WO2013146287A1 - 正極活物質粒子粉末及びその製造方法、並びに非水電解質二次電池 - Google Patents
正極活物質粒子粉末及びその製造方法、並びに非水電解質二次電池 Download PDFInfo
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- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
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- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/56—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO3]2-, e.g. Li2[CoxMn1-xO3], Li2[MyCoxMn1-x-yO3
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/56—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO3]2-, e.g. Li2[NixMn1-xO3], Li2[MyNixMn1-x-yO3
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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
- H01M4/50—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
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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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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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Definitions
- the present invention provides a positive electrode active material particle powder for a non-aqueous electrolyte secondary battery having an excellent discharge capacity.
- LiMn 2 O 4 of spinel structure LiMnO 2 having a zigzag layer structure, LiCoO 2 of layered rock-salt structure, LiNiO 2 and the like are generally known, and lithium ion secondary batteries using LiNiO 2 have attracted attention as batteries having a high charge / discharge capacity.
- this material still has insufficient discharge capacity, and further improvement in characteristics is required.
- Patent Document 1 a positive electrode active material containing Li 2 MnO 3 belonging to a higher capacity C2 / m space group exhibits a high discharge capacity
- Patent Document 2 additives
- Patent Document 3 heat treatment methods
- Patent Document 4 methods for trapping gas generated by charging
- a positive electrode active material for a non-aqueous electrolyte secondary battery having an excellent discharge capacity is currently most demanded, but a material that satisfies the necessary and sufficient requirements has not yet been obtained.
- an object of the present invention is to provide a positive electrode active material particle powder for a nonaqueous electrolyte secondary battery having a large discharge capacity, a method for producing the same, and a nonaqueous electrolyte secondary battery comprising a positive electrode containing the positive electrode active material particle powder. That is.
- the present invention is a positive electrode active material particle powder comprising a compound having at least a crystal system belonging to space group R-3m and a crystal system belonging to space group C2 / m, wherein the compound includes at least Li, Mn, and element A ( 2 ⁇ of a powder X-ray diffraction diagram using a Cu—K ⁇ ray of a positive electrode active material particle powder, which is a composite oxide containing at least one element selected from Si, Zr or Y) and Co and / or Ni.
- the positive electrode active material particle powder having a molar ratio (Mn / (Ni + Co + Mn)) of 0.55 or more and the element A in an amount of 0.03 to 5 wt. % And the tap density is 0.8-2.
- a g / cc a positive electrode active material particles, wherein the compressed density of 2.0 ⁇ 3.1g / cc (the present invention 1).
- the present invention relates to LiM x Mn 1-x O 2 (M is Ni and / or Co, 0 ⁇ x ⁇ 1) as a compound having a crystal system belonging to the space group R-3m, to the space group C2 / m.
- the positive electrode according to the first aspect of the invention comprising Li 2 M ′ (1-y) Mn y O 3 (M ′ is Ni and / or Co, 0 ⁇ y ⁇ 1) as a compound having a crystal system to which it belongs Active material particle powder (Invention 2).
- the present invention provides the composite positive electrode active material particle powder according to any one of the present invention 1 or 2, wherein Li / (Ni + Co + Mn) is in a molar ratio of 1.25 to 1.7. There is (Invention 3).
- the present invention is the positive electrode active material particle powder according to any one of the present inventions 1 to 3, wherein the specific surface area by the BET method is 0.1 to 20 m 2 / g (Invention 4). .
- the present invention provides a positive electrode active material particle powder comprising secondary particles in which primary particles are aggregated, wherein the average secondary particle diameter is 1 to 50 ⁇ m.
- the present invention provides a precursor mainly composed of a composite hydroxide or composite carbonate containing at least Mn, an element A (at least one element selected from Si, Zr or Y), and Co and / or Ni.
- Mn content of the precursor particle powder is Mn / (Ni + Co + Mn) in a molar ratio of 0.55 or more, contains 0.025 to 5.5 wt% of element A, and has an average secondary particle diameter Is a precursor particle powder of a positive electrode active material particle powder according to any one of the present inventions 1 to 5, wherein the particle diameter is 1 to 50 ⁇ m (Invention 6).
- the present invention also provides a method for producing a positive electrode active material particle powder according to any one of the present inventions 1 to 5, wherein the mixture containing the precursor particle powder and the lithium compound according to the present invention 6 is 500 to 1500 ° C. This is a method for producing positive electrode active material particle powder that is fired in the range of (No. 7).
- the present invention is a non-aqueous electrolyte secondary battery using the positive electrode containing the positive electrode active material particle powder according to any one of the present inventions 1 to 5 (Invention 8).
- the positive electrode active material particle powder according to the present invention is suitable as a positive electrode active material particle powder for a non-aqueous electrolyte secondary battery because it has a large discharge capacity and can obtain high energy.
- the positive electrode active material particle powder according to the present invention comprises a compound having at least a crystal system belonging to the space group R-3m and a crystal system belonging to the space group C2 / m, and includes at least Li, Mn, Co and / or Ni. It is a compound comprising a composite oxide and an element A (element A is one or more elements selected from Si, Zr, or Y).
- the compound having a crystal system belonging to the space group R-3m is preferably LiM x Mn 1-x O 2 (M is Ni and / or Co, and the range of x is 0 ⁇ x ⁇ 1). Specifically, LiCo x Mn 1-x O 2, LiNi x Mn 1-x O 2 , Li (Ni, Co) x Mn 1-x O 2 and the like are preferable. It should be noted that the space group R-3m is officially written with a bar on 3 of R3m, but here it is represented as R-3m for convenience.
- the compound having a crystal system belonging to the space group C2 / m is preferably Li 2 M ′ (1-y) Mn y O 3 (M ′ is Ni and / or Co, and the range of y is 0 ⁇ y ⁇ 1). .
- LiM x Mn 1-x which is a compound belonging to a crystal system belonging to space group R-3m
- (A) / (b) is 0.02 to 0.2.
- a preferred relative intensity ratio (a) / (b) is 0.02 to 0.15, more preferably 0.02 to 0.12, and even more preferably 0.025 to 0.08.
- (Li / (Ni + Co + Mn)) is preferably in a molar ratio of 1.25 to 1.7. If (Li / (Ni + Co + Mn)) is less than 1.25, the amount of lithium that can contribute to charging is reduced and the charging capacity is lowered. If it exceeds 1.7, on the contrary, too much lithium cannot enter the crystal structure. Since it becomes a resistance component, the discharge capacity is lowered. More preferably, it is 1.25 to 1.65, still more preferably 1.3 to 1.6, and still more preferably 1.35 to 1.55.
- the positive electrode active material particle powder according to the present invention has a Mn content in a molar ratio of Mn / (Ni + Co + Mn) of 0.55 or more.
- Mn content is below the above range, a compound having a crystal system belonging to the space group C2 / m is not sufficiently formed, and the charge / discharge capacity is lowered.
- Mn content is below the above range, a compound having a crystal system belonging to the space group C2 / m is not sufficiently formed, and the charge / discharge capacity is lowered.
- it is 0.6 or more, More preferably, it is 0.65 or more.
- the upper limit is preferably about 0.8.
- the positive electrode active material particle powder according to the present invention preferably has a Ni content in a molar ratio of Ni / (Ni + Co + Mn) of 0 to 0.45. Exceeding 0.45 is not preferable because the thermal stability is lowered. A more preferable Ni content is 0 to 0.35.
- the positive electrode active material particle powder according to the present invention preferably has a Co content in a molar ratio of Co / (Ni + Co + Mn) of 0 to 0.45. If it exceeds 0.45, the structure becomes unstable, such being undesirable. A more preferable Co content is 0 to 0.35.
- the positive electrode active material particle powder according to the present invention contains 0.03 to 5 wt% of element A.
- element A When the content of element A is less than 0.03 wt%, the effect of preventing sintering when firing is reduced, and the charge / discharge rate characteristics of a secondary battery using the positive electrode active material particle powder can be improved. Absent. If it exceeds 5 wt%, it is too much to become a resistance component, which is not preferable because the discharge capacity decreases.
- the content of element A is preferably 0.03 to 2.3 wt%, more preferably 0.1 to 1.05 wt%, and even more preferably 0.1 to 0.5 wt%.
- the positive electrode active material particle powder according to the present invention has a tap density of 0.8 to 2.4 g / cc.
- the tap density is less than 0.8 g / cc, the primary particle density becomes sparse and electrons cannot be sufficiently transmitted, resulting in a decrease in discharge capacity. If it exceeds 2.4 g / cc, it becomes too dense and smooth electron movement is hindered, and the discharge capacity is lowered.
- the preferred tap density is 1.0 to 2.3 g / cc, more preferably 1.5 to 2.3 g / cc, and even more preferably 1.8 to 2.3 g / cc.
- the positive electrode active material particle powder according to the present invention has a compression density of 2.0 to 3.1 g / cc.
- a compression density of 2.0 to 3.1 g / cc.
- the compression density is less than 2.0 g / cc, the primary particles and the secondary particles are sparse and sufficient electrons are generated. It cannot be transmitted and the discharge capacity decreases. If it exceeds 3.1 g / cc, it becomes too dense, the area where the electrolyte solution comes into contact is reduced, smooth electron movement is hindered, and charge / discharge rate characteristics are deteriorated.
- a preferable compression density is 2.4 to 3.0 g / cc, more preferably 2.4 to 2.9 g / cc, and still more preferably 2.4 to 2.8 g / cc.
- the positive electrode active material particle powder according to the present invention has a specific surface area of 0.1 to 20 m 2 / g by BET method.
- the specific surface area is less than 0.1 m 2 / g, that is, when the primary particle diameter is too large, the distance from the particle center to the surface is too long to transfer electrons quickly and the charge / discharge rate characteristics deteriorate.
- it exceeds 20 m 2 / g the primary particles are too small and the primary particles that are not in contact with the conductive material are increased, and the discharge capacity is reduced.
- a preferred specific surface area is 0.3 to 12 m 2 / g, more preferably 0.3 to 9 m 2 / g, and still more preferably 1 to 7 m 2 / g.
- the average secondary particle diameter of the positive electrode active material particle powder according to the present invention is 1 to 50 ⁇ m.
- the average secondary particle diameter is preferably 2 to 30 ⁇ m, more preferably 2 to 20 ⁇ m, and even more preferably 2 to 16 ⁇ m.
- the positive electrode active material particle powder according to the present invention can be obtained by mixing a preliminarily prepared transition metal, a precursor particle powder containing element A, and a lithium compound, followed by firing.
- the precursor particle powder containing a transition metal in the present invention includes a mixed acid solution containing a predetermined concentration of nickel salt, cobalt salt, manganese salt, zirconium salt, yttrium salt, caustic soda, ammonia, sodium carbonate, water glass and the like.
- the mixed alkaline aqueous solution is supplied to the reaction vessel, and the pH is controlled to be 7.5 to 13, and the overflowed suspension is circulated to the reaction vessel while adjusting the concentration rate in the concentration vessel connected to the overflow pipe.
- the reaction can be carried out until the concentration of the precursor particles in the reaction tank and the sedimentation tank is 0.2 to 15 mol / l. Moreover, you may obtain precursor particle powder by overflow, without providing a concentration tank. After the reaction, washing with water, drying and pulverization may be performed according to a conventional method.
- the precursor particle powder containing a transition metal in the present invention is a hydroxide or carbonate synthesized by coprecipitation of a mixed solution containing element A in a raw material solution.
- the element A can be arranged more uniformly in the secondary particles.
- the zirconium compound used in the present invention is not particularly limited, and various zirconium compounds can be used.
- the zirconium compound include zirconium sulfate, zirconium oxynitrate, zirconium oxychloride, zirconium chloride, zirconium acetate, and zirconium oxalate.
- a soluble zirconium compound is mentioned.
- the yttrium compound used in the present invention is not particularly limited, and various yttrium compounds can be used. Examples thereof include various soluble yttrium compounds such as yttrium sulfate, yttrium nitrate, yttrium chloride, and yttrium acetate.
- the silicon compound used in the present invention is not particularly limited, and various silicon compounds can be used. Examples thereof include various soluble silicon compounds such as sodium silicate, potassium hexafluorosilicate, and ammonium hexafluorosilicate. .
- the precursor particle powder according to the present invention has a Mn content in a molar ratio of Mn / (Ni + Co + Mn) of 0.55 or more.
- Mn content falls below the above range, the positive electrode active material particle powder produced using the precursor particle powder does not sufficiently form a compound having a crystal system belonging to the space group C2 / m, and the charge / discharge capacity decreases.
- it is 0.6 or more, More preferably, it is 0.65 or more.
- the upper limit is preferably about 0.8.
- the precursor particle powder according to the present invention preferably has a Ni content in a molar ratio of Ni / (Ni + Co + Mn) of 0 to 0.45. If it exceeds 0.45, the positive electrode active material particle powder produced using the precursor particle powder is not preferable because the thermal stability is lowered. A more preferable Ni content is 0 to 0.35.
- the precursor particle powder according to the present invention preferably has a Co content in a molar ratio of Co / (Ni + Co + Mn) of 0 to 0.45. If it exceeds 0.45, the positive electrode active material particle powder produced using the precursor particle powder is not preferable because the structure becomes unstable. A more preferable Co content is 0 to 0.35.
- the precursor particle powder according to the present invention contains 0.025 to 5.5 wt% of element A.
- element A When the content of element A is less than 0.025 wt%, the effect of preventing sintering when firing is reduced, and the charge / discharge rate characteristics of a secondary battery using the positive electrode active material particle powder can be improved. Absent. If it exceeds 5.5 wt%, it is too much to become a resistance component, and the discharge capacity is lowered, which is not preferable.
- the content of element A is preferably 0.025 to 2.5 wt%, more preferably 0.08 to 1.1 wt%, and still more preferably 0.08 to 0.55 wt%.
- the average secondary particle diameter of the precursor particle powder according to the present invention is 1 to 50 ⁇ m.
- the average secondary particle diameter is less than 1 ⁇ m, the positive electrode active material particle powder produced using the precursor particle powder has a high reactivity with the electrolyte solution due to an excessive increase in the contact area with the electrolyte solution. Time stability is reduced.
- the average particle diameter exceeds 50 ⁇ m, the positive electrode active material particle powder produced using the precursor particle powder has an increased resistance in the electrode, and the charge / discharge rate characteristics are decreased.
- the average secondary particle diameter is preferably 2 to 30 ⁇ m, more preferably 2 to 20 ⁇ m, and even more preferably 2 to 16 ⁇ m.
- the precursor particle powder according to the present invention preferably has a BET specific surface area of 3 to 400 m 2 / g.
- the lithium compound used in the present invention is not particularly limited, and various lithium salts can be used.
- lithium hydroxide monohydrate, lithium nitrate, lithium carbonate, lithium acetate, lithium bromide examples include lithium chloride, lithium citrate, lithium fluoride, lithium iodide, lithium lactate, lithium oxalate, lithium phosphate, lithium pyruvate, lithium sulfate, and lithium oxide, with lithium carbonate being preferred.
- the mixing ratio is preferably 20 to 100 wt% with respect to the precursor particles.
- the lithium compound used preferably has an average particle size of 50 ⁇ m or less. More preferably, it is 30 ⁇ m or less. When the average particle diameter of the lithium compound exceeds 50 ⁇ m, mixing with the precursor particles becomes non-uniform, and it becomes difficult to obtain composite oxide particle powder having good crystallinity.
- the mixing treatment of the precursor particle powder containing the transition metal and the element A and the lithium compound may be either dry or wet as long as it can be uniformly mixed.
- the mixing treatment of the precursor particle powder containing the transition metal and the element A and the lithium compound may be performed at once, and the fired product obtained by mixing and baking the precursor particle powder containing the transition metal and the element A and the lithium compound; Further, other lithium compounds may be mixed.
- Examples of the method for producing positive electrode active material particle powder according to the present invention include a method of firing a mixture of precursor particles containing transition metal and element A and a lithium compound, and a precursor containing transition metal and element A.
- a slurry containing particle powder and a lithium compound may be sprayed into a high-temperature container at 100 to 400 ° C. to obtain a dry powder and then fired.
- the firing temperature at this time is preferably 500 to 1500 ° C.
- the temperature is less than 500 ° C.
- the reaction between Li and Ni, Co, and Mn does not proceed sufficiently and is not sufficiently combined. Therefore, the positive electrode active material particle powder having the desired compression density cannot be obtained.
- the temperature exceeds 1500 ° C., the sintering proceeds excessively, which is not preferable.
- a temperature range of 700 to 1200 ° C. is more preferable, and a temperature range of 800 to 1050 ° C. is even more preferable.
- the atmosphere during firing is preferably an oxidizing gas atmosphere, and more preferably normal air.
- the firing time is preferably 1 to 30 hours.
- the obtained positive electrode active material particle powder needs to be composed of a compound having at least a crystal system belonging to the space group R-3m and a crystal system belonging to the space group C2 / m in a specific ratio.
- the Mn content is a molar ratio and Mn / (Ni + Co + Mn) is 0.55 or more, preferably 0.
- the precursor particles may be prepared in the range of .55 to 0.8.
- a method for preparing Mn / (Ni + Co + Mn) of the precursor particles within the above range a method of adjusting the amount of nickel salt, cobalt salt and manganese salt as raw materials, a method of adjusting the pH of the reaction solution, ammonia and the like Examples include a method of adjusting with a complexing agent.
- the crystal system belonging to the space group R-3m is derived from the above LiM x Mn 1-x O 2 compound, and the crystal system belonging to the space group C2 / m is the above Li 2 M ′ (1-y ) Although it is derived from Mn y O 3 , these compounds are formed simultaneously by a series of manufacturing methods, and the ratio is basically determined by the Li and Mn contents of the precursor as described above. It is what is done.
- the peak intensity ratio (a) / (b) tends to decrease, that is, Li 2 M ′ (1- y) Mn y O 3 tends to decrease.
- the peak intensity ratio (a) / (b) tends to increase, that is, Li 2 M ′ (1-y) Mn y O 3 having a crystal system belonging to the space group C2 / m increases. It becomes a trend.
- the peak intensity ratio (a) / (b) tends to decrease, that is, it has a crystal system belonging to the space group space group C2 / m. Li 2 M ′ (1-y) Mn y O 3 tends to decrease. Conversely, when a large amount of complexing agent is added, the peak intensity ratio (a) / (b) tends to increase, that is, Li 2 M ′ (1-y) Mn y O 3 having a crystal system belonging to the space group C2 / m. Tends to increase.
- one or more selected from ammonium ion donor, hydrazine, ethylenediaminetetraacetic acid, nitritotriacetic acid, uracil diacetic acid, dimethylglyoxime, dithizone, oxine, acetylacetone or glycine may be used. it can.
- the peak intensity ratio (a) / (b) is different, and when the firing temperature is increased, the peak intensity ratio (a) / (b) tends to decrease, that is, the space group space group C2. Li 2 M ′ (1-y) Mn y O 3 having a crystal system belonging to / m tends to decrease. Conversely, when the firing temperature is lowered, the peak intensity ratio (a) / (b) tends to increase, that is, the amount of Li 2 M ′ (1-y) Mn y O 3 having a crystal system belonging to the space group C2 / m increases. Tend to be.
- a conductive agent and a binder are added and mixed according to a conventional method.
- the conductive agent acetylene black, carbon black, graphite and the like are preferable
- the binder polytetrafluoroethylene, polyvinylidene fluoride and the like are preferable.
- the secondary battery manufactured using the positive electrode containing the positive electrode active material particle powder according to the present invention includes the positive electrode, the negative electrode, and an electrolyte.
- lithium metal lithium metal, lithium / aluminum alloy, lithium / tin alloy, graphite, graphite or the like can be used.
- an organic solvent containing at least one of carbonates such as propylene carbonate and dimethyl carbonate and ethers such as dimethoxyethane can be used as the solvent for the electrolytic solution.
- At least one lithium salt such as lithium perchlorate and lithium tetrafluoroborate can be dissolved in the above solvent and used.
- the secondary battery manufactured using the positive electrode containing the positive electrode active material particle powder according to the present invention has a discharge capacity of 0.1 C of 250 mAh / g or more, preferably 260 mAh / g or more, according to the evaluation method described later. Preferably it is 270 mAh / g or more, and even more preferably 280 mAh / g or more.
- the secondary battery manufactured using the positive electrode containing the positive electrode active material particle powder according to the present invention has a discharge capacity of 1 C of 210 mAh / g or more, preferably 220 mAh / g or more, more preferably, according to an evaluation method described later. It is 230 mAh / g or more, and even more preferably 240 mAh / g or more.
- the present inventors consider that the element A component is dispersed inside and outside the positive electrode active material particles, and the discharge capacity is improved by preventing excessive sintering during firing.
- a typical embodiment of the present invention is as follows.
- the BET specific surface area value was measured by the BET method using nitrogen.
- the tap density value was obtained from the bulk density when a predetermined amount of positive electrode active material particle powder passed through a mesh was passed through a graduated cylinder and tapped 500 times.
- the compression density value was obtained from the bulk density at a pressure of 3 t / cm 2 after filling a predetermined amount of positive electrode active material particle powder through a mesh into a mold having a high sealing property like a tablet molding machine.
- the content of lithium, nickel, cobalt, manganese, yttrium, zirconium, and silicon constituting the positive electrode active material particle powder was determined by dissolving the positive electrode active material particle powder with an acid, and “plasma emission spectroscopic analyzer ICPS-7500” ) Shimadzu Corporation) ”.
- Phase identification and intensity measurement were performed by X-ray diffraction measurement.
- the X-ray diffractometer is “X-ray diffractometer RINT-2000 (Rigaku Corp.)” (tube: Cu, tube voltage: 40 kV, tube current: 40 mA, step angle: 0.020 °, counting time: 0.6 s Divergence slit: 1 °, scattering slit: 1 °, light receiving slit: 0.30 mm).
- the average secondary particle diameter of the particles was observed using a “scanning electron microscope SEM-EDX with energy dispersive X-ray analyzer (Hitachi High-Technologies Corporation)”, and the diameter was converted back to a volume average value to obtain an average secondary particle diameter. The secondary particle size was taken.
- EC ethylene carbonate
- DMC dimethyl carbonate
- Example 1 14 L of water was put into the sealed reaction tank, and kept at 50 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium carbonate and sodium silicate were continuously added while stirring so that the pH was 8.3 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder.
- SEM scanning electron microscope
- the obtained positive electrode active material particle powder contains a crystal system belonging to the space group R-3m and a crystal system belonging to the space group C2 / m, and the peak intensity ratio (a) / (B) was 0.066.
- Si 0.179 wt%, tap density 2.10 g / cc, compression density 2.55 g / cc.
- the BET specific surface area by the nitrogen adsorption method was 5.52 m 2 / g. Moreover, as a result of observing the particles of the positive electrode active material particle powder with a scanning electron microscope (SEM), it was observed that secondary particles having an average secondary particle diameter of 12.1 ⁇ m were formed.
- SEM scanning electron microscope
- Example 2 14 L of water was put into the sealed reaction tank and kept at 60 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium carbonate, sodium silicate, and ammonia were continuously added while stirring so that the pH was 8.5 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium hydroxide powder were weighed and mixed thoroughly. This was fired at 950 ° C. for 5 hours under an air flow using an electric furnace to obtain positive electrode active material particle powder.
- Example 3 14 L of water was put into the sealed reaction tank and kept at 40 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium hydroxide, sodium silicate, and ammonia were continuously added while stirring so that the pH was 9.2 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. This was baked for 5 hours at 900 ° C. under air flow using an electric furnace.
- Example 4 14 L of water was put into the closed reaction tank and kept at 30 ° C. while nitrogen gas was circulated. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium carbonate and sodium silicate were continuously added while stirring so that the pH was 8.9 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. This was fired at 780 ° C. for 10 hours under an air flow using an electric furnace to obtain positive electrode active material particle powder.
- Example 5 14 L of water was put into the sealed reaction tank and kept at 60 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium carbonate, sodium silicate, and ammonia were continuously added with stirring so that the pH was 8.1 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. Using an electric furnace, this was fired at 1080 ° C. for 5 hours under air flow to obtain positive electrode active material particle powder.
- Example 6 14 L of water was put into the sealed reaction tank and kept at 40 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium carbonate and sodium silicate were continuously added while stirring so that the pH was 8.4 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. This was fired at 850 ° C. for 10 hours in an air stream using an electric furnace to obtain positive electrode active material particle powder.
- Example 7 14 L of water was put into the sealed reaction tank and kept at 40 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium hydroxide, sodium silicate, and ammonia were continuously added while stirring so that the pH was 9.6 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. This was baked for 5 hours at 880 ° C. under air flow using an electric furnace.
- Example 9 14 L of water was put into the sealed reaction tank, and kept at 50 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium hydroxide and sodium silicate were continuously added while stirring so that the pH was 9.6 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium hydroxide powder were weighed and mixed thoroughly. This was fired at 550 ° C. for 25 hours under an oxygen flow using an electric furnace.
- Example 10 14 L of water was put into the sealed reaction tank and kept at 40 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, Mn, and Zr and a mixed aqueous solution of sodium hydroxide and ammonia were continuously added with stirring so that the pH was 9.4 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. This was baked for 5 hours at 930 ° C. under air flow using an electric furnace.
- Example 11 14 L of water was put into the closed reaction tank, and kept at 70 ° C. while circulating nitrogen gas. Further, a mixed nitrate aqueous solution of Ni, Co, Mn, and Y and an aqueous sodium carbonate solution were continuously added while stirring so that the pH was 8.6 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium nitrate powder were weighed and mixed well. This was fired at 850 ° C. for 10 hours under an air flow using an electric furnace.
- Example 13 14 L of water was put into the sealed reaction tank, and kept at 50 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, Mn, and Y and a mixed aqueous solution of sodium carbonate and sodium silicate were continuously added with stirring so that the pH was 8.5 ( ⁇ 0.2). During the reaction, the slurry was discharged from the system through an overflow line, and then the coprecipitation product slurry was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. This was fired at 1250 ° C. for 5 hours under an air flow using an electric furnace to obtain positive electrode active material particle powder.
- Example 15 14 L of water was put into the sealed reaction tank, and kept at 50 ° C. while circulating nitrogen gas. Further, a mixed aqueous solution of Ni and Mn sulfate and a mixed aqueous solution of sodium carbonate and sodium silicate were continuously added while stirring so that the pH was 9.1 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. This was fired at 830 ° C. for 10 hours under an air flow using an electric furnace to obtain positive electrode active material particle powder.
- Example 16 14 L of water was put into a closed reaction tank, and kept at 45 ° C. while flowing nitrogen gas. Further, a mixed aqueous solution of Ni and Mn sulfate and a mixed aqueous solution of sodium hydroxide, sodium silicate, and ammonia were continuously added with stirring so that the pH was 9.9 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. This was fired at 850 ° C. for 5 hours under an air flow using an electric furnace to obtain positive electrode active material particle powder.
- Example 17 14 L of water was put into the sealed reaction tank, and kept at 50 ° C. while circulating nitrogen gas. Further, a mixed aqueous solution of Co and Mn sulfate and a mixed aqueous solution of sodium carbonate and sodium silicate were continuously added with stirring so that the pH was 8.5 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. This was fired at 800 ° C. for 10 hours in an air stream using an electric furnace to obtain positive electrode active material particle powder.
- Comparative Example 1 14 L of water was put into the sealed reaction tank and kept at 40 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium carbonate, sodium silicate, and ammonia were continuously added while stirring so that the pH was 9.0 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. This was fired at 600 ° C. for 25 hours in an air stream using an electric furnace to obtain positive electrode active material particle powder.
- Comparative Example 3 14 L of water was put into the sealed reaction tank and kept at 40 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium carbonate and ammonia were continuously added with stirring so that the pH was 8.5 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium hydroxide powder were weighed and mixed thoroughly. This was fired at 1030 ° C. for 5 hours under an air flow using an electric furnace to obtain positive electrode active material particle powder.
- Reference Example 1 and Comparative Example 6 14 L of water was put into the sealed reaction tank, and kept at 50 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium carbonate, sodium silicate, and ammonia were continuously added while stirring so that the pH was 8.8 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder.
- the obtained coprecipitation precursor and lithium hydroxide powder were weighed and mixed thoroughly. This was fired at 430 ° C. for 25 hours under an air flow using an electric furnace to obtain positive electrode active material particle powder.
- this example is a precursor particle powder corresponding to the present invention 6 (Reference Example 1), the firing temperature does not satisfy the present invention 7, and the obtained positive electrode active material particle powder satisfies the present invention 1. No (Comparative Example 6).
- Comparative Example 7 14 L of water was put into the sealed reaction tank and kept at 40 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, Mn, and Zr, and a mixed aqueous solution of sodium hydroxide and ammonia were continuously added while stirring so that the pH was 9.8 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system by a concentrating device, and after the reaction while the solid content was retained in the reaction tank, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. This was fired for 10 hours at 750 ° C. under an air flow using an electric furnace.
- Comparative Example 8 14 L of water was put into the sealed reaction tank and kept at 60 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium carbonate and ammonia were continuously added with stirring so that the pH was 8.0 ( ⁇ 0.2). During the reaction, the slurry was discharged from the system through an overflow line, and then the coprecipitation product slurry was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor, lithium carbonate powder and silicon oxide were weighed and mixed well. This was fired at 900 ° C. for 5 hours under an air flow using an electric furnace to obtain positive electrode active material particle powder.
- Comparative Example 9 14 L of water was put into the sealed reaction tank and kept at 40 ° C. while circulating nitrogen gas. Further, a mixed sulfate aqueous solution of Ni, Co, and Mn and a mixed aqueous solution of sodium carbonate and ammonia were continuously added with stirring so that the pH was 8.8 ( ⁇ 0.2). During the reaction, only the filtrate was discharged out of the system with a concentrating device, and the solid content was retained in the reaction tank. After the reaction, a slurry of the coprecipitation product was collected. The collected slurry was filtered, washed with water, and dried at 105 ° C. overnight to obtain a coprecipitation precursor powder. The obtained coprecipitation precursor and lithium carbonate powder were weighed and mixed thoroughly. This was fired at 700 ° C. for 5 hours under an air flow using an electric furnace to obtain a positive electrode active material particle powder.
- Table 1 shows the characteristics of the precursor particle powders obtained in Examples 1 to 17 and Comparative Examples 1 to 9
- Table 2 shows the characteristics of the positive electrode active material particle powders, and these positive electrode active material particle powders were used.
- Table 3 shows the characteristics of the obtained batteries.
- the positive electrode active material particles obtained in Examples 1 to 17 each have a discharge capacity of 0.1 C of 250 mAh / g or more and a discharge capacity of 1 C of 210 mAh / g or more.
- the positive electrode active material particle powder according to the present invention has a large discharge capacity by having a crystal structure of a space group of 2 C / m, and further, excessive sintering during firing is suppressed by the element A contained therein, and is appropriate. Because of its high tap density and compression density, it is an excellent positive electrode material having a high capacity even at a high discharge rate.
- the comparative example does not contain an appropriate amount of element A, or the one added with element A after synthesis of precursor particles has a lower discharge capacity than the examples, and an appropriate amount of element A is dispersed in the particles and coexists. By doing so, it is recognized that a positive electrode active material for a non-aqueous electrolyte secondary battery having an excellent discharge capacity can be obtained.
- the positive electrode active material particle powder according to the present invention is effective as a positive electrode active material for a non-aqueous electrolyte secondary battery excellent in charge / discharge capacity.
- the positive electrode active material particle powder according to the present invention is suitable as a positive electrode active material particle powder for a non-aqueous electrolyte secondary battery because the charge / discharge capacity is greatly improved.
Abstract
Description
なお、空間群R-3mは正式には、R3mの3の上にバーのついた表記が正しいが、ここでは便宜上、R-3mと記す。
本発明において、元素A成分は正極活物質粒子内外に分散しており、焼成時の過剰な焼結を防ぐことによって、放電容量が向上するものと本発明者らは考えている。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら50℃に保持した。さらにpH=8.3(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と炭酸ナトリウム、珪酸ナトリウムの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
ICP組成分析の結果、それぞれモル比でNi:Co:Mn=18.7:12.4:68.9(Mn/(Ni+Co+Mn)=0.689)であり、Si=0.152wt%であった。また、走査型電子顕微鏡(SEM)によって前記前駆体粒子粉末の粒子を観察した結果、平均二次粒子径が12.7μmの二次粒子を形成している様子が観測された。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下880℃で5hr焼成した。
ICP組成分析の結果、それぞれモル比でLi/(Ni+Co+Mn)=1.42、Ni:Co:Mn=18.7:12.4:68.9(Mn/(Ni+Co+Mn)=0.689)であり、Si=0.179wt%、タップ密度2.10g/cc、圧縮密度2.55g/ccであった。窒素吸着法によるBET比表面積は5.52m2/gであった。また、走査型電子顕微鏡(SEM)によって前記正極活物質粒子粉末の粒子を観察した結果、平均二次粒子径が12.1μmの二次粒子を形成している様子が観測された。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら60℃に保持した。さらにpH=8.5(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と炭酸ナトリウム、珪酸ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と水酸化リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下950℃で5hr焼成し、正極活物質粒子粉末を得た。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら40℃に保持した。さらにpH=9.2(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と水酸化ナトリウム、珪酸ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下900℃で5hr焼成した。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら30℃に保持した。さらにpH=8.9(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と炭酸ナトリウム、珪酸ナトリウムの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下780℃で10hr焼成し、正極活物質粒子粉末を得た。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら60℃に保持した。さらにpH=8.1(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と炭酸ナトリウム、珪酸ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下1080℃で5hr焼成し、正極活物質粒子粉末を得た。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら40℃に保持した。さらにpH=8.4(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と炭酸ナトリウム、珪酸ナトリウムの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下850℃で10hr焼成し、正極活物質粒子粉末を得た。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら40℃に保持した。さらにpH=9.6(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と水酸化ナトリウム、珪酸ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下880℃で5hr焼成した。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら40℃に保持した。さらにpH=10.4(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と水酸化ナトリウム、珪酸ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下700℃で15hr焼成した。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら50℃に保持した。さらにpH=9.6(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と水酸化ナトリウム、珪酸ナトリウムの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と水酸化リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、酸素流通下550℃で25hr焼成した。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら40℃に保持した。さらにpH=9.4(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mn、Zrの混合硫酸塩水溶液と水酸化ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下930℃で5hr焼成した。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら70℃に保持した。さらにpH=8.6(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mn、Yの混合硝酸塩水溶液と炭酸ナトリウム水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と硝酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下850℃で10hr焼成した。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら30℃に保持した。さらにpH=11.5(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mn、Zrの混合塩化物水溶液と水酸化リチウム水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下850℃で5hr焼成した。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら50℃に保持した。さらにpH=8.5(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mn、Yの混合硫酸塩水溶液と炭酸ナトリウム、珪酸ナトリウムの混合水溶液を加えた。反応中はオーバーフローラインによりスラリーを系外に排出させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下1250℃で5hr焼成し、正極活物質粒子粉末を得た。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら40℃に保持した。さらにpH=9.4(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mn、Zrの混合硫酸塩水溶液と水酸化ナトリウム、珪酸ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下900℃で5hr焼成した。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら50℃に保持した。さらにpH=9.1(±0.2)となるよう、攪拌しながら連続的にNi、Mnの混合硫酸塩水溶液と炭酸ナトリウム、珪酸ナトリウムの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下830℃で10hr焼成し、正極活物質粒子粉末を得た。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら45℃に保持した。さらにpH=9.9(±0.2)となるよう、攪拌しながら連続的にNi、Mnの混合硫酸塩水溶液と水酸化ナトリウム、珪酸ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下850℃で5hr焼成し、正極活物質粒子粉末を得た。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら50℃に保持した。さらにpH=8.5(±0.2)となるよう、攪拌しながら連続的にCo、Mnの混合硫酸塩水溶液と炭酸ナトリウム、珪酸ナトリウムの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下800℃で10hr焼成し、正極活物質粒子粉末を得た。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら40℃に保持した。さらにpH=9.0(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と炭酸ナトリウム、珪酸ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下600℃で25hr焼成し、正極活物質粒子粉末を得た。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら40℃に保持した。さらにpH=11.7(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と水酸化ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下1250℃で5hr焼成した。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら40℃に保持した。さらにpH=8.5(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と炭酸ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と水酸化リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下1030℃で5hr焼成し、正極活物質粒子粉末を得た。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら40℃に保持した。さらにpH=11.4(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と水酸化ナトリウム、珪酸ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下1030℃で5hr焼成した。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら10℃に保持した。さらにpH=12.5(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と水酸化ナトリウム、珪酸ナトリウムの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、酸素流通下900℃で5hr焼成した。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら50℃に保持した。さらにpH=8.8(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と炭酸ナトリウム、珪酸ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と水酸化リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下430℃で25hr焼成し、正極活物質粒子粉末を得た。
本例は、本発明6に相当する前駆体粒子粉末であるが(参考例1)、焼成温度が本発明7を満足せず、また、得られた正極活物質粒子粉末は本発明1を満足しない(比較例6)。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら40℃に保持した。さらにpH=9.8(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mn、Zrの混合硫酸塩水溶液と水酸化ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下750℃で10hr焼成した。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら60℃に保持した。さらにpH=8.0(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と炭酸ナトリウム、アンモニアの混合水溶液を加えた。反応中はオーバーフローラインによりスラリーを系外に排出させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末及び酸化珪素を秤量し、十分に混合した。これを電気炉を用いて、空気流通下900℃で5hr焼成し、正極活物質粒子粉末を得た。
密閉型反応槽に水を14L入れ、窒素ガスを流通させながら40℃に保持した。さらにpH=8.8(±0.2)となるよう、攪拌しながら連続的にNi、Co、Mnの混合硫酸塩水溶液と炭酸ナトリウム、アンモニアの混合水溶液を加えた。反応中は濃縮装置により濾液のみを系外に排出して固形分は反応槽に滞留させながら反応後、共沈生成物のスラリーを採取した。採取したスラリーを濾過、水洗し、105℃で一晩乾燥させ、共沈前駆体の粉末を得た。
得られた共沈前駆体と炭酸リチウム粉末を秤量し、十分に混合した。これを電気炉を用いて、空気流通下700℃で5hr焼成し、正極活物質粒子粉末を得た。
Claims (8)
- 少なくとも空間群R-3mに属する結晶系と空間群C2/mに属する結晶系とを有する化合物からなる正極活物質粒子粉末であって、当該化合物は少なくともLiとMnと元素A(Si、Zr又はYから選ばれる少なくとも1種の元素)とCo及び/又はNiとを含有する複合酸化物であり、正極活物質粒子粉末のCu-Kα線を使用した粉末X線回折図の2θ=20.8±1°における最大回折ピークの強度(a)と2θ=18.6±1°における最大回折ピークの強度(b)との相対強度比(a)/(b)が0.02~0.2である正極活物質粒子粉末であり、該正極活物質粒子粉末のMn含有量はモル比(Mn/(Ni+Co+Mn))で0.55以上であって元素Aを0.03~5wt%含有し、タップ密度が0.8~2.4g/ccであり、圧縮密度が2.0~3.1g/ccであることを特徴とする正極活物質粒子粉末。
- 空間群R-3mに属する結晶系を有する化合物としてLiMxMn1-xO2(MはNi及び/またはCo、0<x≦1)を、空間群C2/mに属する結晶系を有する化合物としてLi2M’(1-y)MnyO3(M’はNi及び/またはCo、0<y≦1)を含むことを特徴とする請求項1に記載の正極活物質粒子粉末。
- Li/(Ni+Co+Mn)がモル比で1.25~1.7であることを特徴とする請求項1~2のいずれかに記載の複合化された正極活物質粒子粉末。
- BET法による比表面積が0.1~20m2/gであることを特徴とする請求項1~3のいずれかに記載の正極活物質粒子粉末。
- 一次粒子が凝集した二次粒子からなる正極活物質粒子粉末であって、平均二次粒子径が1~50μmであることを特徴とする請求項1~4のいずれかに記載の正極活物質粒子粉末。
- 少なくともMnと元素A(Si、Zr又はYから選ばれる少なくとも1種の元素)とCo及び/又はNiとを含有する複合水酸化物又は複合炭酸塩を主成分とする前駆体粒子粉末であり、該前駆体粒子粉末のMn含有量はモル比でMn/(Ni+Co+Mn)が0.55以上であり、元素Aを0.025~5.5wt%含み、平均二次粒子径が1~50μmであることを特徴とする請求項1~5のいずれかに記載の正極活物質粒子粉末の前駆体粒子粉末。
- 請求項1~5のいずれかに記載の正極活物質粒子粉末の製造方法であって、請求項6記載の前駆体粒子粉末及びリチウム化合物を含有する混合物を500~1500℃の範囲で焼成する正極活物質粒子粉末の製造方法。
- 請求項1~5のいずれかに記載の正極活物質粒子粉末を含有する正極を用いたことを特徴とする非水電解質二次電池。
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