or more and 20 ⁇ m or less.
• the standard of the average particle diameter is a volume standard.
• the charge / discharge capacity and cycle characteristics can be increased more effectively when used as the active material of the positive electrode of the electrochemical device.
• the BET specific surface area of the lithium cobalt composite oxide is less than 0.10 m 2 / g or more 2.00m 2 / g, 0.10m 2 / g or more 1.5 m 2 / g that less is it is more preferable, and even more preferably less 0.10 m 2 / g or more 1.0 m 2 / g.
• the BET specific surface area means a surface area per unit mass determined by the BET method (a method in which gas particles such as nitrogen are adsorbed on solid particles and the surface area is measured from the adsorbed amount).
• the charge / discharge capacity and cycle characteristics can be increased more effectively when used as the active material of the positive electrode of the electrochemical device.
• lithium cobalt-based composite oxide described above is used as an active material for the positive electrode of an electrochemical device, lithium ions can be smoothly inserted and removed, thereby stably supplying lithium ions appropriately. Therefore, high cycle characteristics can be obtained with a high charge / discharge capacity.
• the method for producing a lithium cobalt composite oxide of the present invention has the following general formula (1): Li 1 ⁇ x Co 1 ⁇ z M z O 2 ⁇ a F a ( ⁇ 0.1 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ a ⁇ 2) (1) (Wherein, M represents one or more metal elements selected from the group consisting of Mn, Ni, Fe, V, Cr, Al, Nb, Ti, Cu, and Zn).
• x is more preferably 0 ⁇ x ⁇ 0.5, and further preferably 0 ⁇ x ⁇ 0.3.
• y is more preferably 0 ⁇ y ⁇ 0.8, and more preferably 0 ⁇ y ⁇ 0.6.
• z is more preferably 0 ⁇ z ⁇ 0.7, and further preferably 0 ⁇ z ⁇ 0.4. That is, it is preferable that the content of cobalt in the lithium cobalt composite oxide precursor is large. This is because if the content of cobalt is large, the used positive electrode can be easily regenerated, and high charge / discharge capacity and high cycle characteristics can be easily obtained.
• the elution amount of fluorine ions can be controlled, for example, by controlling the amount of the electrolyte solution containing fluorine when the lithium phosphorus complex oxide precursor and the lithium compound are reacted. That is, when the fluorine is insufficient, the electrolytic solution is added and regenerated.
• the amount of fluorine ions eluted can be controlled by discharging the electrolytic solution by centrifugation or the like.
• the elution amount of lithium ions can be controlled by, for example, the amount of lithium source other than the electrolyte, the firing temperature, etc., if the elution amount of fluorine ions is determined.
• the lithium cobalt composite oxide precursor from which lithium has been extracted is, for example, one that is taken out from the used electrode after charge / discharge using an organic solvent.
• Chemically extracted lithium state in which lithium ions are scattered by baking at high temperature, state after lithium is extracted from powder or pellets by charge and discharge, and the like.
• lithium cobalt composite oxide precursor from which lithium is partially removed lithium remains partially, so that it is easier to produce a lithium cobalt composite oxide than when a coprecipitate raw material is used.
• the amount of the lithium compound used can be reduced, and the lithium cobalt composite oxide can be produced at a low cost.
• lithium is extracted electrochemically (specifically, by charge / discharge).
• Such a method can be suitably used as a method for extracting lithium. This is because lithium can be easily extracted.
• the lithium cobalt composite oxide precursor is molded with a thickness of 1.0 mm or more, more preferably 5.0 mm or more. It is preferable that it is pulled out.
• Such a method can be suitably used as a method for extracting lithium. This is because if the lithium cobalt based composite oxide precursor is molded with the above thickness, handling of the lithium cobalt based composite oxide precursor is good.
• the lithium compound is, for example, lithium carbonate, lithium hydroxide, lithium oxide, lithium oxalate, lithium phosphate, lithium hexafluorophosphate, or lithium tetrafluoroborate.
• it is lithium hydroxide, more preferably lithium hydroxide and lithium hexafluorophosphate, or a mixture of lithium hydroxide and lithium tetrafluoroborate, more preferably hydroxide. It is a mixture of lithium and lithium hexafluorophosphate.
• Lithium hydroxide is particularly preferable because it is easily available industrially, has high reactivity, and is inexpensive. Further, it is a good lithium conductor contained as an electrolyte in a lithium hexafluorophosphate electrolyte and a lithium tetrafluoroborate electrolyte, and is an ideal lithium compound for obtaining an excellent charge / discharge capacity.
• the step of reacting includes a step of firing, and in the step of firing, the firing temperature is preferably 600 ° C. or higher and 1100 ° C. or lower, and 700 ° C. or higher and 1100 ° C. or lower. More preferably, it is 800 degreeC or more and 1100 degrees C or less.
• a method for reacting the lithium cobalt complex oxide precursor and the lithium compound a method of performing firing in the above temperature range can be suitably used.
• Calcination time is preferably 1 hour to 50 hours, more preferably 2 hours to 15 hours, and further preferably 2 hours to 8 hours. Furthermore, it is preferable to perform a calcining step before firing, the calcining temperature is preferably 150 ° C. or higher and 450 ° C. or lower, more preferably 200 ° C. or higher and 300 ° C. or lower, and the calcining time is 30 minutes. It is preferably 5 hours or less and more preferably 2 hours or more and 5 hours or less.
• the above firing is preferably performed in an air atmosphere or an oxygen atmosphere. Since it is desirable that oxygen be present during the reaction between the lithium cobalt complex oxide precursor and the lithium compound, it is preferable to carry out the reaction in an air atmosphere containing oxygen or an oxygen atmosphere. If firing is performed in an air atmosphere, adjustment of the firing atmosphere is unnecessary, which can reduce the manufacturing cost and is more preferable.
• lithium cobalt type complex oxide it can also bake together with another lithium containing compound.
• the lithium-containing compound include a composite oxide composed of lithium and a transition metal element, or a phosphate compound having lithium and a transition metal element.
• these lithium-containing compounds compounds having at least one of nickel, iron, manganese, and cobalt are preferable.
• These chemical formulas are represented by, for example, Li c M1O 2 or Li d M2PO 4 .
• M1 and M2 represent at least one or more transition metal elements, and the values of c and d vary depending on the battery charge / discharge state, but generally 0.05 ⁇ c ⁇ 1.1, 0.05 ⁇ d ⁇ 1.1.
• Examples of the composite oxide having lithium and a transition metal element include lithium cobalt composite oxide (Li c CoO 2 ) and lithium nickel composite oxide (Li c NiO 2 ).
• a method other than firing may be used, or firing and other methods. You may use together. For example, when the reaction is performed, hydrothermal treatment may be performed, the number of firings may be increased, pellet molding may be performed, and firing may be performed.
• the method for producing a lithium-cobalt composite oxide described above is used, even if the lithium-cobalt composite oxide regenerated from a used positive electrode is used as an active material for the positive electrode of an electrochemical device, it is highly charged. Since high cycle characteristics can be obtained together with the discharge capacity, it is possible to produce a lithium-cobalt composite oxide that can provide high cycle characteristics together with a high charge / discharge capacity when used as an active material for a positive electrode of an electrochemical device at a low cost. .
• the lithium cobalt based composite oxide can be used as a positive electrode active material for various electrochemical devices (for example, batteries, sensors, electrolytic cells, etc.).
• electrochemical device refers to a device including an electrode plate material through which an electric current flows, that is, a device that can extract electric energy in general, and includes an electrolytic cell, a primary battery, and a secondary battery. It is a concept that includes.
• the “secondary battery” is a concept including so-called storage batteries such as lithium ion secondary batteries, nickel hydride batteries, nickel cadmium batteries, and power storage elements such as electric double layer capacitors.
• Said lithium cobalt type complex oxide is especially suitable as an electrode material of a lithium ion secondary battery and an electrolytic cell.
• the shape of the electrolytic cell may be any shape as long as it contains an electrode plate material that allows current to flow.
• the shape of the lithium ion secondary battery can be applied to any of coins, buttons, sheets, cylinders, and square shapes.
• the use of the lithium ion secondary battery to which the lithium cobalt based composite oxide of the present invention is applied is not particularly limited.
• the positive electrode active material layer preferably contains 50 to 100% by mass of the lithium cobalt composite oxide of the present invention. Further, it contains any one or more of positive electrode active materials capable of occluding and releasing lithium ions, and may contain other materials such as binders, conductive assistants, and dispersants depending on the design. Good.
• the positive electrode has, for example, a positive electrode active material layer on both sides or one side of the current collector.
• the current collector may be formed of a conductive material such as aluminum, for example.
• the negative electrode active material is preferably any one of silicon oxides represented by the general formula SiO x (0.5 ⁇ x ⁇ 1.6) or a mixture of two or more thereof.
• the negative electrode active material layer contains the above negative electrode active material, and may contain other materials such as a binder, a conductive additive, and a dispersant depending on the design.
• the negative electrode has the same configuration as the positive electrode described above, and has, for example, a negative electrode active material layer on one side or both sides of a current collector. It is preferable that the negative electrode has a larger negative electrode charge capacity than the electric capacity (charge capacity as a battery) obtained from the positive electrode active material agent. This is for suppressing the deposition of lithium metal on the negative electrode.
• binder for example, any one or more of a polymer material and a synthetic rubber can be used.
• the polymer material include polyvinylidene fluoride, polyimide, polyamideimide, aramid, polyacrylic acid, lithium polyacrylate, and carboxymethylcellulose.
• the synthetic rubber is, for example, styrene butadiene rubber, fluorine rubber, ethylene propylene diene, or the like.
• any 1 or more types of carbon materials such as carbon black, acetylene black, graphite, ketjen black, a carbon nanotube, carbon nanofiber, can be used, for example.
• Electrode At least a part of the active material layer or the separator is impregnated with a liquid electrolyte (electrolytic solution).
• This electrolytic solution has an electrolyte salt dissolved in a solvent, and may contain other materials such as additives.
• the solvent include non-aqueous solvents.
• the non-aqueous solvent include the following materials. Ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, 1,2-dimethoxyethane or tetrahydrofuran.
• At least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate is desirable. This is because better characteristics can be obtained. In this case, more advantageous characteristics can be obtained by combining a high viscosity solvent such as ethylene carbonate or propylene carbonate and a low viscosity solvent such as dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate. This is because the dissociation property and ion mobility of the electrolyte salt are improved.
• the solvent contains at least one of a halogenated chain carbonate or a halogenated cyclic carbonate.
• a halogenated chain carbonate is a chain carbonate having halogen as a constituent element (at least one hydrogen is replaced by a halogen).
• the halogenated cyclic carbonate is a cyclic carbonate having halogen as a constituent element (at least one hydrogen is replaced by halogen).
• the kind of halogen is not particularly limited, but fluorine is more preferable. This is because a film having a higher quality than other halogens is formed. Further, the larger the number of halogens, the more desirable, because the resulting coating is more stable and the decomposition reaction of the electrolyte is reduced.
• the halogenated chain carbonate include fluoromethyl methyl carbonate and difluoromethyl methyl carbonate.
• halogenated cyclic carbonate include 4-fluoro-1,3-dioxolane-2-one and 4,5-difluoro-1,3-dioxolane-2-one.
• the solvent additive contains an unsaturated carbon bond cyclic carbonate. This is because a stable film is formed on the surface of the negative electrode during charging and discharging, and the decomposition reaction of the electrolyte can be suppressed.
• the unsaturated carbon bond cyclic ester carbonate include vinylene carbonate and vinyl ethylene carbonate.
• sultone cyclic sulfonate ester
• sultone include propane sultone and propene sultone.
• the solvent preferably contains an acid anhydride. This is because the chemical stability of the electrolytic solution is improved.
• the acid anhydride include propanedisulfonic acid anhydride.
• the electrolyte salt can contain, for example, any one or more of light metal salts such as lithium salts.
• the lithium salt include lithium hexafluorophosphate (LiPF 6 ) and lithium tetrafluoroborate (LiBF 4 ).
• the content of the electrolyte salt is preferably 0.5 mol / kg or more and 2.5 mol / kg or less with respect to the solvent. This is because high ionic conductivity is obtained.
• the current collector of the electrode is not particularly limited as long as it is an electronic conductor that does not cause a chemical change in the configured lithium ion secondary battery and electrochemical device, but for example, stainless steel, nickel, aluminum, titanium, The surface of calcined carbon, aluminum or stainless steel is surface-treated with carbon, nickel, copper, titanium or silver.
• the negative electrode is made of copper, in addition to stainless steel, nickel, copper, titanium, aluminum, calcined carbon, etc. Or a surface of stainless steel treated with carbon, nickel, titanium, silver, or the like, or an Al—Cd alloy is used.
• the separator separates the positive electrode and the negative electrode and allows lithium ions to pass through while preventing current short-circuiting due to both-pole contact.
• This separator is formed of, for example, a porous film made of synthetic resin or ceramic, and may have a laminated structure in which two or more kinds of porous films are laminated.
• the synthetic resin include polytetrafluoroethylene, polypropylene, and polyethylene.
• the electrochemical device of the present invention comprises a negative electrode active material layer containing negative electrode active material particles having a charge / discharge efficiency of 80% or less when used as a negative electrode active material of an electrochemical device, and a negative electrode current collector, An electrochemical device having a positive electrode active material layer containing the lithium cobalt-based composite oxide and a positive electrode comprising a positive electrode current collector.
• the electrochemical device of the present invention includes a negative electrode active material layer containing negative electrode active material particles containing silicon oxide represented by a composition formula of SiO x (0.5 ⁇ x ⁇ 1.6) and a negative electrode current collector.
• It may be an electrochemical device having a negative electrode composed of a body, and a positive electrode composed of a positive electrode active material layer containing the lithium cobalt composite oxide and a positive electrode current collector. Note that the negative electrode and the positive electrode may not include a current collector.
• Such an electrochemical device can have high cycle characteristics as well as high charge / discharge capacity.
• the regenerated lithium cobalt composite oxide tends to increase the powder resistance.
• the charge / discharge efficiency decreases. Therefore, the negative electrode active material particles having a charge / discharge efficiency of 80% or less are used. When used, it is sufficient in terms of the balance between the charge and discharge efficiency of the positive electrode and the negative electrode, and a stable charge and discharge current is obtained, which is preferable.
• the lithium secondary battery of the present invention comprises a negative electrode active material layer containing negative electrode active material particles having a charge / discharge efficiency of 80% or less when used as a negative electrode active material of a lithium ion secondary battery, and a negative electrode current collector. And a positive electrode made of a positive electrode active material layer containing the lithium cobalt-based composite oxide and a positive electrode current collector. Further, the lithium secondary battery of the present invention includes a negative electrode active material layer containing negative electrode active material particles containing silicon oxide represented by a composition formula of SiO x (0.5 ⁇ x ⁇ 1.6), and a negative electrode collector.
• It may be a lithium ion secondary battery having a negative electrode made of an electric conductor, a positive electrode active material layer containing the lithium cobalt-based composite oxide, and a positive electrode made of a positive electrode current collector. Note that the negative electrode and the positive electrode may not include a current collector.
• Such a lithium secondary battery can have high cycle characteristics as well as high charge / discharge capacity.
• Example 1 In a button-type coin battery (CR2032), Li 0.5 CoO 2 in the form of pellets (thickness 15 mm) from which lithium was extracted with a constant current was dried together with an electrolyte using lithium hexafluorophosphate (LiPF 6 ) as an electrolyte. Then, lithium carbonate (Li 2 CO 3 ) was mixed with the lightly pulverized powder so that the equivalent ratio of Li / Co was 1.00 / 1.00. The mixture was fired in the atmosphere (800 ° C. for 5 hours), then cooled and finely pulverized. Then classified with a sieve having a mesh opening 75 [mu] m, to produce a lithium-cobalt composite oxide having the composition of LiCoO 2.
• LiPF 6 lithium hexafluorophosphate
• Example 2 In an electrolytic cell, Li 0.5 CoO 2 in the form of a pellet (thickness 20 mm) from which lithium was extracted at a constant current was dried together with an electrolyte using lithium hexafluorophosphate (LiPF 6 ) as an electrolyte, and lightly pulverized. Lithium carbonate (Li 2 CO 3 ) was mixed with the powder so that the equivalent ratio of Li / Co was 1.00 / 1.00. The mixture was fired in the atmosphere (850 ° C. for 3 hours), then cooled and finely pulverized. Then classified with a sieve having a mesh opening 75 [mu] m, to produce a lithium-cobalt composite oxide having the composition of LiCoO 2.
• LiPF 6 lithium hexafluorophosphate
• Example 3 Take out the positive electrode plate from the already used lithium ion secondary battery, dissolve the positive electrode active material applied on the aluminum foil together with the electrolyte using lithium hexafluorophosphate (LiPF 6 ) as the electrolyte, The extracted Li 0.5 CoO 2 was filtered and dried, and mixed with lightly pulverized powder so that lithium carbonate (Li 2 CO 3 ) had an equivalent ratio of Li / Co of 1.00 / 1.00. The mixture was fired in the atmosphere (800 ° C. for 4 hours), then cooled and finely pulverized. Then classified with a sieve having a mesh opening 75 [mu] m, to produce a lithium-cobalt composite oxide having the composition of LiCoO 2.
• LiPF 6 lithium hexafluorophosphate
• Example 4 A positive electrode plate is taken out from a lithium ion secondary battery that has already been used, and the positive electrode is applied on an aluminum foil in DMC (dimethyl carbonate) together with an electrolytic solution using lithium hexafluorophosphate (LiPF 6 ) as an electrolyte.
• the active material was dissolved, the extracted Li 0.5 CoO 2 was filtered and dried, and the powder was lightly pulverized, and lithium carbonate (Li 2 CO 3 ) was added to a Li / Co equivalent ratio of 1.00 / 1.00. And mixed.
• the mixture was fired in the air (800 ° C. for 8 hours), then cooled and finely pulverized. Then classified with a sieve having a mesh opening 75 [mu] m, to produce a lithium-cobalt composite oxide having the composition of LiCoO 2.
• Example 5 Lithium carbonate (Li 2 CO 3 ), cobalt oxide (particle size: 2 ⁇ m), and lithium hexafluorophosphate (LiPF 6 ) powder so that the equivalent ratio of Li / Co is 1.00 / 1.00 Mixed.
• the mixture was fired in the air (800 ° C. for 10 hours), then cooled and finely pulverized. Then classified with a sieve having a mesh opening 75 [mu] m, to produce a lithium-cobalt composite oxide having the composition of LiCoO 2.
• Example 6 Lithium carbonate (Li 2 CO 3 ), cobalt oxide (particle size: 2 ⁇ m), and lithium tetrafluoroborate (LiBF 4 ) powder so that the equivalent ratio of Li / Co is 1.00 / 1.00 Mixed.
• the mixture was fired in the air (800 ° C. for 6 hours), then cooled and finely pulverized. Then classified with a sieve having a mesh opening 75 [mu] m, to produce a lithium-cobalt composite oxide having the composition of LiCoO 2.
• Example 7 Li 0.5 Ni 1/3 Mn 1/3 Co 1/3 O 2 in the form of pellets (thickness 20 mm) from which lithium was extracted at a constant current in an electrolytic cell, and lithium hexafluorophosphate (LiPF) as the electrolyte 6 ) Lithium carbonate (Li 2 CO 3 ) was mixed with the electrolyte solution using ( 4 ) and lightly pulverized so that the equivalent ratio of Li / (Ni + Mn + Co) was 1.05 / 1.00. The mixture was fired in the atmosphere (700 ° C. for 5 hours), then cooled and finely pulverized. Subsequently, the mixture was classified with a sieve having an opening of 75 ⁇ m to produce a lithium cobalt composite oxide having a composition of LiNi 1/3 Mn 1/3 Co 1/3 O 2 .
• Example 8 Li 0.5 Ni 1/3 Mn 1/3 Co 1/3 O 2 in the form of pellets (thickness 15 mm) from which lithium was extracted at a constant current in an electrolytic cell, and lithium hexafluorophosphate (LiPF) as the electrolyte 6 ) Lithium carbonate (Li 2 CO 3 ) was mixed with the electrolyte solution using ( 4 ) and lightly pulverized so that the equivalent ratio of Li / (Ni + Mn + Co) was 1.02 / 1.00. The mixture was baked in the atmosphere for about 5 hours (700 ° C. for 5 hours), then cooled and finely pulverized. Subsequently, the mixture was classified with a sieve having an opening of 75 ⁇ m to produce a lithium cobalt composite oxide having a composition of LiNi 1/3 Mn 1/3 Co 1/3 O 2 .
• Example 9 Li 0.5 Ni 0.5 Mn 0.3 Co 0.2 O 2 in the form of a pellet (thickness 12 mm) from which lithium was extracted with a constant current using a button-type coin battery (CR 2032) was washed with DMC and filtered. After drying, the powder of lightly pulverized powder is mixed with lithium carbonate (Li 2 CO 3 ) and lithium hexafluorophosphate (LiPF 6 ) with an equivalent ratio of Li / (Ni + Mn + Co) of 1.00 / 1.00 Mixed. The mixture was fired in the atmosphere (750 ° C. for 5 hours), then cooled and finely pulverized. Subsequently, the mixture was classified with a sieve having an opening of 75 ⁇ m to produce a lithium cobalt composite oxide having a composition of LiNi 0.5 Mn 0.3 Co 0.2 O 2 .
• LiPF 6 lithium hexafluorophosphate
• Example 10 Li 0.5 Ni 0.6 Mn 0.2 Co 0.2 O 2 in the form of a pellet (thickness 10 mm) obtained by extracting lithium with a constant current using a button-type coin battery (CR 2032), and phosphorous hexafluoride as an electrolyte Lithium carbonate (Li 2 CO 3 ) and Li / (Ni + Mn + Co) in an equivalent ratio of 1.00 / 1.00 to a powder that has been dried and lightly pulverized with an electrolyte using lithium acid (LiPF 6 ) Mixed.
• the mixture was fired in the atmosphere (750 ° C. for 5 hours), then cooled and finely pulverized. Subsequently, the mixture was classified with a sieve having an opening of 75 ⁇ m to produce a lithium cobalt composite oxide having a composition of LiNi 0.6 Mn 0.2 Co 0.2 O 2 .
• Li 0.5 Ni 0.8 Mn 0.1 Co 0.1 O 2 in the form of a pellet (thickness 5 mm) obtained by extracting lithium with a constant current with a button-type coin battery (CR 2032) was used as the electrolyte.
• Lithium hydroxide (LiOH.H 2 O) in Li / (Ni + Mn + Co) equivalent ratio is 1.02 / 1.00 in a powder that has been dried and lightly pulverized with an electrolyte using lithium acid (LiPF 6 ) Mixed.
• the mixture was fired in O 2 gas (700 ° C. for 5 hours), then cooled and finely pulverized. Subsequently, the mixture was classified with a sieve having an opening of 75 ⁇ m to produce a lithium cobalt composite oxide having a composition of LiNi 0.8 Mn 0.1 Co 0.1 O 2 .
• Example 12 Using a button-type coin battery (CR2032), Li 0.5 Ni 0.8 Al 0.05 Co 0.15 O 2 in the form of a pellet (thickness 2 mm) from which lithium was extracted at a constant current was washed with DMC.
• the powder of lithium hydroxide (LiOH.H 2 O), lithium hexafluorophosphate (LiPF 6 ), and lithium tetrafluoroborate (LiBF 4 ) was mixed with Li / (Ni + Al + Co) into the powder that was filtered and dried and lightly pulverized. Were mixed so that the equivalent ratio of 1.00 / 1.00.
• the mixture was fired in O 2 gas (700 ° C. for 5 hours), then cooled and finely pulverized. Subsequently, the mixture was classified with a sieve having an opening of 75 ⁇ m to produce a lithium cobalt composite oxide having a composition of LiNi 0.8 Al 0.05 Co 0.15 O 2 .
• Li 0.5 CoO 2 in the form of pellets (thickness 4 mm) from which lithium was extracted at a constant current was washed with DMC, filtered and dried, and lightly pulverized into lithium carbonate.
• Li 2 CO 3 ) and lithium hexafluorophosphate (LiPF 6 ) powder were mixed so that the equivalent ratio of Li / Co was 1.00 / 1.00. This mixture was fired in the atmosphere (900 ° C., 0.5 hour), then cooled and finely pulverized. Then classified with a sieve having a mesh opening 75 [mu] m, to produce a lithium-cobalt composite oxide having the composition of LiCoO 2.
• Li 0.5 CoO 2 in the form of pellets (thickness 5 mm) from which lithium was extracted at a constant current was washed with DMC, filtered, dried, and lightly pulverized into lithium carbonate. (Li 2 CO 3 ) was mixed so that the equivalent ratio of Li / Co was 1.04 / 1.00.
• This mixture was calcined (950 ° C., 20 hours) in an N 2 —H 2 mixed gas having a H 2 concentration of 5%, then cooled and finely pulverized. Then classified with a sieve having a mesh opening 75 [mu] m, to produce a lithium-cobalt composite oxide having the composition of LiCoO 2.
• Li 0.5 CoO 2 in the form of pellets (thickness 8 mm) from which lithium was drawn at a constant current was washed with DMC, filtered, dried, and lightly pulverized into lithium carbonate. (Li 2 CO 3 ) was mixed so that the equivalent ratio of Li / Co was 1.00 / 1.00. The mixture was fired in the atmosphere (650 ° C. for 8 hours), then cooled and finely pulverized. Then classified with a sieve having a mesh opening 75 [mu] m, to produce a lithium-cobalt composite oxide having the composition of LiCoO 2.
• the measured value is expressed in ppm of the mass ratio with respect to the lithium cobalt complex oxide.
• Table 1 shows the measurement results of the amounts of ultrapure water-eluting fluorine ions and lithium ions. Further, the ratio thereof (the mass of fluorine ions / the mass of lithium ions) is also shown in Table 1.
• ⁇ Battery performance test> 95% by mass of the lithium cobalt composite oxide of Example 1-12 and Comparative Example 1-5 produced as described above, 2.5% by mass of graphite powder, and 2.5% by mass of polyvinylidene fluoride were mixed.
• NMP N-methyl-2-pyrrolidinone
• a SiO negative electrode was produced.
• a raw material in which metallic silicon and silicon dioxide were mixed was placed in a reaction furnace, deposited in a vacuum of 10 Pa, cooled sufficiently, and then the deposit was taken out and pulverized by a ball mill. After adjusting the particle size, the carbon layer was coated by pyrolysis CVD.
• the prepared powder was subjected to bulk modification using an electrochemical method in a 1: 1 mixed solvent of propylene carbonate and ethylene carbonate (electrolyte salt 1.3 mol / kg).
• the obtained negative electrode active material particles were dried in a carbon dioxide atmosphere.
• the negative electrode active material particles, the precursor of the negative electrode binder, the conductive auxiliary agent 1 (Ketjen black), and the conductive auxiliary agent 2 (acetylene black) are dried at 80: 8: 10: 2.
• the mixture was mixed at a mass ratio to obtain a negative electrode agent, and diluted with NMP to obtain a paste-like negative electrode mixture slurry.
• NMP was used as a solvent for polyamic acid (a binder precursor).
• the negative electrode mixture slurry was applied to the negative electrode current collector with a coating apparatus and then dried.
• the negative electrode binder (polyimide) was formed. After firing, it was punched into a disk having a diameter of 16 mm by a press to obtain a negative electrode plate.
• a coin-type non-aqueous electrolyte secondary battery was manufactured using each member such as the prepared positive electrode plate and negative electrode plate, separator, current collector plate, mounting bracket, external terminal, electrolyte, and the like.
• the electrolytic solution one obtained by dissolving 1 mol of LiPF 6 in 1 liter of a 2: 7: 1 kneaded solution of ethylene carbonate, didiethyl carbonate, and fluoroethylene carbonate was used.
• the lithium cobalt composite oxide of Example 1-11 in which the fluorine ions eluted in the eluate dispersed with ultrapure water are in a mass ratio of 500 ppm to 15000 ppm with respect to the lithium cobalt composite oxide.
• a comparative example in which the fluorine ions eluted in the eluate dispersed with ultrapure water are less than 500 ppm or more than 15000 ppm in a mass ratio with respect to the lithium cobalt complex oxide.
• a high cycle capacity and a high cycle characteristic are obtained.
• the present invention is not limited to the above embodiment.
• the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

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