WO2023182458A1 - リチウムイオン電池用正極活物質、リチウムイオン電池用正極、リチウムイオン電池、全固体リチウムイオン電池用正極活物質、全固体リチウムイオン電池用正極、全固体リチウムイオン電池、リチウムイオン電池用正極活物質の製造方法及び全固体リチウムイオン電池用正極活物質の製造方法 - Google Patents
リチウムイオン電池用正極活物質、リチウムイオン電池用正極、リチウムイオン電池、全固体リチウムイオン電池用正極活物質、全固体リチウムイオン電池用正極、全固体リチウムイオン電池、リチウムイオン電池用正極活物質の製造方法及び全固体リチウムイオン電池用正極活物質の製造方法 Download PDFInfo
- Publication number
- WO2023182458A1 WO2023182458A1 PCT/JP2023/011631 JP2023011631W WO2023182458A1 WO 2023182458 A1 WO2023182458 A1 WO 2023182458A1 JP 2023011631 W JP2023011631 W JP 2023011631W WO 2023182458 A1 WO2023182458 A1 WO 2023182458A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- active material
- electrode active
- lithium ion
- ion battery
- Prior art date
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- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- LQJIDIOGYJAQMF-UHFFFAOYSA-N lambda2-silanylidenetin Chemical compound [Si].[Sn] LQJIDIOGYJAQMF-UHFFFAOYSA-N 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a positive electrode active material for lithium ion batteries, a positive electrode for lithium ion batteries, a lithium ion battery, a positive electrode active material for all solid lithium ion batteries, a positive electrode for all solid lithium ion batteries, an all solid lithium ion battery, and a positive electrode for lithium ion batteries.
- the present invention relates to a method of manufacturing a positive electrode active material and a method of manufacturing a positive electrode active material for an all-solid-state lithium ion battery.
- Lithium ion secondary batteries include liquid-based lithium ion secondary batteries that use an electrolyte, as well as all-solid lithium ion batteries that use a solid electrolyte, and have been attracting attention in recent years.
- LiCoO2 Li(Ni, Co, Al)O 2 and Li(Ni, Co, Mn)O 2 with a high Ni ratio have been replaced since the 2010s to solve problems such as longer cruising range due to the rise of EVs.
- the demand for such products is increasing.
- Li (Ni, Co, Al) O 2 and Li (Ni, Co, Mn) O 2 are increasingly being used due to their high capacity, but they have low thermal stability and cycle characteristics. There are issues such as poor performance.
- a method has been adopted in which the surface of the positive electrode material is modified with an element such as Zr, W, Nb, or Ta, which has a large ionic radius and has a high affinity for oxygen.
- Patent Document 1 discloses a positive electrode active material that is a lithium-nickel-cobalt-manganese composite oxide containing tungsten and niobium. The document also states that with such a configuration, it is possible to provide a positive electrode active material that has excellent output characteristics and generates little gas, and a battery using the same.
- Patent Document 2 discloses that when a transition metal hydroxide containing Ni and Mn as essential and a lithium source are mixed and fired to produce a lithium-containing composite oxide, the space group P- of the X-ray diffraction pattern is A method for producing a lithium-containing composite oxide is disclosed, which is characterized in that a transition metal hydroxide having a (100) plane crystallite diameter of 35 nm or less in a 3m1 crystal structure model is used.
- the document also states that with such a configuration, it is possible to provide a method for producing a lithium-containing composite oxide that can improve performance such as cycle characteristics and rate characteristics of a lithium ion secondary battery.
- Patent Documents 1 and 2 describe that battery characteristics such as cycle characteristics, thermal stability, and rate characteristics are improved by surface modification with elements such as Zr, W, and Nb.
- an oxide of an element different from the element constituting the precursor (a different element) is dry kneaded into a precursor or a calcined powder of the precursor at the same time as a lithium source, and then fired.
- a manufacturing method is described that aims to dissolve elements into a positive electrode active material.
- the present invention has been made to solve the above-mentioned problems, and provides a positive electrode active material for lithium ion batteries, a positive electrode for lithium ion batteries, and a lithium ion battery that exhibits good battery characteristics when used in lithium ion batteries.
- the present invention aims to provide a battery and a method for manufacturing a positive electrode active material for a lithium ion battery.
- the purpose of the present invention is to provide a method for producing a positive electrode active material.
- a positive electrode active material for lithium ion batteries that does not exist as independent particles that are not attached to the surface of material particles.
- 2. The positive electrode active material for lithium ion batteries as described in 1 above, wherein the 50% cumulative volume particle size D50 of the positive electrode active material for lithium ion batteries is 3 to 18 ⁇ m.
- 3. A positive electrode for a lithium ion battery, comprising the positive electrode active material for a lithium ion battery according to 1 or 2 above. 4.
- a lithium ion battery comprising the positive electrode and negative electrode for a lithium ion battery according to 3 above. 5.
- the positive electrode active material for lithium ion batteries according to 1 or 2 above A coating layer made of an oxide of Li and Nb provided on the surface of the positive electrode active material particles of the positive electrode active material for a lithium ion battery; Positive electrode active materials for all-solid-state lithium-ion batteries. 6. 5. The positive electrode active material for an all-solid-state lithium-ion battery as described in 5 above, wherein the Nb content in the positive-electrode active material for an all-solid-state lithium-ion battery is 0.5 to 0.8% by mass. 7. A positive electrode for an all-solid lithium ion battery, comprising the positive electrode active material for an all-solid lithium ion battery according to 5 above. 8.
- An all-solid lithium ion battery comprising the positive electrode and negative electrode for an all-solid lithium ion battery according to 7 above.
- a step of preparing a precursor of a positive electrode active material for a lithium ion battery represented by the composition shown in the following formula (2), Ni b Co c Mnd (OH) 2 (2) (In the above formula (2), 0.8 ⁇ b ⁇ 0.9, 0.07 ⁇ c ⁇ 0.15, and b+c+d 1.)
- At least one selected from Zr oxide, Ta oxide, and W oxide having a 50% cumulative volume particle size D50 of 1 ⁇ m or less is wet-mixed with the precursor of the positive electrode active material for lithium ion batteries. obtaining a mixture; Dry mixing the mixture with a lithium source and firing at 700° C.
- a method for producing a positive electrode active material for a lithium ion battery comprising: 10. 10. The method for producing a positive electrode active material for a lithium ion battery according to 9 above, wherein the Zr oxide, Ta oxide, and W oxide have a D50 of 0.3 to 1.0 ⁇ m. 11. 10. The method for producing a positive electrode active material for a lithium ion battery according to 9 above, wherein in the step of baking the mixture, the mixture is dry mixed with a lithium source and baked at 700 to 800° C. for 4 to 12 hours. 12.
- a positive electrode active material for a lithium ion battery that has good battery characteristics when used in a lithium ion battery, a positive electrode for a lithium ion battery, a lithium ion battery, and a method for producing a positive electrode active material for a lithium ion battery can be provided.
- a positive electrode active material for an all-solid-state lithium-ion battery that has good battery characteristics when used in an all-solid-state lithium-ion battery, a positive electrode for an all-solid-state lithium-ion battery, an all-solid-state lithium-ion battery, and A method for producing a positive electrode active material for an all-solid lithium ion battery can be provided.
- FIG. 6 is an FE-EPMA SEM image of positive electrode active material particles shown in Example 6
- FIG. 1 is a WDX mapping image of Zr obtained by FE-EPMA, which corresponds to the left diagram in FIG.
- the figure on the left is an FE-EPMA SEM image of positive electrode active material particles showing an example of a state (Comparative Example 5) in which the oxide of M exists as independent particles that are not attached to the surface of positive electrode active material particles.
- FIG. 2 is a WDX mapping image of Zr obtained by FE-EPMA, which corresponds to the left diagram in FIG. 1 is a FE-EPMA SEM image of the positive electrode active material particles of Examples 1 to 6, and a WDX mapping image of Zr obtained by FE-EPMA corresponding to the SEM image.
- 1 is a schematic diagram of an all-solid-state lithium ion battery according to an embodiment of the present invention.
- a positive electrode active material for a lithium ion battery according to an embodiment of the present invention is represented by a composition shown in the following formula (1).
- a which indicates the lithium composition
- a is controlled to be 1.0 ⁇ a ⁇ 1.05. Since a indicating the lithium composition is 1.0 or more, reduction of nickel due to lithium deficiency can be suppressed. In addition, since a, which indicates the lithium composition, is 1.05 or less, residual alkali components such as lithium carbonate and lithium hydroxide present on the surface of the positive electrode active material particles, which can become a resistance component when used as a battery, are suppressed. be able to.
- b which indicates the nickel composition
- of the positive electrode active material for lithium ion batteries is controlled to be 0.8 ⁇ b ⁇ 0.9, and has a so-called high nickel composition. Since b, which indicates the nickel composition, is 0.8 or more, a good battery capacity of the lithium ion battery can be obtained.
- the positive electrode active material for lithium ion batteries mostly has the form of secondary particles in which a plurality of primary particles are aggregated, and partially contains primary particles that are not aggregated as secondary particles.
- the shapes of the primary particles constituting the secondary particles and the primary particles that exist alone are not particularly limited, and may have various shapes such as approximately spherical, approximately elliptical, approximately plate-like, approximately acicular, etc. Good too.
- the form in which a plurality of primary particles agglomerate for example, the form in which they agglomerate in random directions, or the form in which they agglomerate almost uniformly radially from the center to form approximately spherical or approximately elliptical secondary particles. It may be in various forms such as a form in which it is formed.
- the positive electrode active material for lithium ion batteries satisfies 0.0025 ⁇ e/(b+c+d+e) ⁇ 0.016, and M is at least one selected from Zr, Ta, and W. That is, the positive electrode active material for lithium ion batteries contains at least one element selected from Zr, Ta, and W.
- the element By solidly dissolving the element inside the positive electrode active material, the element has the effect of reducing the expansion and contraction behavior of the crystal lattice due to insertion and desorption of lithium during charging and discharging. Therefore, when the composition ratio of the element, e/(b+c+d+e), is 0.0025 or more, the cycle characteristics are improved. On the other hand, this element does not contribute to charge compensation during charging and discharging.
- e/(b+c+d+e) which is the composition ratio of the element, is 0.016 or less, it has the effect of suppressing a decrease in discharge capacity. Further, preferably 0.003 ⁇ e/(b+c+d+e) ⁇ 0.012, and more preferably 0.003 ⁇ e/(b+c+d+e) ⁇ 0.008.
- the positive electrode active material for lithium ion batteries is subjected to WDX mapping analysis (Wave Length-dispersive) of the positive electrode active material particles in a field of view of 50 ⁇ m x 50 ⁇ m using FE-EPMA (Field Emission-Electron Probe Micro Analysis).
- WDX mapping analysis Wide Length-dispersive
- FE-EPMA Field Emission-Electron Probe Micro Analysis
- X In -ray mapping spectroscopy wavelength dispersive X-ray mapping analysis
- the oxide of M is attached to the surface of the positive electrode active material particles, and the oxide of M is not attached to the surface of the positive electrode active material particles. It does not exist as an independent particle.
- a small amount of a different element (an element different from Li, Ni, Co, and Mn, which are elements constituting the positive electrode active material for lithium ion batteries), such as M (Zr, Ta, and W), is present.
- M Zr, Ta, and W
- WDX mapping analysis of the positive electrode active material particles in a field of view of 50 ⁇ m x 50 ⁇ m using FE-EPMA can be carried out by performing stage scanning under the conditions of an acceleration voltage of 15.0 kV and an irradiation current of 2.0 x 10 -8 A. can.
- the left diagram in Figure 1 shows the above-mentioned "M oxide is attached to the surface of the positive electrode active material particles, and the M oxide exists as an independent particle that is not attached to the surface of the positive electrode active material particles.”
- 2 is an FE-EPMA SEM image of positive electrode active material particles showing an example of a state in which "no" state is observed.
- the right diagram in FIG. 1 is a WDX mapping image of Zr obtained by FE-EPMA, which corresponds to the left diagram in FIG.
- the left diagram of FIG. 2 is an FE-EPMA SEM image of the positive electrode active material particles showing an example of a state in which the oxide of M exists as an independent particle that is not attached to the surface of the positive electrode active material particles.
- FIG. 2 is a WDX mapping image of Zr obtained by FE-EPMA, which corresponds to the left diagram in FIG.
- the oxide of M exists attached to the surface and does not exist as an independent particle with respect to the positive electrode active material particles as shown in Figure 2.
- FIG. 1 corresponds to positive electrode active material particles of Example 6, which will be described later
- FIG. 2 corresponds to positive electrode active material particles of Comparative Example 5, which will be described later.
- the 50% cumulative volume particle size D50 of the positive electrode active material for lithium ion batteries is 3 to 18 ⁇ m.
- the 50% cumulative volume particle size D50 is the volume particle size at 50% accumulation in a volume-based cumulative particle size distribution curve.
- the 50% cumulative volume particle size D50 of the positive electrode active material for lithium ion batteries is 3 ⁇ m or more, the specific surface area can be suppressed and the amount of coverage of Li and Nb oxides can be suppressed.
- the 50% cumulative volume particle size D50 of the positive electrode active material for lithium ion batteries is 18 ⁇ m or less, it is possible to prevent the specific surface area from becoming excessively small.
- the 50% cumulative volume particle size D50 of the positive electrode active material for lithium ion batteries is more preferably 3 to 15 ⁇ m, even more preferably 3 to 10 ⁇ m, and even more preferably 3 to 8 ⁇ m.
- the above 50% cumulative volume particle size D50 can be measured, for example, as follows. That is, first, 100 mg of the positive electrode active material powder was dispersed by irradiating 40 W ultrasonic waves for 60 seconds at a flow rate of 50% using Microtrac's laser diffraction particle size distribution analyzer "MT3300EXII", and then the particle size distribution was determined. and obtain a volume-based cumulative particle size distribution curve.
- the volume particle size at 50% accumulation is defined as the 50% cumulative volume particle size D50 of the positive electrode active material powder.
- the water-soluble solvent used in the measurement was passed through a filter with a solvent refractive index of 1.333, a particle permeability condition of 1.81, a non-spherical shape, and a measurement range of 0.021 to 2000 ⁇ m. , the measurement time is 30 seconds.
- the positive electrode active material for an all-solid-state lithium ion battery according to the embodiment of the present invention includes the positive electrode active material for a lithium ion battery according to the embodiment of the present invention described above, and the positive electrode active material particle surface of the positive electrode active material for a lithium ion battery. and a coating layer made of oxides of Li and Nb provided on the oxide layer.
- the oxide of Li and Nb constituting the coating layer may contain lithium niobate (LiNbO 3 ) or may be LiNbO 3 .
- the content of Nb in the positive electrode active material for an all-solid lithium ion battery is preferably 0.5 to 0.8% by mass.
- the content of Nb is 0.5% by mass or more, the entire surface of the active material is coated, and an increase in resistance due to an interfacial reaction between the solid electrolyte and the positive electrode active material when exposed to a high potential during charging is suppressed.
- Ru When the Nb content is 0.8% by mass or less, the coating layer is formed as thin as possible, so the movement of Li ions in the coating layer during charging and discharging becomes short, and the diffusion movement resistance can be reduced.
- the content of Nb in the positive electrode active material for an all-solid-state lithium ion battery is more preferably 0.6 to 0.7% by mass.
- the thickness of the coating layer is preferably 10 nm or less, more preferably 6 nm or less. When the thickness of the coating layer is 6 nm or less, adverse effects such as inhibition of Li ion movement can be better avoided.
- the lower limit of the thickness of the coating layer is not particularly limited, but is typically 4 nm or more, preferably 5 nm or more. Note that the thickness of the coating layer can be measured by elemental mapping analysis and line analysis using a scanning transmission electron microscope (STEM).
- a basic aqueous solution containing (a) a nickel salt, (b) a cobalt salt, (c) a manganese salt, and (d) ammonia and an alkali metal are prepared.
- An aqueous solution containing a basic aqueous solution of is prepared.
- the nickel salt include nickel sulfate, nickel nitrate, and nickel hydrochloride.
- the cobalt salt include cobalt sulfate, cobalt nitrate, and cobalt hydrochloride.
- Manganese salts include manganese sulfate, manganese nitrate, manganese hydrochloride, and the like.
- Examples of the basic aqueous solution containing ammonia include ammonia aqueous solution, ammonium sulfate, ammonium carbonate, ammonium hydrochloride, and the like.
- the basic aqueous solution of the alkali metal may be an aqueous solution of sodium hydroxide, potassium hydroxide, carbonate, or the like.
- examples of the aqueous solution of the carbonate include aqueous solutions using a salt of a carbonate group, such as an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous sodium bicarbonate solution, and an aqueous potassium bicarbonate solution.
- a salt of a carbonate group such as an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous sodium bicarbonate solution, and an aqueous potassium bicarbonate solution.
- composition of the aqueous solution can be adjusted as appropriate depending on the composition of the precursor to be produced; (c) an aqueous solution containing 1 to 4 g/L of manganese ions, (d) aqueous ammonia of 10 to 28% by mass, and a basic aqueous solution with an alkali metal concentration of 10 to 30% by mass.
- an aqueous solution containing the above-mentioned (a) nickel salt, (b) cobalt salt, (c) manganese salt, and (d) a basic aqueous solution containing ammonia and a basic aqueous solution of an alkali metal is used as a reaction liquid.
- the coprecipitation reaction is carried out while controlling the pH in the reaction solution to 10.8 to 11.4, the ammonium ion concentration to 10 to 22 g/L, and the liquid temperature to 55 to 65°C.
- At least one selected from Zr oxide, Ta oxide, and W oxide having a 50% cumulative volume particle size D50 of 1 ⁇ m or less is added to the precursor of a positive electrode active material for lithium ion batteries by wet process. Mix to get a mixture.
- the total amount of at least one selected from Zr oxide, Ta oxide, and W oxide to be mixed can be adjusted as appropriate depending on the composition of the target positive electrode active material for lithium ion batteries.
- ZrO 2 can be used as the Zr oxide
- Ta 2 O 5 can be used as the Ta oxide
- WO 2 or WO 3 can be used as the W oxide.
- the wet mixing involves adding a precursor of a positive electrode active material for lithium ion batteries and at least one selected from Zr oxide, Ta oxide, and W oxide to an aqueous solvent, and then mechanically mixing the mixture.
- a slurry is prepared by mixing by means. Next, the slurry is allowed to stand still and is dried. In the present invention, it is necessary to dry the slurry while it is left still.
- high-pressure air is sprayed from a spray nozzle to disperse the slurry. Some of the oxides such as 3 are peeled off by high-pressure air, leaving the oxides as independent particles.
- the slurry When the slurry is left to dry as in the present invention, water is simply evaporated by heating, so that the oxides attached during slurry mixing can be prevented from peeling off. Further, in the present invention, it is necessary to prepare the slurry so that the total solid content of the slurry is 40 to 60% by mass, preferably 50% by mass.
- oxides such as ZrO 2 , Ta 2 O 5 , WO 2 or WO 3
- the distance between particles during wet stirring and mixing is far away, and aggregation (adhesion) between particles is difficult to occur; however, in the case of a high slurry concentration, the distance between particles is short, so aggregation (adhesion) between particles is likely to occur. Therefore, when the solid content of the slurry is low, such as about 10% by mass, oxide particles such as ZrO 2 , Ta 2 O 5 , WO 2 or WO 3 are not completely removed during wet stirring and mixing.
- Zr oxide, Ta oxide, and W oxide are wet-mixed to form a solid.
- the rate of adhesion of oxides of different elements (Zr, Ta, W) to the surface of the precursor of the positive electrode active material for lithium ion batteries is improved.
- the D50 of the particles of Zr oxide, Ta oxide, and W oxide to be mixed to 1 ⁇ m or less, positive electrode active materials for lithium ion batteries using oxides of different elements (Zr, Ta, and W) can be obtained.
- the adhesion rate of the substance precursor to the surface is improved.
- the D50 of the particles of the Zr oxide, Ta oxide, and W oxide to be mixed is preferably 0.3 to 1.0 ⁇ m, more preferably 0.3 to 0.5 ⁇ m.
- a lithium source was added to the mixture of the precursor of the positive electrode active material for lithium ion batteries obtained as described above and at least one of an oxide of Zr, an oxide of Ta, and an oxide of W. to form a lithium mixture.
- the amount of the lithium source to be mixed can be adjusted as appropriate depending on the composition of the target positive electrode active material for lithium ion batteries.
- Lithium sources include lithium hydroxide.
- the mixing method the mixing ratio of each raw material is adjusted and dry mixing is carried out using a Henschel mixer, an automatic mortar, a V-type mixer, or the like.
- the lithium mixture obtained as described above is fired at 700° C. or higher for 4 hours or more.
- the lithium mixture is fired at a temperature of 700°C or higher for a long time of 4 hours or more, thereby allowing different elements (Zr, Ta, W) to enter the inside of the positive electrode active material for lithium ion batteries.
- the solid solution rate of is improved. Furthermore, this can prevent oxides of different elements (Zr, Ta, W) from adhering to the surface of the positive electrode active material particles for lithium ion batteries and from existing as independent particles.
- the firing temperature is preferably 700 to 800°C, and the firing time is preferably 4 to 12 hours.
- the firing atmosphere is preferably an oxygen atmosphere.
- a powder of a positive electrode active material for a lithium ion battery can be obtained by crushing the fired body using, for example, a pulverizer.
- the method for producing a positive electrode active material for an all-solid-state lithium ion battery first includes positive electrode active material particles of a positive electrode active material for a lithium ion battery produced by the above-described method for producing a positive electrode active material for a lithium ion battery.
- the surface is coated with an aqueous solution (coating liquid) containing Li and Nb.
- the coating liquid include a peroxo complex aqueous solution of lithium niobate (LiNbO 3 ), an oxalic acid aqueous solution, and the like.
- the coating method is not particularly limited as long as it is a method that allows the solution to be deposited on the surface of the positive electrode active material. A method may also be used.
- the positive electrode for a lithium ion battery according to an embodiment of the present invention is, for example, a positive electrode mixture prepared by mixing a positive electrode active material for a lithium ion battery having the above-mentioned configuration, a conductive additive, and a binder. It has a structure provided on one or both sides. Furthermore, the lithium ion battery according to the embodiment of the present invention includes a lithium ion battery positive electrode having such a configuration and a known lithium ion battery negative electrode.
- conductive additives examples include metallic conductive additives (aluminum, stainless steel (SUS), silver, gold, copper, titanium, etc.), carbon-based conductive additives (graphite and carbon black (acetylene black, Ketjen black, furnace black, channel black, thermal lamp black), and mixtures thereof. These conductive aids may be used alone or in combination of two or more. Further, alloys or metal oxides of these may be used. Among them, from the viewpoint of electrical stability, aluminum, stainless steel, silver, gold, copper, titanium, carbon-based conductive additives, and mixtures thereof are more preferred, and even more preferred are silver, gold, aluminum, stainless steel, and carbon. A carbon-based conductive additive is particularly preferred.
- these conductive aids may be those in which a particulate ceramic material or a resin material is coated with a conductive material (preferably a metal among the above conductive aids) by plating or the like.
- the shape (form) of the conductive auxiliary material is not limited to the particle form, and may be in a form other than the particle form, such as carbon nanofibers, carbon nanotubes, etc., which have been put into practical use as so-called filler-based conductive auxiliary materials. It's okay.
- binders include substances commonly used in positive electrode mixtures for lithium-ion batteries, including copolymers with a structure derived from vinylidene fluoride, polyvinylidene fluoride (PVDF), and tetrafluoroethylene (TEF). ) or a copolymer or homopolymer having a structure derived from hexafluoropropylene (HFP). Specific examples include PVDF-HFP, PVDF-HFP-TEF, PVDF-TEF, and TEF-HFP.
- the positive electrode composite material is made by mixing a positive electrode active material for lithium ion batteries, a conductive additive, and a binder in a solvent to form a positive electrode composite slurry, which is applied to one or both sides of a current collector, and then dried and collected. It is provided on the electric body and constitutes a positive electrode active material layer.
- organic solvents such as hydrocarbon organic solvents, amide compounds, lactam compounds, urea compounds, organic sulfur compounds, cyclic organic phosphorus compounds, etc. can be used alone or as a mixture. Can be used as a solvent.
- hydrocarbon organic solvent saturated hydrocarbons, unsaturated hydrocarbons, or aromatic hydrocarbons can be used. Examples of saturated hydrocarbons include hexane, pentane, 2-ethylhexane, heptane, decane, cyclohexane, and the like. Examples of unsaturated hydrocarbons include hexene, heptene, and cyclohexene.
- aromatic hydrocarbons include toluene, xylene, decalin, 1,2,3,4-tetrahydronaphthalene, and the like. Among these, toluene and xylene are particularly preferred.
- the material constituting the current collector examples include metal materials such as copper, aluminum, titanium, stainless steel, nickel, and alloys thereof, as well as fired carbon, conductive polymer materials, conductive glass, and the like. Among these, aluminum is more preferred from the viewpoints of weight reduction, corrosion resistance, and high conductivity.
- the current collector is preferably a resin current collector made of a conductive polymer material.
- the shape of the current collector is not particularly limited, and may be a sheet-like current collector made of the above-mentioned material or a deposited layer made of fine particles made of the above-mentioned material.
- the thickness of the current collector is not particularly limited, but is preferably 50 to 500 ⁇ m.
- the conductive polymer material constituting the resin current collector for example, a conductive polymer or a resin prepared by adding a conductive agent as necessary can be used.
- the thickness of the positive electrode for lithium ion batteries is preferably 150 to 600 ⁇ m, more preferably 200 to 450 ⁇ m.
- a lithium ion battery using a positive electrode for a lithium ion battery can be obtained by combining a negative electrode serving as a counter electrode, storing it together with a separator in a cell container, injecting an electrolyte, and sealing the cell container.
- a positive electrode is formed on one side of the current collector and a negative electrode is formed on the other side to create a bipolar (bipolar) type electrode, and the bipolar (bipolar) type electrode is laminated with a separator to form a cell container. It can also be obtained by storing the cell, injecting electrolyte, and sealing the cell container.
- the negative electrode examples include those containing a negative electrode active material, a conductive additive, a current collector, and the like.
- a negative electrode active material known negative electrode active materials for lithium ion batteries can be used. coke (e.g., pitch coke, needle coke, petroleum coke, etc.), carbon fiber, etc.), silicon-based materials (silicon, silicon oxide (SiO x ), silicon-carbon composites (carbon particles whose surface is made of silicon and/or silicon carbide, silicon particles or silicon oxide particles whose surfaces are coated with carbon and/or silicon carbide, silicon carbide, etc.) and silicon alloys (silicon-aluminum alloy, silicon-lithium alloy, silicon- (nickel alloy, silicon-iron alloy, silicon-titanium alloy, silicon-manganese alloy, silicon-copper alloy, silicon-tin alloy, etc.), conductive polymers (such as polyacetylene and polypyrrole, etc.), metals (tin, aluminum, Zirconium and titanium, etc.), metal oxide
- Examples of the current collector include those similar to those constituting the positive electrode described above, and from the viewpoint of weight reduction, corrosion resistance, and high conductivity, copper is preferable. Moreover, a resin current collector may be used, and the same current collector as the one constituting the above-mentioned positive electrode can be suitably used.
- the thickness of the current collector is not particularly limited, but is preferably 10 to 60 ⁇ m.
- porous films made of polyethylene or polypropylene, laminated films of porous polyethylene films and porous polypropylene, nonwoven fabrics made of synthetic fibers (polyester fibers, aramid fibers, etc.) or glass fibers, etc., and silica on their surfaces are used.
- separators for lithium ion batteries such as those to which fine ceramic particles of alumina, titania, etc. are attached.
- An all-solid-state lithium-ion battery including a positive electrode formed by the positive electrode active material for an all-solid-state lithium ion battery according to an embodiment of the present invention, the positive electrode as a positive electrode layer, the positive electrode layer, a solid electrolyte layer, and a negative electrode layer. It can be made.
- the solid electrolyte layer and negative electrode layer that constitute the all-solid-state lithium ion battery according to the embodiment of the present invention are not particularly limited, and can be formed of known materials and have a known configuration as shown in FIG. I can do it.
- the positive electrode layer of the all-solid-state lithium ion battery can be formed by forming a layered positive electrode mixture formed by mixing the positive electrode active material for all-solid lithium-ion batteries according to the embodiment of the present invention and a solid electrolyte. .
- the content of the positive electrode active material in the positive electrode layer is, for example, preferably 50% by mass or more and 99% by mass or less, and more preferably 60% by mass or more and 90% by mass or less.
- the positive electrode mixture may further contain a conductive additive.
- a conductive aid a carbon material, a metal material, or a mixture thereof can be used.
- Conductive aids include, for example, carbon, nickel, copper, aluminum, indium, silver, cobalt, magnesium, lithium, chromium, gold, ruthenium, platinum, beryllium, iridium, molybdenum, niobium, osnium, rhodium, tungsten and zinc. It may contain at least one element selected from the group.
- the conductive aid is preferably a highly conductive elemental carbon, an elemental metal, a mixture, or a compound containing carbon, nickel, copper, silver, cobalt, magnesium, lithium, ruthenium, gold, platinum, niobium, osnium, or rhodium.
- carbon black such as Ketjen black, acetylene black, Denka black, thermal black, channel black, graphite, carbon fiber, activated carbon, etc. can be used.
- the average thickness of the positive electrode layer of an all-solid-state lithium ion battery is not particularly limited, and can be appropriately designed depending on the purpose.
- the average thickness of the positive electrode layer of the all-solid-state lithium ion battery may be, for example, 1 ⁇ m to 100 ⁇ m, or 1 ⁇ m to 10 ⁇ m.
- the method for forming the positive electrode layer of an all-solid-state lithium ion battery is not particularly limited, and can be appropriately selected depending on the purpose.
- Examples of the method for forming the positive electrode layer of an all-solid lithium ion battery include a method of compression molding a positive electrode active material for an all-solid lithium ion battery.
- the negative electrode layer of the all-solid-state lithium ion battery may be formed by forming a layer of a known negative electrode active material for all-solid-state lithium ion batteries. Further, the negative electrode layer may be formed in a layered form of a negative electrode mixture formed by mixing a known negative electrode active material for all-solid-state lithium ion batteries and a solid electrolyte.
- the content of the negative electrode active material in the negative electrode layer is, for example, preferably 10% by mass or more and 99% by mass or less, and more preferably 20% by mass or more and 90% by mass or less.
- the negative electrode layer may contain a conductive additive like the positive electrode layer.
- the same material as the material explained for the positive electrode layer can be used as the conductive aid.
- negative electrode active materials include carbon materials, specifically, artificial graphite, graphite carbon fiber, resin-sintered carbon, pyrolytic vapor grown carbon, coke, mesocarbon microbeads (MCMB), and furfuryl alcohol resin-sintered carbon. , polyacene, pitch-based carbon fiber, vapor-grown carbon fiber, natural graphite, non-graphitizable carbon, etc., or a mixture thereof can be used.
- metals themselves such as metallic lithium, metallic indium, metallic aluminum, metallic silicon, etc., or alloys in combination with other elements or compounds can be used.
- the average thickness of the negative electrode layer of the all-solid lithium ion battery is not particularly limited, and can be appropriately selected depending on the purpose.
- the average thickness of the negative electrode layer of the all-solid lithium ion battery may be, for example, 1 ⁇ m to 100 ⁇ m, or 1 ⁇ m to 10 ⁇ m.
- the method for forming the negative electrode layer of an all-solid-state lithium ion battery is not particularly limited, and can be appropriately selected depending on the purpose.
- Examples of methods for forming the negative electrode layer of an all-solid-state lithium ion battery include a method of compression molding negative electrode active material particles, a method of vapor depositing a negative electrode active material, and the like.
- solid electrolyte a known solid electrolyte for all-solid lithium ion batteries can be used.
- solid electrolyte an oxide-based solid electrolyte, a sulfide-based solid electrolyte, or the like can be used.
- oxide-based solid electrolytes examples include LiTi 2 (PO 4 ) 3 , Li 2 O-B 2 O 3 -P 2 O 5 , Li 2 O-SiO 2 , Li 2 O-B 2 O 3 , and Li 2 O--B 2 O 3 --ZnO and the like.
- Examples of the sulfide solid electrolyte include LiI-Li 2 S-P 2 S 5 , LiI-Li 2 SB 2 S 3 , Li 3 PO 4 -Li 2 S-Si 2 S, Li 3 PO 4 - Li 2 S-SiS 2 , LiPO 4 -Li 2 S-SiS, LiI-Li 2 SP 2 O 5 , LiI-Li 3 PO 4 -P 2 S 5 , Li 3 PS 4 , and Li 2 SP 2 S 5 etc.
- the average thickness of the solid electrolyte layer of the all-solid lithium ion battery is not particularly limited, and can be appropriately designed depending on the purpose.
- the average thickness of the solid electrolyte layer of the all-solid lithium ion battery may be, for example, 50 ⁇ m to 500 ⁇ m, or 50 ⁇ m to 100 ⁇ m.
- the method for forming the solid electrolyte layer of the all-solid lithium ion battery is not particularly limited, and can be appropriately selected depending on the purpose.
- Examples of methods for forming the solid electrolyte layer of an all-solid-state lithium ion battery include sputtering using a solid electrolyte target material, and compression molding of a solid electrolyte.
- Other members constituting the all-solid-state lithium ion battery are not particularly limited and can be appropriately selected depending on the purpose, and include, for example, a positive electrode current collector, a negative electrode current collector, and a battery case.
- the size and structure of the positive electrode current collector are not particularly limited, and can be appropriately selected depending on the purpose.
- Examples of the material of the positive electrode current collector include die steel, stainless steel, aluminum, aluminum alloy, titanium alloy, copper, gold, and nickel.
- Examples of the shape of the positive electrode current collector include foil, plate, and mesh shapes.
- the average thickness of the positive electrode current collector may be, for example, 10 ⁇ m to 500 ⁇ m, or 50 ⁇ m to 100 ⁇ m.
- the size and structure of the negative electrode current collector are not particularly limited, and can be appropriately selected depending on the purpose.
- Examples of the material for the negative electrode current collector include die steel, gold, indium, nickel, copper, and stainless steel.
- Examples of the shape of the negative electrode current collector include a foil shape, a plate shape, and a mesh shape.
- the average thickness of the negative electrode current collector may be, for example, 10 ⁇ m to 500 ⁇ m, or 50 ⁇ m to 100 ⁇ m.
- the battery case is not particularly limited, and can be appropriately selected depending on the purpose.
- Examples include known laminate films that can be used in conventional all-solid-state batteries.
- Examples of the laminate film include a resin laminate film and a film in which a metal is vapor-deposited on a resin laminate film.
- the shape of the battery is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a cylindrical shape, a square shape, a button shape, a coin shape, and a flat shape.
- Example 1 a precursor of a positive electrode active material for a lithium ion battery represented by the composition formula: Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 was prepared.
- a precursor of a positive electrode active material for lithium ion batteries and ZrO 2 having a D50 of 0.35 ⁇ m were added to the water solvent in an amount of 0.4 mol%, and this was mixed by mechanical means ( A slurry was prepared by wet mixing). At this time, the slurry was prepared so that the total solid content of the slurry was 50% by mass. Next, the slurry was left to stand and dried to obtain a mixture.
- lithium hydroxide lithium source
- Henschel mixer dry mixing
- Examples 2 to 17, Comparative Examples 6 and 7 The composition of the precursor of the positive electrode active material, the type of mixed oxide of a different element, the particle size of the oxide of the different element, the amount of charged oxide of the different element, the firing temperature, and the firing time are shown in Table 1, respectively.
- a positive electrode active material was produced in the same manner as in Example 1 except for the following conditions.
- the positive electrode active material was prepared in the same manner as in Example 1, except that the oxide of a different element was not mixed in the positive electrode active material precursor, and the composition and firing temperature of the positive electrode active material precursor were set to the conditions shown in Table 1. was created.
- Example 5 By mixing the oxide of a different element with the precursor of the positive electrode active material using a Henschel mixer (dry mixing), a mixture of the precursor of the positive electrode active material and the oxide of a different element is created, and the precursor of the positive electrode active material is A positive electrode active material was produced in the same manner as in Example 1, except that the body composition and firing temperature were set to the conditions shown in Table 1.
- Example 18 First, a precursor of a positive electrode active material for a lithium ion battery represented by the composition formula: Ni 0.82 Co 0.15 Mn 0.03 (OH) 2 was prepared. Next, a precursor of a positive electrode active material for lithium ion batteries and ZrO 2 having a D50 of 0.35 ⁇ m were added to the water solvent in an amount of 0.3 mol%, and these were mixed by mechanical means ( A slurry was prepared by wet mixing). At this time, the slurry was prepared so that the total solid content of the slurry was 50% by mass. Next, the slurry was left to stand and dried to obtain a mixture.
- a precursor of a positive electrode active material for a lithium ion battery represented by the composition formula: Ni 0.82 Co 0.15 Mn 0.03 (OH) 2 was prepared.
- a precursor of a positive electrode active material for lithium ion batteries and ZrO 2 having a D50 of 0.35 ⁇ m were added to the water solvent in an amount of 0.3 mol%, and these were
- lithium hydroxide lithium source
- a Henschel mixer dry mixing
- the lithium mixture obtained as described above was baked at 720° C. for 12 hours in an oxygen atmosphere to prepare a positive electrode active material.
- a LiNbO 3 peroxo complex aqueous solution with an Nb content of 0.20 mol/L was prepared as a coating liquid, and an oxide containing Li and Nb was coated on the surface of the prepared positive electrode active material using a tumbling fluidized bed coating device.
- a positive electrode active material having a LiNbO 3 coating layer provided on the surface was produced by coating the precursor and performing heat treatment at 250° C. in an oxygen atmosphere.
- Example 19 A precursor of a positive electrode active material for lithium ion batteries and WO 2 having a D50 of 0.56 ⁇ m are added to an aqueous solvent at a charging amount of 0.5 mol%, and the mixture is mixed by mechanical means (wet mixing).
- a positive electrode active material having a LiNbO 3 coating layer on its surface was prepared in the same manner as in Example 18, except that a slurry was prepared.
- Example 20 A precursor of a positive electrode active material for lithium ion batteries and Ta 2 O 5 having a D50 of 0.31 ⁇ m were added to an aqueous solvent in an amount of 0.5 mol %, and mixed by mechanical means (wet method). A positive electrode active material provided with a LiNbO 3 coating layer on the surface was prepared in the same manner as in Example 18, except that a slurry was prepared by mixing).
- composition of positive electrode active material Weighed 0.2 g of each positive electrode active material sample (powder) obtained, decomposed it by an alkali melting method, and then used an inductively coupled plasma optical emission spectrometer (ICP-OES) "PS7800" manufactured by Hitachi High-Tech Corporation. Compositional analysis was performed. The oxygen content was determined by subtracting the impurity concentration and residual alkali amount from the total amount of the analysis sample in addition to the analytical values of Li and metal components, and thereby f of "O f " in equation (1) was calculated.
- ICP-OES inductively coupled plasma optical emission spectrometer
- the water-soluble solvent during the measurement was passed through a filter, the solvent refractive index was 1.333, the particle permeability conditions were passed, the particle refractive index was 1.81, the shape was non-spherical, and the measurement range was 0.021 to 2000 ⁇ m. , the measurement time was 30 seconds.
- WDX mapping analysis by FE-EPMA Using field emission electron microanalyzer (FE-EPMA) "JXA-8500F" manufactured by JEOL Ltd., magnification: 50 ⁇ m x 50 ⁇ m viewing area, acceleration voltage: 15.0 kV, irradiation current: 2.0 x 10 -8 WDX mapping analysis was performed using stage scan under conditions of A. Regarding the measurement samples, about 0.3 g of the sample (powder) of each positive electrode active material obtained was sprinkled onto a carbon tape attached to a stage holder, and then the stage holder was introduced into the apparatus and measured.
- FE-EPMA field emission electron microanalyzer
- FIG. Examples 1 to 6 Figure 4 (Examples 7 to 12), Figure 5 (Examples 13 to 17), Figure 6 (Comparative Examples 5 to 7), and Figure 7 (Examples 18 to 20).
- FIG. 7 shows WDX mapping images of uncoated positive electrode active material particles. Note that for Comparative Examples 1 to 4 and 8 to 10, since the samples were not doped with Zr, Ta, or W, SEM images and WDX mapping images of the positive electrode active material particles were not obtained.
- the initial capacity 25°C, upper limit charge voltage: 4.3V, lower limit discharge voltage: 3.0V
- high temperature cycle characteristics at 55°C after 20 cycles at a charge/discharge rate of 1C were measured, and the 20 cycle capacity retention rate ( %) was calculated.
- the initial DC resistance and the DC resistance after 20 cycles are calculated by dividing the voltage change ⁇ V 2 seconds after the start of discharge by the current value, and ((DC resistance after 20 cycles - initial DC resistance)/( The resistance increase rate (%) after 20 cycles was calculated using the formula: initial DC resistance)) x 100 [%].
- the positive electrode composite slurry was applied to the surface of the positive electrode current collector by using an applicator with a gap of 400 ⁇ m and moving the applicator at a moving speed of 15 mm/s.
- the positive electrode current collector whose surface was coated with the positive electrode mixture slurry was dried on a hot plate at 100°C for 30 minutes to remove the solvent, thereby forming a positive electrode mixture layer on the surface of the positive electrode current collector. did.
- the above-mentioned positive electrode composite layer was placed on a sulfide-based solid electrolyte having the same composition as the sulfide-based solid electrolyte used in producing the positive electrode composite material layer, and pressed at 333 MPa to form a solid electrolyte layer.
- a laminate of /positive electrode mixture layer/positive electrode current collector was produced.
- a metal Li--In alloy was pressure bonded to the negative electrode side of the solid electrolyte layer at 37 MPa to form a negative electrode layer.
- the thus produced laminate was placed in a battery test cell made of SUS304 and a confining pressure was applied to form an all-solid-state secondary battery. Furthermore, the all-solid-state secondary battery that was subjected to the confining pressure was placed in an airtight container to block the atmosphere.
- the discharge capacity of the all-solid-state battery was evaluated by measuring the impedance to determine the resistance after the initial charge at 0.1C at 55°C, and then discharging at 0.1C.
- the resistance of the all-solid-state battery was evaluated as the resistance after the first charge by measuring AC impedance from 0.1 Hz to 1 MHz and analyzing the resulting Cole-Cole plot.
- the rate characteristics (%) of the all-solid-state lithium ion battery were determined by measuring the initial capacity obtained at a discharge rate of 0.1C (55°C, upper charge voltage: 3.7V, lower discharge limit voltage: 2.5V vs Li-In), Next, the high rate capacity obtained at a discharge rate of 0.5C (55°C, charging upper limit voltage: 3.7V, discharge lower limit voltage: 2.5V vs Li-In) was measured, and (high rate capacity) / (initial capacity) The ratio was evaluated as a percentage.
- the positive electrode active materials of Examples 1 to 17 all had the composition of the following formula (1). Note that “Li/Me ratio” in Tables 2 and 4 indicates the composition ratio of Li to the total of Ni, Co, Mn, and M of the positive electrode active material.
- M is at least one selected from Zr, Ta, and W.
- M oxide was attached to the surface of the positive electrode active material particles in WDX mapping analysis of the positive electrode active material particles in a field of view of 50 ⁇ m x 50 ⁇ m using FE-EPMA.
- the oxide of M did not exist as independent particles that were not attached to the surface of the positive electrode active material particles. Therefore, the initial discharge capacity and 20-cycle capacity retention rate evaluated using a coin cell were good, and the resistance increase rate after 20 cycles was kept low, indicating good battery characteristics.
- the positive electrode active materials of Comparative Examples 1 to 4 and 8 to 10 did not contain a different element, the 20-cycle capacity retention rate evaluated using a coin cell was poor, and the resistance increase rate after 20 cycles was high.
- the D50 of the mixed Zr oxide, Ta oxide, and W oxide exceeded 1 ⁇ m, so the M oxide adhered to the surface of the positive electrode active material particles. It did not exist as an independent particle. Therefore, the 20-cycle capacity retention rate evaluated using the coin cell was poor, and the resistance increase rate after 20 cycles was high.
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Abstract
Description
1.下記式(1)に示す組成で表されるリチウムイオン電池用正極活物質であり、
LiaNibCocMndMeOf (1)
(前記式(1)中、1.0≦a≦1.05、0.8≦b≦0.9、b+c+d+e=1、1.8≦f≦2.2、0.0025≦e/(b+c+d+e)≦0.016、MはZr、Ta及びWから選ばれる少なくとも1種である。)
FE-EPMAによる50μm×50μmの視野における正極活物質粒子のWDXマッピング分析において、前記正極活物質粒子の表面に前記Mの酸化物が付着しており、且つ、前記Mの酸化物が前記正極活物質粒子の表面に付着していない独立した粒子として存在しない、リチウムイオン電池用正極活物質。
2.前記リチウムイオン電池用正極活物質の50%累積体積粒度D50が3~18μmである、前記1に記載のリチウムイオン電池用正極活物質。
3.前記1または2に記載のリチウムイオン電池用正極活物質を含む、リチウムイオン電池用正極。
4.前記3に記載のリチウムイオン電池用正極及び負極を含む、リチウムイオン電池。
5.前記1または2に記載のリチウムイオン電池用正極活物質と、
前記リチウムイオン電池用正極活物質の、正極活物質粒子表面に設けられたLiとNbとの酸化物からなる被覆層と、
を含む、全固体リチウムイオン電池用正極活物質。
6.前記全固体リチウムイオン電池用正極活物質におけるNbの含有量が、0.5~0.8質量%である、前記5に記載の全固体リチウムイオン電池用正極活物質。
7.前記5に記載の全固体リチウムイオン電池用正極活物質を含む、全固体リチウムイオン電池用正極。
8.前記7に記載の全固体リチウムイオン電池用正極及び負極を含む、全固体リチウムイオン電池。
9.下記式(2)に示す組成で表されるリチウムイオン電池用正極活物質の前駆体を準備する工程と、
NibCocMnd(OH)2 (2)
(前記式(2)中、0.8≦b≦0.9、0.07≦c≦0.15、及び、b+c+d=1である。)
50%累積体積粒度D50が1μm以下である、Zrの酸化物、Taの酸化物及びWの酸化物から選ばれる少なくとも1種を前記リチウムイオン電池用正極活物質の前駆体に湿式で混合して混合物を得る工程と、
前記混合物をリチウム源と乾式で混合し、700℃以上で4時間以上焼成する工程と、
を含む、リチウムイオン電池用正極活物質の製造方法。
10.前記Zrの酸化物、Taの酸化物及びWの酸化物は、前記D50が0.3~1.0μmである、前記9に記載のリチウムイオン電池用正極活物質の製造方法。
11.前記混合物を焼成する工程において、前記混合物をリチウム源と乾式で混合し、700~800℃で4~12時間焼成する、前記9に記載のリチウムイオン電池用正極活物質の製造方法。
12.前記9~11のいずれかに記載の方法で製造されたリチウムイオン電池用正極活物質を準備する工程と、
前記リチウムイオン電池用正極活物質の正極活物質粒子表面に、LiとNbとを含む水溶液を用いて、LiとNbとの酸化物からなる被覆層を形成する工程と、
を含む、全固体リチウムイオン電池用正極活物質の製造方法。
本発明において、単に「リチウムイオン電池用正極活物質」と示すときは、電解液を用いた液系のリチウムイオン電池用正極活物質及び電解質を固体とした全固体リチウムイオン電池用正極活物質のいずれも含むものとする。
本発明の実施形態に係るリチウムイオン電池用正極活物質は、下記式(1)に示す組成で表される。
LiaNibCocMndMeOf (1)
(前記式(1)中、1.0≦a≦1.05、0.8≦b≦0.9、b+c+d+e=1、1.8≦f≦2.2、0.0025≦e/(b+c+d+e)≦0.016、MはZr、Ta及びWから選ばれる少なくとも1種である。)
本発明の実施形態に係る全固体リチウムイオン電池用正極活物質は、上述の本発明の実施形態に係るリチウムイオン電池用正極活物質と、リチウムイオン電池用正極活物質の、正極活物質粒子表面に設けられたLiとNbとの酸化物からなる被覆層とを含む。被覆層を構成するLiとNbの酸化物は、ニオブ酸リチウム(LiNbO3)を含んでもよく、LiNbO3であってもよい。
次に、本発明の実施形態に係るリチウムイオン電池用正極活物質の製造方法について詳述する。本発明の実施形態に係るリチウムイオン電池用正極活物質の製造方法は、まず、下記式(2)に示す組成で表されるリチウムイオン電池用正極活物質の前駆体を準備する。
NibCocMnd(OH)2 (2)
(前記式(2)中、0.8≦b≦0.9、0.07≦c≦0.15、及び、b+c+d=1である。)
また、本発明では、当該スラリーの固形分量が全体で40~60質量%の濃度、好ましくは50質量%の濃度となるようにスラリーを調製する必要がある。スラリーの固形分濃度に関する、ZrO2、Ta2O5、WO2またはWO3などの酸化物の表面付着への影響については、低スラリー濃度の場合は湿式での攪拌混合中の粒子同士の距離が遠く、粒子間の凝集(付着)が起こり難いが、高スラリー濃度の場合は粒子同士の距離が近いため、粒子間の凝集(付着)が起こりやすくなる。そのため、スラリーの固形分濃度が例えば10質量%程度のような低スラリー濃度では、湿式での攪拌混合中に完全にはZrO2、Ta2O5、WO2またはWO3などの酸化物粒子の付着が行われず、一部独立した粒子として存在するが、本発明のようにスラリーの固形分濃度が40~60質量%であると、完全にZrO2、Ta2O5、WO2またはWO3などの酸化物粒子の付着が行われる。
本発明の実施形態に係る全固体リチウムイオン電池用正極活物質の製造方法は、まず、上述のリチウムイオン電池用正極活物質の製造方法で製造したリチウムイオン電池用正極活物質の正極活物質粒子表面に、LiとNbとを含む水溶液(被覆液)をコーティングする。このとき、被覆液としては、例えば、ニオブ酸リチウム(LiNbO3)のペルオキソ錯体水溶液、蓚酸水溶液等が挙げられる。また、コーティング方法としては、正極活物質の表面上に溶液を付着可能な方法であれば特に限定されるものではないが、例えば、転動流動層を有するコート装置を用いる方法や、噴霧乾燥による方法を用いてもよい。
本発明の実施形態に係るリチウムイオン電池用正極は、例えば、上述の構成のリチウムイオン電池用正極活物質と、導電助材と、バインダーとを混合して調製した正極合材を集電体の片面または両面に設けた構造を有している。また、本発明の実施形態に係るリチウムイオン電池は、このような構成のリチウムイオン電池用正極と、公知のリチウムイオン電池用負極とを備えている。
本発明の実施形態に係る全固体リチウムイオン電池用正極活物質によって正極を形成し、当該正極を正極層とし、当該正極層と、固体電解質層と、負極層とを含む全固体リチウムイオン電池を作製することができる。本発明の実施形態に係る全固体リチウムイオン電池を構成する固体電解質層及び負極層は、特に限定されず、公知の材料で形成することができ、図8に示すような公知の構成とすることができる。
正極集電体の材質としては、例えば、ダイス鋼、ステンレス鋼、アルミニウム、アルミニウム合金、チタン合金、銅、金、ニッケルなどが挙げられる。
正極集電体の形状としては、例えば、箔状、板状、メッシュ状などが挙げられる。
正極集電体の平均厚みとしては、例えば、10μm~500μmであってもよく、50μm~100μmであってもよい。
負極集電体の材質としては、例えば、ダイス鋼、金、インジウム、ニッケル、銅、ステンレス鋼などが挙げられる。
負極集電体の形状としては、例えば、箔状、板状、メッシュ状などが挙げられる。
負極集電体の平均厚みとしては、例えば、10μm~500μmであってもよく、50μm~100μmであってもよい。
電池の形状については特に限定されず、目的に応じて適宜選択することができ、例えば、円筒型、角型、ボタン型、コイン型、扁平型などが挙げられる。
まず、組成式:Ni0.8Co0.1Mn0.1(OH)2で表されるリチウムイオン電池用正極活物質の前駆体を準備した。
次に、水溶媒にリチウムイオン電池用正極活物質の前駆体と、D50が0.35μmであるZrO2を0.4mol%の仕込み量となるように添加し、これを機械的手段で混合(湿式混合)してスラリーを調製した。このとき、スラリーの固形分量が全体で50質量%の濃度となるようにスラリーを調製した。次いで、当該スラリーを静置させた状態で乾燥させることで混合物を得た。
次に、得られた混合物に対し、水酸化リチウム(リチウム源)を添加してヘンシェルミキサーで混合(乾式混合)して、リチウム混合物を形成した。
次に、上述のようにして得られたリチウム混合物を、酸素雰囲気にて800℃で4時間焼成することで、正極活物質を作製した。
正極活物質の前駆体の組成、混合した異種元素の酸化物の種類、当該異種元素の酸化物の粒径、当該異種元素の酸化物の仕込み量、焼成温度及び焼成時間について、それぞれ表1の条件とした以外は、実施例1と同様にして正極活物質を作製した。
正極活物質の前駆体に異種元素の酸化物を混合せず、正極活物質の前駆体の組成及び焼成温度について、それぞれ表1の条件とした以外は、実施例1と同様にして正極活物質を作製した。
正極活物質の前駆体に異種元素の酸化物をヘンシェルミキサーによって混合(乾式で混合)することで、正極活物質の前駆体と異種元素の酸化物との混合物を作製し、正極活物質の前駆体の組成及び焼成温度について、それぞれ表1の条件とした以外は、実施例1と同様にして正極活物質を作製した。
まず、組成式:Ni0.82Co0.15Mn0.03(OH)2で表されるリチウムイオン電池用正極活物質の前駆体を準備した。
次に、水溶媒にリチウムイオン電池用正極活物質の前駆体と、D50が0.35μmであるZrO2を0.3mol%の仕込み量となるように添加し、これを機械的手段で混合(湿式混合)してスラリーを調製した。このとき、スラリーの固形分量が全体で50質量%の濃度となるようにスラリーを調製した。次いで、当該スラリーを静置させた状態で乾燥させることで混合物を得た。
次に、得られた混合物に対し、水酸化リチウム(リチウム源)を添加してヘンシェルミキサーで混合(乾式混合)して、リチウム混合物を形成した。
次に、上述のようにして得られたリチウム混合物を、酸素雰囲気にて720℃で12時間焼成することで、正極活物質を作製した。
次に、被覆液としてNb含有量0.20mol/LのLiNbO3ペルオキソ錯体水溶液を準備し、転動流動層コーティング装置を用いて、作製した正極活物質の表面にLiとNbとを含む酸化物前駆体を被覆し、酸素雰囲気にて250℃で熱処理を行い、LiNbO3の被覆層を表面に設けた正極活物質を作製した。
水溶媒にリチウムイオン電池用正極活物質の前駆体と、D50が0.56μmであるWO2を0.5mol%の仕込み量となるように添加し、これを機械的手段で混合(湿式混合)してスラリーを調製した以外は、実施例18と同様にLiNbO3の被覆層を表面に設けた正極活物質を作製した。
水溶媒にリチウムイオン電池用正極活物質の前駆体と、D50が0.31μmであるTa2O5を0.5mol%の仕込み量となるように添加し、これを機械的手段で混合(湿式混合)してスラリーを調製した以外は、実施例18と同様にLiNbO3の被覆層を表面に設けた正極活物質を作製した。
比較例2と同条件で作製した正極活物質の表面に、被覆液をLiNbO3水溶液とし、転動流動層コーティング装置を用いて、酸素雰囲気にて熱処理温度250℃で転動流動層コーティングを行い、LiNbO3の被覆層を表面に設けた正極活物質を作製した。
得られた各正極活物質のサンプル(粉末)を0.2gはかり取り、アルカリ溶融法で分解後、日立ハイテク社製の誘導結合プラズマ発光分光分析装置(ICP-OES)「PS7800」を用いて、組成分析を行った。
酸素含有量は、Li及び金属成分の分析値に加え、不純物濃度、残留アルカリ量を、分析試料全量から差し引くことにより求め、これにより式(1)における「Of」のfを算出した。
得られた各正極活物質のサンプル(粉末)100mgを、Microtrac製レーザー回折型粒度分布測定装置「MT3300EXII」を用いて、50%の流速中、40Wの超音波を60秒間照射して分散後、粒度分布を測定し、体積基準の累積粒度分布曲線を得た。次に、得られた累積粒度分布曲線において、50%累積時の体積粒度を、正極活物質の粉末の50%累積体積粒度D50とした。なお、測定の際の水溶性溶媒はフィルターを通し、溶媒屈折率を1.333、粒子透過性条件を透過、粒子屈折率1.81、形状を非球形とし、測定レンジを0.021~2000μm、測定時間を30秒とした。
日本電子社製、電界放出型電子線マイクロアナライザ(FE-EPMA)「JXA-8500F」を用いて、倍率:50μm×50μmの視野面積、加速電圧:15.0kV、照射電流:2.0×10-8Aの条件でステージスキャンにて、WDXマッピング分析を実施した。測定試料については、得られた各正極活物質のサンプル(粉末)約0.3gを、ステージホルダ上に貼りつけたカーボンテープへ振りかけた後、ステージホルダを装置内へ導入し、測定した。
当該WDXマッピング分析において、正極活物質粒子の表面にMの酸化物が付着していたものを表2において「A」と記載し、正極活物質粒子の表面にMの酸化物が付着していなかったものを表2において「B」と記載した。
また、当該WDXマッピング分析において、Mの酸化物が正極活物質粒子の表面に付着していない独立した粒子として存在していなかったものを表2において「A」と記載し、Mの酸化物が正極活物質粒子の表面に付着していない独立した粒子として存在していたものを表2において「B」と記載した。
また、実施例1~17及び比較例5~7の正極活物質粒子のFE-EPMAによるSEM像及び当該SEM像に対応するFE-EPMAによるZr、TaまたはWのWDXマッピング像を、図3(実施例1~6)、図4(実施例7~12)、図5(実施例13~17)、図6(比較例5~7)、及び、図7(実施例18~20)に示す。図7(実施例18~20)は、被覆していない状態の正極活物質粒子に係るWDXマッピング像を示す。なお、比較例1~4及び8~10については、Zr、TaまたはWのドーピングを行っていないサンプルであるため、正極活物質粒子のSEM像及びWDXマッピング像は取得していない。
<初回放電容量、20サイクル容量維持率>
正極活物質と、導電助材と、バインダーを90:5:5mol%の割合で秤量した。次に、バインダーを有機溶媒(N-メチルピロリドン)に溶解したものに、正極活物質と導電助材とを混合してスラリー化し、Al箔上に塗布して乾燥後にプレスして正極とした。続いて、対極をLiとした評価用の2032型コインセルを作製し、電解液として1M-LiPF6をEC-DMC(1:1)に溶解したものを用いて、放電レート0.1Cで得られた初期容量(25℃、充電上限電圧:4.3V、放電下限電圧:3.0V)、充放電レート1Cでの20サイクル後の55℃高温サイクル特性、を測定し、20サイクル容量維持率(%)を算出した。
上述のコインセル評価における、放電開始2秒後の電圧変化ΔVを電流値で割ることによって、初回直流抵抗及び20サイクル後直流抵抗を算出し、((20サイクル後直流抵抗-初回直流抵抗)/(初回直流抵抗))×100[%]の式によって20サイクル後抵抗上昇率(%)を算出した。
<全固体電池の作製方法>
実施例18~20、比較例10で得られた正極活物質と硫化物系固体電解質(75Li2S-25P2S5)とアセチレンブラックとバインダーとをこの順で60:35:5:1.5の質量比で混合し、スラリーの固形分が65質量%となるようにアニソールを溶媒として加え、マゼルスターで400秒混合して正極合材スラリーとし、これを正極集電体である厚さ0.03mmのアルミニウム箔の表面に塗工した。このとき、ギャップが400μmのアプリケーターを使用して15mm/sの移動速度でアプリケーターを移動させることで当該正極合材スラリーを正極集電体表面に塗工した。
次に、正極合材スラリーを表面に塗工した正極集電体をホットプレート上で100℃、30分乾燥して溶媒を除去することで、正極集電体の表面に正極合材層を形成した。
次に、正極合材層の作製の際に用いた硫化物系固体電解質と同組成の硫化物系固体電解質の上に上述の正極合材層を載せて、333MPaでプレスして、固体電解質層/正極合材層/正極集電体の積層体を作製した。
次に、固体電解質層の負極側に、金属Li-In合金を37MPaで圧着して負極層とした。このように作製した積層体をSUS304製の電池試験セルに入れて拘束圧をかけて全固体二次電池とした。また、当該拘束圧をかけて全固体二次電池としたものについて、大気を遮断するために密閉容器に入れた。
全固体電池の放電容量は、55℃での0.1Cでの初回充電後にインピーダンスを測定し抵抗を求め、続いて0.1Cで放電することで、初回放電容量を評価した。
全固体電池の抵抗は、交流インピーダンス測定を0.1Hz~1MHzまで行い、得られたCole-Coleプロットを解析することで初回充電後抵抗として評価した。
全固体リチウムイオン電池のレート特性(%)は、放電レート0.1Cで得られた初期容量(55℃、充電上限電圧:3.7V、放電下限電圧:2.5VvsLi-In)を測定し、次に放電レート0.5Cで得られた高率容量(55℃、充電上限電圧:3.7V、放電下限電圧:2.5VvsLi-In)を測定し、(高率容量)/(初期容量)の比を百分率として評価した。
全固体リチウムイオン電池の容量維持率は、55℃で0.5Cの放電電流で得られた初期放電容量で、20サイクル後の放電容量を除することで、20サイクル容量維持率として評価した。
上記製造条件及び試験結果を表1~4に示す。
実施例1~17の正極活物質は、いずれも、下記式(1)の組成を有していた。なお、表2、4の「Li/Me比」は、正極活物質のNi、Co、Mn及びMの合計に対するLiの組成比を示す。
LiaNibCocMndMeOf (1)
(前記式(1)中、1.0≦a≦1.05、0.8≦b≦0.9、b+c+d+e=1、1.8≦f≦2.2、0.0025≦e/(b+c+d+e)≦0.016、MはZr、Ta及びWから選ばれる少なくとも1種である。)
また、実施例1~20の正極活物質は、いずれも、FE-EPMAによる50μm×50μmの視野における正極活物質粒子のWDXマッピング分析において、正極活物質粒子の表面にMの酸化物が付着しており、且つ、Mの酸化物が正極活物質粒子の表面に付着していない独立した粒子として存在していなかった。
このため、コインセルで評価した初回放電容量及び20サイクル容量維持率が良好であり、20サイクル後抵抗上昇率が低く抑えられており、良好な電池特性を示した。
比較例5~7の正極活物質は、混合したZrの酸化物、Taの酸化物及びWの酸化物のD50が1μmを超えていたため、Mの酸化物が正極活物質粒子の表面に付着していない独立した粒子として存在していた。従って、コインセルで評価した20サイクル容量維持率が不良であり、20サイクル後抵抗上昇率が高かった。
Claims (12)
- 下記式(1)に示す組成で表されるリチウムイオン電池用正極活物質であり、
LiaNibCocMndMeOf (1)
(前記式(1)中、1.0≦a≦1.05、0.8≦b≦0.9、b+c+d+e=1、1.8≦f≦2.2、0.0025≦e/(b+c+d+e)≦0.016、MはZr、Ta及びWから選ばれる少なくとも1種である。)
FE-EPMAによる50μm×50μmの視野における正極活物質粒子のWDXマッピング分析において、前記正極活物質粒子の表面に前記Mの酸化物が付着しており、且つ、前記Mの酸化物が前記正極活物質粒子の表面に付着していない独立した粒子として存在しない、リチウムイオン電池用正極活物質。 - 前記リチウムイオン電池用正極活物質の50%累積体積粒度D50が3~18μmである、請求項1に記載のリチウムイオン電池用正極活物質。
- 請求項1または2に記載のリチウムイオン電池用正極活物質を含む、リチウムイオン電池用正極。
- 請求項3に記載のリチウムイオン電池用正極及び負極を含む、リチウムイオン電池。
- 請求項1または2に記載のリチウムイオン電池用正極活物質と、
前記リチウムイオン電池用正極活物質の、正極活物質粒子表面に設けられたLiとNbとの酸化物からなる被覆層と、
を含む、全固体リチウムイオン電池用正極活物質。 - 前記全固体リチウムイオン電池用正極活物質におけるNbの含有量が、0.5~0.8質量%である、請求項5に記載の全固体リチウムイオン電池用正極活物質。
- 請求項5に記載の全固体リチウムイオン電池用正極活物質を含む、全固体リチウムイオン電池用正極。
- 請求項7に記載の全固体リチウムイオン電池用正極及び負極を含む、全固体リチウムイオン電池。
- 下記式(2)に示す組成で表されるリチウムイオン電池用正極活物質の前駆体を準備する工程と、
NibCocMnd(OH)2 (2)
(前記式(2)中、0.8≦b≦0.9、0.07≦c≦0.15、及び、b+c+d=1である。)
50%累積体積粒度D50が1μm以下である、Zrの酸化物、Taの酸化物及びWの酸化物から選ばれる少なくとも1種を前記リチウムイオン電池用正極活物質の前駆体に湿式で混合して混合物を得る工程と、
前記混合物をリチウム源と乾式で混合し、700℃以上で4時間以上焼成する工程と、
を含む、リチウムイオン電池用正極活物質の製造方法。 - 前記Zrの酸化物、Taの酸化物及びWの酸化物は、前記D50が0.3~1.0μmである、請求項9に記載のリチウムイオン電池用正極活物質の製造方法。
- 前記混合物を焼成する工程において、前記混合物をリチウム源と乾式で混合し、700~800℃で4~12時間焼成する、請求項9に記載のリチウムイオン電池用正極活物質の製造方法。
- 請求項9~11のいずれか一項に記載の方法で製造されたリチウムイオン電池用正極活物質を準備する工程と、
前記リチウムイオン電池用正極活物質の正極活物質粒子表面に、LiとNbとを含む水溶液を用いて、LiとNbとの酸化物からなる被覆層を形成する工程と、
を含む、全固体リチウムイオン電池用正極活物質の製造方法。
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