WO2011162178A1 - リチウムイオン二次電池 - Google Patents
リチウムイオン二次電池 Download PDFInfo
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- WO2011162178A1 WO2011162178A1 PCT/JP2011/063916 JP2011063916W WO2011162178A1 WO 2011162178 A1 WO2011162178 A1 WO 2011162178A1 JP 2011063916 W JP2011063916 W JP 2011063916W WO 2011162178 A1 WO2011162178 A1 WO 2011162178A1
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- positive electrode
- active material
- electrode active
- ion secondary
- secondary battery
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- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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
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- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a lithium ion secondary battery excellent in output characteristics and cycle characteristics.
- the lithium ion secondary battery includes a positive electrode and a negative electrode, and a non-aqueous electrolyte interposed between the two electrodes, and performs charging / discharging as lithium ions in the electrolyte move between the electrodes.
- As an active material that reversibly occludes and releases lithium ions in the positive electrode lithium-containing transition metal oxides are mainly used.
- Patent documents 1 and 2 are mentioned as technical literature about a cathode material.
- lithium ion secondary batteries In recent years, with the expansion of the use of lithium ion secondary batteries, various performance improvements are desired depending on the application. For applications such as automobiles where output and input at a high rate can be repeated, more excellent output characteristics and durability (cycle characteristics and the like) are required.
- a lithium ion secondary battery having excellent output characteristics not only at room temperature but also at low temperatures (for example, ⁇ 10 ° C. or lower) and having high durability (such as cycle characteristics) even at relatively high temperatures (for example, about 60 ° C.) is provided. Is useful.
- An object of the present invention is to provide a lithium ion secondary battery in which excellent output characteristics and cycle characteristics are simultaneously realized.
- a lithium ion secondary battery including a positive electrode, a negative electrode, and a non-aqueous electrolyte.
- the positive electrode includes a lithium-containing composite oxide having a layered structure (typically, a rock salt-type crystal structure) as a positive electrode active material (typically a lithium transition metal composite oxide containing a transition metal as a constituent metal element) ).
- the positive electrode active material includes at least one metal element M 0 among nickel (Ni), cobalt (Co), and manganese (Mn), and further includes at least one metal element M ′ among Zr, Nb, and Al. Furthermore, W is included. Then, 2 g of the positive electrode active material powder and 100 g of pure water are stirred to prepare a suspension.
- the filtrate obtained by the filtration is subjected to inductively coupled plasma mass spectrometry (ICP). -MS), the W elution amount per 1 g of the filtrate is 0.025 mmol or less.
- ICP inductively coupled plasma mass spectrometry
- -MS inductively coupled plasma mass spectrometry
- the W elution amount per 1 g of the filtrate is 0.025 mmol or less.
- Another lithium ion secondary battery provided by the present invention includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, and the positive electrode has a general formula (I): Li x Ni a Co b as a positive electrode active material.
- a lithium-containing composite oxide (lithium transition metal composite oxide) represented by Mn c M ′ d M ′′ e O 2 ;
- M ′ is selected from Zr, Nb, and Al.
- M ′′ is at least one of W and Mo.
- M ′′ includes at least W.
- e is greater than 0 (ie, e> 0).
- 2 g of the positive electrode active material powder and 100 g of pure water are further stirred to prepare a suspension.
- the filtrate obtained by the filtration is obtained.
- the M ′′ elution amount per 1 g of the filtrate obtained by ICP-MS is 0.025 mmol or less.
- M ′′ is at least W (For example, substantially all of M ′′ is W), and the elution amount of W is 0.025 mmol or less.
- Such a lithium ion secondary battery has the characteristics that the positive electrode active material contains M ′ and M ′′ together with the predetermined amount and the M ′′ elution amount is 0.025 mmol / g or less.
- the reaction resistance is low and the output characteristics can be excellent.
- it can be excellent in durability (for example, cycle characteristics) against high-rate charge / discharge at a relatively high temperature (about 60 ° C.).
- M ′ is preferably substantially entirely Zr (zirconium).
- M ′′ is preferably substantially all W (tungsten).
- x is 1.0 ⁇ x ⁇ 1.20 (for example, 0.05 ⁇ x ⁇ 1).
- a may be 0.1 ⁇ a ⁇ 1 (eg, 0.3 ⁇ a ⁇ 0.9, preferably 0.3 ⁇ a ⁇ 0.6)
- b may be 0 ⁇ 0.
- b ⁇ 0.5 e.g. 0.1 ⁇ b ⁇ 0.4, preferably 0.3 ⁇ b ⁇ 0.6
- c may be 0 ⁇ c ⁇ 0.5 (e.g.
- the technique disclosed herein may further include other elements (eg, Cr, Fe). , V, Ti, Cu, Zn, Ga, In, Sn, La, Ce, Ca, Mg and Na) In the lithium ion secondary battery having a case oxide as the positive electrode active material may be applied.
- the lithium ion secondary battery disclosed herein is a SEM-EDX image taken with the procedure and conditions described in the examples for the surface of the positive electrode active material layer (typically, the surface of the positive electrode sheet) (for example, ⁇ with a magnification of about 1000), at least a significant deviation (aggregate, etc.) in the element distribution of M ′′ (for example, W) may not be observed. Any element distribution of M ′′ and M ′ (for example, Zr) In addition, it is preferable that no significant deviation (agglomerate or the like) is observed.
- the positive electrode active material in the technology disclosed herein may be in the form of secondary particles in which primary particles of a lithium transition metal composite oxide having a layered structure are collected.
- M ′′ for example, W contained in the positive electrode active material is present (distributed) biased toward the surface of the primary particles (that is, concentrated on the surface rather than inside the primary particles).
- the surface of the positive electrode active material layer using a positive electrode active material is preferably a positive electrode active material having no significant deviation in the distribution of W.
- the positive electrode active material has a small amount of W elution and realizes a high-performance battery. possible.
- the manufacturing method includes preparing an aqueous solution Aq A containing the M 0 and the M ′.
- the method includes preparing an aqueous solution Aq C containing W.
- the aqueous solution Aq A and the aqueous solution Aq C are mixed under alkaline conditions (for example, while maintaining the pH at 11 to 14) to obtain a hydroxide (precursor) containing the M 0 , the M ′, and the W Precipitation.
- the manufacturing method may further include mixing the hydroxide and a lithium compound, and firing the mixture to form the lithium transition metal composite oxide.
- the present invention also provides another method for producing any of the positive electrode active materials disclosed herein. Its manufacturing method is: (A) An aqueous solution containing a nickel salt, a cobalt salt, a manganese salt, and an M′-containing salt at a predetermined concentration in a basic aqueous solution having a pH of 11 to 14, and an aqueous solution containing an M ′′ -containing salt at a predetermined concentration.
- M ′ is at least one selected from Zr, Nb, and Al.
- M ′′ is at least one of W and Mo.
- M ′′ includes at least W. Substantially all of M ′′ (95% or more, for example, 98% or more, or 100% in terms of the number of atoms) may be W.
- the positive electrode active material is preferably produced.
- D: e is preferably about 2: 1 to 1:10, a: b: c is not particularly limited, and at least a is larger than 0 (in other words, at least Ni is included). Is preferred.
- a may be 0.1 ⁇ a ⁇ 1 (for example, 0.3 ⁇ a ⁇ 0.9, preferably 0.3 ⁇ a ⁇ 0.6).
- b may be 0 ⁇ b ⁇ 0.5 (for example, 0.1 ⁇ b ⁇ 0.4, preferably 0.3 ⁇ b ⁇ 0.6).
- c may be 0 ⁇ c ⁇ 0.5 (eg, 0.1 ⁇ c ⁇ 0.4, preferably 0.3 ⁇ c ⁇ 0.6).
- any of the lithium ion secondary batteries disclosed herein is suitable as a power source used in a vehicle because it has excellent output characteristics at room temperature and low temperature and good durability at high temperature. is there. Therefore, according to this invention, the vehicle provided with one of the lithium ion secondary batteries disclosed here is provided.
- a vehicle for example, an automobile
- a lithium ion secondary battery as a power source (typically, a power source of a hybrid vehicle or an electric vehicle) is preferable.
- FIG. 1 is a perspective view schematically showing an outer shape of a lithium ion secondary battery according to an embodiment.
- 2 is a cross-sectional view taken along line II-II in FIG.
- FIG. 3 is a side view schematically showing a vehicle (automobile) provided with the lithium ion secondary battery of the present invention.
- FIG. 4 is an image obtained by SEM-EDX (energy dispersive X-ray spectroscopy) showing the Zr element distribution of the positive electrode active material particles of Example 3.
- FIG. 5 is an SEM-EDX image showing the W element distribution of the positive electrode active material particles of Example 3.
- FIG. 6 is a SEM-EDX image showing the Zr element distribution of the positive electrode active material particles of Example 6.
- FIG. 7 is an SEM-EDX image showing the W element distribution of the positive electrode active material particles of Example 6.
- the lithium-containing composite oxide (i) represented by the above general formula (I) is included as the positive electrode active material.
- M ′ is preferably Zr.
- M ′′ is preferably W.
- the molar ratio of M ′ to M ′′ (ie, d: e) is preferably about 2: 1 to 1:10.
- a: b: c is not particularly limited.
- the lithium ion secondary battery is further prepared by stirring 2 g of the positive electrode active material powder and 100 g of pure water to prepare a suspension, and filtering the suspension, the filtrate obtained by the filtration.
- the M ′′ elution amount per gram of the filtrate determined by ICP-MS is 0.025 mmol or less.
- the M ′′ elution amount is preferably 0.020 mmol / g or less.
- the lithium ion secondary battery disclosed herein is also a SEM-EDX image taken in accordance with the procedures and conditions described in the examples for the surface of the positive electrode active material layer (typically, the surface of the positive electrode sheet).
- the element distribution of M ′ and M ′′ may be such that no significant deviation (agglomerate etc.) is observed.
- the positive electrode active material in the technology disclosed herein may be in the form of secondary particles in which primary particles of a lithium transition metal composite oxide having a layered structure are collected.
- the positive electrode active material contains W, and the W is present (distributed) biased toward the surface of the primary particles (that is, concentrated on the surface rather than inside the primary particles).
- W is “biased on the surface of the primary particles” means that W is present (distributed) concentrated on the surface (grain boundaries) of the primary particles compared to the inside of the primary particles. means. Therefore, it does not mean only an aspect in which W exists only at the grain boundary (in other words, it does not exist at all inside the primary particle).
- the presence of W on the surface of primary particles is, for example, the distribution of W using energy dispersive X-ray spectroscopy (EDX; Energy Dispersive X-ray Spectroscopy) for active material particles (secondary particles).
- EDX Energy Dispersive X-ray Spectroscopy
- W is concentrated and present at the grain boundary (the amount of W present per area at the grain boundary is larger than that inside the primary particle).
- the position of the grain boundary (primary particle surface) can be grasped by, for example, observation of a cross section of the positive electrode active material particles by a transmission electron microscope (TEM).
- TEM transmission electron microscope
- the positive electrode active material disclosed herein for example, the composite oxide (i)
- an appropriate method is adopted in which the M ′′ elution amount obtained as described above is 0.025 mmol / g or less. do it.
- the precursor (ii) prepared by wet mixing as described above can be mixed with an appropriate lithium salt and fired at a predetermined temperature.
- wet mixing refers to an aqueous solution (hereinafter referred to as NiCoMnM ′) containing a nickel salt, a cobalt salt, a manganese salt, and an M′-containing salt in a basic aqueous solution having an initial pH of 11 to 14 while maintaining the initial pH.
- an aqueous solution containing an M ′′ -containing salt hereinafter also referred to as an M ′′ aqueous solution
- the temperature of the reaction solution is preferably in the range of 20 to 60 ° C.
- the lithium-containing composite oxide having an M ′′ elution amount of 0.025 mmol / g or less ( i) can be suitably formed.
- Such a composite oxide may have a more uniform distribution of M ′ element and M ′′ element in the crystal and / or on the crystal surface, and segregation of these elements may be suppressed.
- a lithium ion secondary battery using such a composite oxide as a positive electrode active material can be excellent in both output characteristics and cycle characteristics.
- both the positive electrode active material manufactured by this method and the lithium ion secondary battery provided with the positive electrode which has the positive electrode active material manufactured by this method as a main component are included in the scope of the present invention.
- the basic aqueous solution includes a strong base (such as an alkali metal hydroxide) and a weak base (such as ammonia).
- a strong base such as an alkali metal hydroxide
- a weak base such as ammonia
- the liquid temperature is 25 ° C.
- Those having a pH of about 11 to 14 and not inhibiting the formation of the precursor (ii) can be preferably used, typically using a mixed solution of aqueous sodium hydroxide and aqueous ammonia.
- the mixed solution is preferably prepared so that the pH is in the range of 11 to 14 (for example, about pH 12) and the ammonia concentration is 3 to 25 g / L.
- the ammonia concentration of the reaction solution is about 3 to 25 g / L. Is preferably maintained.
- the NiCoMnM ′ aqueous solution can be prepared by dissolving a predetermined amount of a desired nickel salt, cobalt salt, manganese salt, and M′-containing salt in an aqueous solvent.
- the order in which these salts are added to the aqueous solvent is not particularly limited. Moreover, you may prepare by mixing the aqueous solution of each salt. Or you may mix the aqueous solution of M 'containing salt with the aqueous solution containing nickel salt, cobalt salt, and manganese salt.
- the anions of these metal salts (the nickel salt, cobalt salt, manganese salt, and M′-containing salt) may be selected so that the salt has a desired water solubility.
- the metal salts may be nickel, cobalt, manganese, M ′ sulfate, nitrate, hydrochloride, and the like. All or part of these metal salt anions may be the same or different from each other. These salts may be solvates such as hydrates. The order of addition of these metal salts is not particularly limited.
- the concentration of the NiCoMnM ′ aqueous solution is preferably about 1 to 2.2 mol / L in total of all transition metals (Ni, Co, Mn, M ′).
- the above M ′′ aqueous solution can be similarly prepared by dissolving a predetermined amount of M ′′ -containing salt in an aqueous solvent.
- M ′′ -containing salt a salt of an oxo acid (tungstic acid, molybdic acid, etc.) having M ′′ as a central element is typically used.
- the cation contained in the M ′′ -containing salt may be selected so that the salt is water-soluble.
- it may be an ammonium ion, sodium ion, potassium ion, etc.
- ammonium paratungstate can be preferably used.
- the M ′′ -containing salt may be a solvate such as a hydrate.
- concentration of the M ′′ aqueous solution is preferably about 0.01 to 1 mol / L based on the M ′′ element.
- the aqueous solvent used in preparing the NiCoMnM ′ aqueous solution and the M ′′ aqueous solution is typically water.
- a reagent acid, base, etc.
- M ′ is Nb
- Ni salt, Co salt, Mn An aqueous NiCoMnM ′ solution may be prepared by adding an acidic aqueous solution containing an Nb salt to an aqueous salt solution.
- the use amount of the Ni salt, Co salt, Mn salt, M′-containing salt, and M ′′ -containing salt is such that a, b, c, d, and e in the above formula (I) have a desired ratio.
- Mn, M ′, M ′′ may be selected and appropriately determined based on the selected molar ratio.
- M ′ and M ′′ are Salts containing (eg, M ′′ oxoacid salts containing the cation of M ′) may precipitate out.
- M ′′ -containing salt is dissolved in water together with Ni salt, Co salt and Mn salt instead of M′-containing salt, a salt containing Ni, Co, Mn, M ′′ (for example, Ni, Co, Mn cation) M ′′ oxoacid salt containing) can be precipitated.
- NiCoMnM ′ aqueous solution typically acidic solution
- M ′′ aqueous solution eg, W aqueous solution
- a hydroxide (lithium) suitable for the production of a positive electrode active material in which M ′′ (for example, W) is distributed on the crystal surface of the lithium transition metal composite oxide (the surface of the primary particles, in other words, the grain boundary) is distributed.
- M ′′ for example, W
- a composite hydroxide containing Ni, Co, and Mn produced by a conventional method, an M′-containing salt, and an M ′′ -containing salt are dried. Mixed (without solvent, powder After leaving mixing) of solid, when firing the resulting mixture, the distribution of M 'and / or M "may become uneven.
- the precursor (ii) obtained by mixing and precipitating the above basic aqueous solution, NiCoMnM ′ aqueous solution and M ′′ aqueous solution at a predetermined rate under pH control is washed with water, filtered and dried after crystallization is completed.
- the precursor (ii) is heated in an air atmosphere at a temperature of 100 to 300 ° C. for a predetermined time (for example, 5 to 24 hours) and then subjected to the next step. It is preferable to provide.
- the composite oxide (i) can be formed by firing a mixture of the precursor (ii) and an appropriate lithium salt, typically in air.
- the general lithium salt used for formation of lithium complex oxide can be especially used without a restriction
- the mixing ratio of the precursor (ii) to the lithium salt is the sum of all transition metals contained in the precursor (ii) so that (a + b + c + d + e): x in the formula (I) is a desired ratio.
- the number of moles of lithium salt relative to the number of moles may be selected and appropriately determined based on the selected number.
- the firing temperature is preferably in the range of about 700 to 1000 ° C. Firing may be performed at the same temperature at a time, or may be performed stepwise at different temperatures. The firing time can be appropriately selected. For example, after baking at about 700 to 800 ° C. for about 1 to 12 hours, baking can be performed at about 800 to 1000 ° C. for about 2 to 24 hours.
- the lithium-containing composite oxide (i) thus obtained is preferably used after being pulverized and sieved to a desired particle size as necessary.
- the average particle diameter of the composite oxide (i) as the positive electrode active material is usually preferably about 3 ⁇ m to 7 ⁇ m.
- the specific surface area is preferably in the range of 0.5 to 1.8 m 2 / g.
- the tap density is preferably in the range of 1 to 2.2 g / cm 3 .
- a lithium ion secondary battery comprising a positive electrode having any of the positive electrode active materials disclosed herein.
- An embodiment of such a lithium ion secondary battery will be described in detail by taking as an example a lithium ion secondary battery 100 (FIG. 1) having a configuration in which an electrode body and a non-aqueous electrolyte are accommodated in a rectangular battery case.
- the technology disclosed herein is not limited to such an embodiment. That is, the shape of the lithium ion secondary battery disclosed herein is not particularly limited, and the battery case, electrode body, and the like can be appropriately selected in material, shape, size, and the like according to the application and capacity. .
- the battery case may have a rectangular parallelepiped shape, a flat shape, a cylindrical shape, or the like.
- symbol is attached
- the dimensional relationships (length, width, thickness, etc.) in each drawing do not reflect actual dimensional relationships.
- the lithium ion secondary battery 100 includes a wound electrode body 20 and a flat box-shaped battery case 10 corresponding to the shape of the electrode body 20 together with an electrolyte (not shown). It can be constructed by being housed inside the opening 12 and closing the opening 12 of the case 10 with a lid 14.
- the lid body 14 is provided with a positive terminal 38 and a negative terminal 48 for external connection so that a part of the terminals protrudes to the surface side of the lid body 14.
- the electrode body 20 includes a positive electrode sheet 30 in which a positive electrode active material layer 34 is formed on the surface of a long sheet-like positive electrode current collector 32, and a negative electrode active material layer on the surface of a long sheet-like negative electrode current collector 42.
- the negative electrode sheet 40 on which the electrode 44 is formed is rolled up with two long sheet-like separators 50, and the obtained wound body is crushed from the side surface and ablated to form a flat shape. ing.
- the positive electrode sheet 30 is formed such that the positive electrode active material layer 34 is not provided (or removed) at one end along the longitudinal direction, and the positive electrode current collector 32 is exposed.
- the negative electrode sheet 40 to be wound is not provided with (or removed from) the negative electrode active material layer 44 at one end along the longitudinal direction so that the negative electrode current collector 42 is exposed. Is formed.
- the positive electrode terminal 38 is joined to the exposed end portion of the positive electrode current collector 32, and the negative electrode terminal 48 is joined to the exposed end portion of the negative electrode current collector 42, respectively.
- the positive electrode sheet 30 or the negative electrode sheet 40 is electrically connected.
- the positive and negative terminals 38 and 48 and the positive and negative current collectors 32 and 42 can be joined by, for example, ultrasonic welding, resistance welding, or the like.
- the positive electrode sheet 30 is, for example, a paste-like or slurry-like composition in which any positive electrode active material disclosed herein is dispersed in an appropriate solvent together with a conductive material, a binder (binder) or the like as necessary. It can preferably be produced by applying the product (positive electrode mixture) to the positive electrode current collector 32 and drying the composition.
- a conductive powder material such as carbon powder or carbon fiber is preferably used.
- carbon powder various carbon blacks such as acetylene black, furnace black, ketjen black, and graphite powder are preferable.
- a conductive material can be used alone or in combination of two or more.
- the amount of the conductive material contained in the positive electrode active material layer may be appropriately selected, and may be, for example, about 5 to 12% by mass.
- a water-soluble polymer that dissolves in water for example, a water-soluble polymer that dissolves in water, a polymer that disperses in water, a polymer that dissolves in a non-aqueous solvent (organic solvent), and the like can be selected as appropriate. Moreover, only 1 type may be used independently and 2 or more types may be used in combination.
- the water-soluble polymer include carboxymethylcellulose (CMC), methylcellulose (MC), cellulose acetate phthalate (CAP), hydroxypropylmethylcellulose (HPMC), hydroxypropylmethylcellulose phthalate (HPMCP), and polyvinyl alcohol (PVA). It is done.
- water-dispersible polymer examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetra Fluorine resins such as fluoroethylene copolymer (ETFE), vinyl acetate copolymer, styrene butadiene block copolymer (SBR), acrylic acid-modified SBR resin (SBR latex), rubbers such as gum arabic, etc. It is done.
- PTFE polytetrafluoroethylene
- PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- EFE ethylene-tetra Fluorine resins
- ETFE fluoroethylene copolymer
- SBR s
- Examples of the polymer dissolved in the non-aqueous solvent (organic solvent) include, for example, polyvinylidene fluoride (PVDF), polyvinylidene chloride (PVDC), polyethylene oxide (PEO), polypropylene oxide (PPO), and polyethylene oxide-propylene oxide copolymer. (PEO-PPO) and the like.
- PVDF polyvinylidene fluoride
- PVDC polyvinylidene chloride
- PEO polyethylene oxide
- PPO polypropylene oxide
- PEO-PPO polyethylene oxide-propylene oxide copolymer.
- the amount of the binder contained in the positive electrode active material layer may be appropriately selected and can be, for example, about 1.5 to 10% by mass.
- a conductive member made of a metal having good conductivity is preferably used.
- aluminum or an alloy containing aluminum as a main component can be used.
- the shape of the positive electrode current collector 32 may vary depending on the shape of the lithium ion secondary battery, and is not particularly limited, and may be various forms such as a rod shape, a plate shape, a sheet shape, a foil shape, and a mesh shape.
- a sheet-like aluminum positive electrode current collector 32 is used, and can be preferably used for the lithium ion secondary battery 100 including the wound electrode body 20.
- an aluminum sheet having a thickness of about 10 ⁇ m to 30 ⁇ m can be preferably used.
- the negative electrode sheet 40 is made of, for example, a paste or slurry-like composition (negative electrode mixture) in which a negative electrode active material is dispersed in a suitable solvent together with a binder (binder) as necessary. It can preferably be prepared by applying and drying the composition.
- a carbon particle is mentioned as a suitable negative electrode active material.
- a particulate carbon material (carbon particles) containing a graphite structure (layered structure) at least partially is preferably used. Any carbon material of a so-called graphitic material (graphite), a non-graphitizable carbonaceous material (hard carbon), a graphitizable carbonaceous material (soft carbon), or a combination of these materials is preferably used. obtain. Among these, graphite particles such as natural graphite can be preferably used.
- the same positive electrode as that described above can be used alone or in combination of two or more.
- the amount of the binder contained in the negative electrode active material layer may be appropriately selected, and may be, for example, about 1.5 to 10% by mass.
- a conductive member made of a highly conductive metal is preferably used.
- copper or an alloy containing copper as a main component can be used.
- the shape of the negative electrode current collector 42 may vary depending on the shape of the lithium ion secondary battery and the like, so there is no particular limitation, and various shapes such as a rod shape, a plate shape, a sheet shape, a foil shape, and a mesh shape possible.
- a sheet-like copper negative electrode current collector 42 is used, and can be preferably used for the lithium ion secondary battery 100 including the wound electrode body 20.
- a copper sheet having a thickness of about 6 to 30 ⁇ m can be preferably used.
- the non-aqueous electrolyte contains an electrolyte (supporting salt) in a non-aqueous solvent (organic solvent).
- a lithium salt used as an electrolyte in a general lithium ion secondary battery can be appropriately selected and used.
- the lithium salt include LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , Li (CF 3 SO 2 ) 2 N, LiCF 3 SO 3 and the like. These lithium salts can be used alone or in combination of two or more.
- a particularly preferred example is LiPF 6 .
- the non-aqueous electrolyte is preferably prepared so that the electrolyte concentration is within a range of 0.7 to 1.3 mol / L, for example.
- an organic solvent used for a general lithium ion secondary battery can be appropriately selected and used.
- particularly preferred non-aqueous solvents include carbonates such as ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and propylene carbonate (PC).
- EC ethylene carbonate
- DEC diethyl carbonate
- DMC dimethyl carbonate
- EMC ethyl methyl carbonate
- EMC ethyl methyl carbonate
- VC vinylene carbonate
- PC propylene carbonate
- the These organic solvents can be used alone or in combination of two or more.
- a mixed solvent of EC and DEC can be preferably used.
- the separator 50 is a layer interposed between the positive electrode sheet 30 and the negative electrode sheet 40, and typically has a sheet shape, and the positive electrode active material layer 34 of the positive electrode sheet 30 and the negative electrode active material layer of the negative electrode sheet 40. 44 to be in contact with each other. Then, prevention of short circuit due to the contact between the electrode active material layers 34 and 44 in the positive electrode sheet 30 and the negative electrode sheet 40, and the conduction path between the electrodes (conductive path) by impregnating the electrolyte in the pores of the separator 50. ).
- this separator 50 a conventionally well-known thing can be especially used without a restriction
- a porous polyolefin resin sheet such as polyethylene (PE), polypropylene (PP), and polystyrene is preferred.
- PE polyethylene
- PP polypropylene
- polystyrene polystyrene
- a PE sheet, a PP sheet, a multilayer structure sheet in which a PE layer and a PP layer are laminated, and the like can be suitably used.
- the thickness of the separator is preferably set within a range of about 10 ⁇ m to 40 ⁇ m, for example.
- Example 1 A reaction vessel equipped with a stirrer and a nitrogen introduction tube was charged with about half of its capacity, and heated to 40 ° C. with stirring. After replacing the reaction vessel with nitrogen, an appropriate amount of 3.25% aqueous sodium hydroxide solution and 25% aqueous ammonia was added in a nitrogen stream, and the pH at the liquid temperature of 25 ° C. was 12.0, and the ammonia concentration in the liquid phase was 20 g. / L was adjusted to obtain a basic aqueous solution. The oxygen concentration in the reaction vessel was about 2.0%.
- Nickel sulfate, cobalt sulfate, manganese sulfate, and zirconium sulfate have a molar ratio of these elements Ni: Co: Mn: Zr of 0.33: 0.33: 0.33: 0.005, and the total concentration of these transition metals is
- a NiCoMnZr aqueous solution was prepared by dissolving in water so as to be 1.8 mol / L.
- Ammonium paratungstate was dissolved in water to prepare a W aqueous solution having a tungsten (W) concentration of 0.05 mol / L.
- NiCoMnZr aqueous solution and W aqueous solution obtained above were added to and mixed with the basic aqueous solution while maintaining the pH at 12.0, and the element molar ratio Ni: Co: Mn: Zr: W was 0.33: 0.33: 0.33: 0.005: 0.005 hydroxide (Ni 0.33 Co 0.33 Mn 0.33 Zr 0.005 W 0.005 (OH) 2 + ⁇ (0 ⁇ ⁇ ⁇ 0 .5); Precursor) was obtained.
- the hydroxide particles were heated in an air atmosphere at a temperature of 150 ° C. for 12 hours.
- the total molar number of transition metals (ie, Ni, Co, Mn, Zr, W) in the hydroxide is M, and the molar ratio of lithium to M (Li / M) is 1.15.
- the lithium carbonate was weighed and mixed with the hydroxide particles after the heat treatment. The obtained mixture was calcined at 760 ° C. for 4 hours in air of 21 vol% oxygen, and then calcined at 950 ° C. for 10 hours to obtain a lithium-containing composite oxide (Li 1.15 Ni 0.33 Co 0. 33 Mn 0.33 Zr 0.005 W 0.005 O 2 ).
- the powdered positive electrode active material, acetylene black (conductive material), and PVDF were mixed so that the ratio of the positive electrode active material: conductive material: PVDF was 89: 8: 3, and N-methyl-2-pyrrolidone (NMP ) Was added to obtain a paste-like mixture.
- NMP N-methyl-2-pyrrolidone
- This paste-like mixture was applied to each surface of a long aluminum foil having a thickness of 15 ⁇ m so that the applied amount was 12.8 mg / cm 2 in total on both surfaces. This was dried and rolled to obtain a positive electrode sheet having a total thickness of 65 ⁇ m.
- Natural graphite, SBR, and CMC were mixed at a mass ratio of 98: 1: 1, and ion-exchanged water was added to obtain a paste-like mixture.
- This mixture was applied to each surface of a long copper foil having a thickness of 10 ⁇ m so that the applied amount was 8 mg / cm 2 in total on both surfaces. This was dried and rolled to obtain a negative electrode sheet having a total thickness of 68 ⁇ m.
- the positive electrode sheet and the negative electrode sheet were wound in the longitudinal direction together with two separators (long porous polyethylene sheet having a thickness of 20 ⁇ m) to produce an electrode body.
- This electrode body is housed in a cylindrical container together with a 1 mol / L LiPF 6 solution (EC, DMC, EMC mixed solvent (volume ratio 1: 1: 1)), and is 18650 type (diameter 18 mm, height 65 mm). A lithium ion secondary battery was obtained.
- Example 2 In the same manner as in Example 1 except that the element molar ratio Ni: Co: Mn: Zr: W was 0.33: 0.33: 0.33: 0.002: 0.005, the average particle size was 4.2 ⁇ m, A powdered positive electrode active material having a specific surface area of 1.15 m 2 / g was obtained. A lithium ion secondary battery of this example was obtained in the same manner as in Example 1 except that this positive electrode active material was used.
- Example 3 In the same manner as in Example 1 except that the element molar ratio Ni: Co: Mn: Zr: W was 0.33: 0.33: 0.33: 0.005: 0.008, the average particle size was 4.0 ⁇ m, A powdered positive electrode active material having a specific surface area of 1.08 m 2 / g was obtained. A lithium ion secondary battery of this example was obtained in the same manner as in Example 1 except that this positive electrode active material was used.
- Example 4 In the same manner as in Example 1 except that the element molar ratio Ni: Co: Mn: Zr: W was 0.33: 0.33: 0.33: 0.005: 0.01, the average particle diameter was 4.1 ⁇ m, A powdered positive electrode active material having a specific surface area of 1.13 m 2 / g was obtained. A lithium ion secondary battery of this example was obtained in the same manner as in Example 1 except that this positive electrode active material was used.
- Example 5 A reaction vessel equipped with a stirrer and a nitrogen introduction tube was charged with about half of its capacity, and heated to 40 ° C. with stirring. After replacing the reaction vessel with nitrogen, an appropriate amount of 3.25% aqueous sodium hydroxide solution and 25% aqueous ammonia was added in a nitrogen stream, and the pH at the liquid temperature of 25 ° C. was 12.0, and the ammonia concentration in the liquid phase was 20 g. / L was adjusted to obtain a basic aqueous solution. The oxygen concentration in the reaction vessel was about 2.0%.
- Ni: Co: Mn 0.33: 0.33: 0.33
- the total concentration of Ni, Co, and Mn 1.8 mol / L.
- Example 6> The elemental molar ratio Li: Ni: Co: Mn: Zr: W was set to 1.15: 0.33: 0.33: 0.33: 0.005: 0.008, and the average was obtained in the same manner as in Example 5.
- a lithium ion secondary battery of this example was obtained in the same manner as in Example 1 except that this positive electrode active material was used.
- Each battery is charged with a constant current (CC) for 3 hours at a rate of 1 / 10C (1C is a current value that can be fully charged and discharged in 1 hour), and then 4.1V at a rate of 1 / 3C.
- CC constant current
- the operation of charging up to 3 V and the operation of discharging to 3 V at a rate of 1/3 C were repeated three times.
- SEM-EDX analysis Each battery separately constructed and initially charged for SEM-EDX analysis was discharged at a rate of 1 C until the voltage between both terminals reached 3 V, and then discharged at that voltage for 3 hours. The battery after discharging was disassembled, and the positive electrode sheet was taken out and washed with diethyl carbonate (DEC). Using an SEM (-EDX apparatus (SEM: model “S-5500” manufactured by Hitachi High-Technologies Corporation; EDX: model “Genesis4000” manufactured by EDAX)), an image of the surface of the positive electrode plate was taken at a magnification of ⁇ 1000.
- FIG. 4 shows an image showing the Zr element distribution on the surface of the positive electrode active material particles of Example 3
- Fig. 5 an image showing the W element distribution
- Fig. 6 shows the W element distribution.
- each of the batteries of Examples 1 to 4 in which the positive electrode active material contains 2 mol% or less of Zr and W in total and the W elution amount is 0.025 mmol / g or less has the same positive electrode active material.
- the reaction resistance is lower at both temperatures of 25 ° C. and ⁇ 30 ° C., and the output characteristics are superior. there were.
- the capacity retention rate after the high-rate charge / discharge cycle at 60 ° C.
- the positive electrode active materials of Examples 1 to 4 showed no segregation of both Zr element and W element in the SEM-EDX analysis of the particle surface, and these elements were uniformly distributed. It was found that it was distributed.
- FIGS. 6 and 7 in the positive electrode active materials of Examples 5 and 6, segregation (aggregation) of these elements was observed on the particle surface.
- the positive electrode active materials of Examples 1 to 4 were all in the form of secondary particles in which a plurality of primary particles were collected, and the surface of the primary particles It was confirmed that W was distributed in a biased manner.
Abstract
Description
かかるリチウムイオン二次電池は、上記正極活物質がM’とM”とを併せて上記所定量含み、且つ上記M”溶出量が0.025mmol/g以下であるという特性を有することから、常温(25℃)および-30℃程度の低温のいずれにおいても、反応抵抗が低く、出力特性に優れたものであり得る。同時に、比較的高温(60℃程度)でのハイレート充放電に対する耐久性(例えば、サイクル特性)にも優れたものであり得る。
(A)pH11~14の塩基性水溶液に、ニッケル塩、コバルト塩、マンガン塩、およびM’含有塩をそれぞれ所定濃度で含む水溶液と、M”含有塩を所定濃度で含む水溶液とを、所望の速度で添加して反応混合液を調製し、当該混合液を攪拌させる湿式混合によって、一般式(II):NiaCobMncM’dM”e(OH)2+α;で表される前駆体(ii)を調製すること;および
(B)上記前駆体(ii)とリチウム塩との混合物を焼成して上記一般式(I)で表されるリチウム含有複合酸化物(i)を調製すること;
を包含する。上記式(II)中、M’はZr,Nb,Alから選択される少なくとも一種である。M”はWおよびMoの少なくともいずれかである。好ましい一態様では、M”が少なくともWを含む。M”の実質的に全部(原子数換算で95%以上、例えば98%以上であり、100%であってもよい。)がWであってもよい。a,b,c,d,eは、a+b+c+d+e=1および0.001≦(d+e)≦0.02を満たす。a,b,cのうち少なくとも一つは0よりも大である。また、dは0よりも大(すなわち、d>0)である。また、eは0よりも大(すなわち、e>0)である。αは、0≦α≦0.5を満たす。かかる方法によると、上記正極活物質を好適に製造することができる。なお、d:eは、2:1~1:10程度が好ましい。a:b:cは、特に制限されない。少なくともaが0より大である(換言すれば、少なくともNiを含む)ことが好ましい。
水溶性ポリマーとしては、例えば、カルボキシメチルセルロース(CMC)、メチルセルロース(MC)、酢酸フタル酸セルロース(CAP)、ヒドロキシプロピルメチルセルロース(HPMC)、ヒドロキシプロピルメチルセルロースフタレート(HPMCP)、ポリビニルアルコール(PVA)等が挙げられる。
水分散性ポリマーとしては、例えば、ポリテトラフルオロエチレン(PTFE)、テトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重含体(PFA)、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体(FEP)、エチレン-テトラフルオロエチレン共重合体(ETFE)等のフッ素系樹脂、酢酸ビニル共重合体、スチレンブタジエンブロック共重合体(SBR)、アクリル酸変性SBR樹脂(SBR系ラテックス)、アラビアゴム等のゴム類等が挙げられる。
非水溶媒(有機溶媒)に溶解するポリマーとしては、例えば、ポリフッ化ビニリデン(PVDF)、ポリ塩化ビニリデン(PVDC)、ポリエチレンオキサイド(PEO)、ポリプロピレンオキサイド(PPO)、ポリエチレンオキサイド-プロピレンオキサイド共重合体(PEO-PPO)等が挙げられる。
正極活物質層に含まれる結着剤の量は、適宜選択すればよく、例えば、1.5~10質量%程度とすることができる。
攪拌装置および窒素導入管を備えた反応容器に、その容量の半分程度の水を入れ、攪拌しながら40℃に加熱した。該反応容器を窒素置換した後、窒素気流下、3.25%水酸化ナトリウム水溶液と25%アンモニア水とを適量ずつ加え、液温25℃におけるpHが12.0、液相のアンモニア濃度が20g/Lとなるように調整して、塩基性水溶液を得た。なお、反応容器内の酸素濃度は2.0%程度であった。
硫酸ニッケル、硫酸コバルト、硫酸マンガン、硫酸ジルコニウムを、これらの元素モル比Ni:Co:Mn:Zrが0.33:0.33:0.33:0.005となり、これら遷移金属の合計濃度が1.8mol/Lとなるよう、水に溶解させてNiCoMnZr水溶液を調製した。
パラタングステン酸アンモニウムを水に溶解させ、タングステン(W)濃度が0.05mol/LのW水溶液を調製した。
上記水酸化物中の全遷移金属(すなわち、Ni,Co,Mn,Zr,W)のモル数の合計をMとして、該Mに対するリチウムのモル比(Li/M)が1.15となるように、炭酸リチウムを秤量し、上記加熱処理後の水酸化物粒子と混合した。得られた混合物を、酸素21体積%の空気中にて、760℃で4時間焼成した後、950℃で10時間焼成し、リチウム含有複合酸化物(Li1.15Ni0.33Co0.33Mn0.33Zr0.005W0.005O2)を得た。これを粉砕・篩分して、平均粒径3.9μm,比表面積0.98m2/g,タップ密度1.78g/cm3の粉末状正極活物質を得た。
天然黒鉛とSBRとCMCとを、質量比98:1:1で混合し、イオン交換水を加えてペースト状の混合物を得た。この混合物を、厚さ10μmの長尺状銅箔の各面に、付与量が両面合計で8mg/cm2となるように塗付した。これを乾燥後圧延して総厚68μmの負極シートを得た。
上記正極シートと上記負極シートとを、二枚のセパレータ(厚さ20μmの長尺状多孔質ポリエチレンシート)ととともに長手方向に捲回して電極体を作製した。この電極体を、1mol/LのLiPF6溶液(EC,DMC,EMCの混合溶媒(体積比1:1:1))とともに円筒型容器に収容して、18650型(直径18mm,高さ65mm)リチウムイオン二次電池を得た。
元素モル比Ni:Co:Mn:Zr:Wを0.33:0.33:0.33:0.002:0.005とした他は例1と同様にして、平均粒径4.2μm,比表面積1.15m2/gの粉末状正極活物質を得た。この正極活物質を用いた他は例1と同様にして、本例のリチウムイオン二次電池を得た。
元素モル比Ni:Co:Mn:Zr:Wを0.33:0.33:0.33:0.005:0.008とした他は例1と同様にして、平均粒径4.0μm,比表面積1.08m2/gの粉末状正極活物質を得た。この正極活物質を用いた他は例1と同様にして、本例のリチウムイオン二次電池を得た。
元素モル比Ni:Co:Mn:Zr:Wを0.33:0.33:0.33:0.005:0.01とした他は例1と同様にして、平均粒径4.1μm,比表面積1.13m2/gの粉末状正極活物質を得た。この正極活物質を用いた他は例1と同様にして、本例のリチウムイオン二次電池を得た。
攪拌装置および窒素導入管を備えた反応容器に、その容量の半分程度の水を入れ、攪拌しながら40℃に加熱した。該反応容器を窒素置換した後、窒素気流下、3.25%水酸化ナトリウム水溶液と25%アンモニア水とを適量ずつ加え、液温25℃におけるpHが12.0、液相のアンモニア濃度が20g/Lとなるように調整して、塩基性水溶液を得た。なお、反応容器内の酸素濃度は2.0%程度であった。
硫酸ニッケル、硫酸コバルト、硫酸マンガンを、これらの元素モル比Ni:Co:Mnが0.33:0.33:0.33となり、Ni,Co,Mnの合計濃度が1.8mol/Lとなるよう、上記反応容器中の水に加え、攪拌して溶解させた。析出した生成物を分離・水洗・乾燥して、NiCoMnの複合水酸化物(Ni0.33Co0.33Mn0.33(OH)2)を得た。
元素モル比Li:Ni:Co:Mn:Zr:Wを1.15:0.33:0.33:0.33:0.005:0.008とした他は例5と同様にして、平均粒径4.0μm,比表面積0.99m2/gの粉末状正極活物質を得た。この正極活物質を用いた他は例1と同様にして、本例のリチウムイオン二次電池を得た。
各例の粉末状正極活物質につき、上述した方法に従って、W溶出量(mmol/g)を測定した。ICP-MS装置としては、島津製作所社製の型式「ICPM8500」を使用した。それらの結果を、表1に示す。
各電池に対して、1/10C(1Cは、1時間で満充放電可能な電流値)のレートで3時間の定電流(CC)充電を行い、次いで、1/3Cのレートで4.1Vまで充電する操作と、1/3Cのレートで3Vまで放電させる操作とを3回繰り返した。
両端子間電圧4.1Vに初期充電させた各電池を、温度25℃にて、1Cのレートで両端子間電圧が3VとなるまでCC放電させ、次いで同電圧で2時間定電圧(CV)放電させた。10分休止後、1Cのレートで両端子間電圧が4.1VとなるまでCC充電し、次いで同電圧で2.5時間CV充電した。10分休止後、0.5Cのレートで両端子間の電圧が3VとなるまでCC放電させ、次いで同電圧で2時間CV放電させ、このCCCV放電時に測定された総放電容量を初期容量とした。
SOC60%に調整した各電池に対し、温度25℃、周波数0.001Hz~10000Hz、印加電圧10mVの条件にて、交流インピーダンス測定を行い、Nyquistプロットの等価回路フィッティングにより25℃反応抵抗(mΩ)を求めた。
SOC40%に調整した各電池に対し、測定温度を-30℃とした他は上記と同様の条件にて、-30℃反応抵抗(mΩ)を求めた。
SOC100%に調整した各電池を、温度60℃にて、1000サイクルの充放電に供した。1サイクルは、4Cのレートで電圧が3VとなるまでCC放電させる操作と、次いで4Cのレートで電圧が4.1VとなるまでCC充電する操作とした。1000サイクル完了時点において、4Cのレートで電圧が3VとなるまでCC放電させ、このときの放電容量を測定した。初期容量に対するサイクル終了後の放電容量の百分率を、容量維持率として求めた。
SEM-EDX分析用に別途構築し初期充電させた各電池を、両端子間電圧が3Vとなるまで1Cのレートで放電させ、次いで当該電圧にて3時間放電させた。放電後の該電池を解体し、正極シートを取り出して、炭酸ジエチル(DEC)により洗浄した。SEM(-EDX装置(SEM:日立ハイテクノロジーズ社製の型式「S-5500」;EDX:EDAX社製の型式「Genesis4000」)を用いて、×1000の倍率にてこの正極板表面の画像を撮影した。それら画像のうち、例3の正極活物質粒子表面のZr元素分布を示す画像を図4に、W元素分布を示す画像を図5に示す。同様に、例7に係るZr元素分布を図6に、W元素分布を図7に示す。
なお、図4,5に代表されるように、例1~4の正極活物質は、その粒子表面のSEM-EDX分析において、Zr元素およびW元素ともに偏析が認められず、これら元素が均一に分布していることがわかった。一方、図6,7に代表されるように、例5,6の正極活物質は、その粒子表面において、これら元素の偏析(凝集)が認められた。また、TEM-EDX分析を行ってWの分布をマッピングしたところ、例1~4の正極活物質は、いずれも、複数の一次粒子が集まった二次粒子の形態であり、該一次粒子の表面に偏ってWが分布していることが確認された。
20 捲回電極体
30 正極シート
32 正極集電体
34 正極活物質層
38 正極端子
40 負極シート
42 負極集電体
44 負極活物質層
48 負極端子
50 セパレータ
100 リチウムイオン二次電池
Claims (8)
- 正極と負極と非水電解液とを備えたリチウムイオン二次電池であって、
前記正極は、正極活物質として、層状構造を有するリチウム遷移金属複合酸化物を有し、
前記正極活物質は、Ni,CoおよびMnのうち少なくとも一種の金属元素M0を含み、さらにZr,Nb,Alのうち少なくとも一種の金属元素M’を含み、さらにWを含み、
前記正極活物質の粉末2gと純水100gとを攪拌して懸濁液を調製し、その懸濁液を濾過した場合において、前記濾過により得られた濾液について誘導結合プラズマ質量分析により求められる当該濾液1g当たりのW溶出量が0.025mmol以下である、リチウムイオン二次電池。 - 正極と負極と非水電解液とを備えるリチウムイオン二次電池であって、
前記正極は、正極活物質として、一般式(I):
LixNiaCobMncM’dWeO2 (I)
(ここで、M’はZr,Nb,Alから選択される少なくとも一種であり、xは、1.0≦x≦1.25を満たし、a,b,c,d,eは、a+b+c+d+e=1および0.001≦(d+e)≦0.02を満たし、a,b,cのうち少なくとも一つは0よりも大きく、d>0であり、e>0である。);
で表されるリチウム遷移金属複合酸化物を含み、
前記正極活物質の粉末2gと純水100gとを攪拌して懸濁液を調製し、その懸濁液を濾過した場合において、前記濾過により得られた濾液について誘導結合プラズマ質量分析により求められる当該濾液1g当たりのW溶出量が0.025mmol以下である、
リチウムイオン二次電池。 - 前記M’がZrである、請求項1または2に記載のリチウムイオン二次電池。
- 前記d:eが2:1~1:10である、請求項2または3に記載のリチウムイオン二次電池。
- 前記正極活物質は、層状構造を有するリチウム遷移金属複合酸化物の一次粒子が集まった二次粒子の形態をなし、
該正極活物質に含まれるWは、前記一次粒子の表面に偏って存在している、請求項1から4のいずれか一項に記載のリチウムイオン二次電池。 - 請求項1から5のいずれか一項に記載のリチウムイオン二次電池用の正極活物質を製造する方法であって:
前記M0と前記M’とを含む水溶液AqAを準備すること;
Wを含む水溶液AqCを準備すること;
前記水溶液AqAと前記水溶液AqCとをアルカリ性条件下で混合して、前記M0,前記M’およびWを含む水酸化物を析出させること;
前記水酸化物とリチウム化合物とを混合すること;および、
前記混合物を焼成して前記リチウム遷移金属複合酸化物を生成させること;
を包含する、正極活物質製造方法。 - 請求項2から5のいずれか一項に記載のリチウムイオン二次電池用の正極活物質を製造する方法であって:
(A)pH11~14の塩基性水溶液に、ニッケル塩、コバルト塩、マンガン塩、およびM’含有塩をそれぞれ所定濃度で含む水溶液と、W含有塩を所定濃度で含む水溶液とを、所望の速度で添加して反応混合液を調製し、当該混合液を攪拌させる湿式混合によって、一般式(II):
NiaCobMncM’dWe(OH)2+α (II)
(ここで、M’はZr,Nb,Alから選択される少なくとも一種であり、a,b,c,d,eは、a+b+c+d+e=1および0.001≦(d+e)≦0.02を満たし、a,b,cのうち少なくとも一つは0よりも大きく、d>0であり、e>0であり、αは0≦α≦0.5を満たす。);で表される前駆体(ii)を調製すること;および
(B)前記前駆体(ii)とリチウム塩との混合物を焼成して前記一般式(I)で表されるリチウム遷移金属複合酸化物(i)を調製すること;
を包含する、正極活物質製造方法。 - 請求項1から5のいずれか一項に記載のリチウムイオン二次電池を備えるか、または、請求項6または7に記載の方法によって製造された正極活物質を含むリチウムイオン二次電池を備える、車両。
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