WO2015025844A1 - リチウム鉄マンガン系複合酸化物およびそれを用いたリチウムイオン二次電池 - Google Patents
リチウム鉄マンガン系複合酸化物およびそれを用いたリチウムイオン二次電池 Download PDFInfo
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- WO2015025844A1 WO2015025844A1 PCT/JP2014/071657 JP2014071657W WO2015025844A1 WO 2015025844 A1 WO2015025844 A1 WO 2015025844A1 JP 2014071657 W JP2014071657 W JP 2014071657W WO 2015025844 A1 WO2015025844 A1 WO 2015025844A1
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/36—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
- H01M4/50—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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- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- 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
- This embodiment relates to a lithium iron manganese based composite oxide and a lithium ion secondary battery using the same.
- a lithium ion secondary battery comprising a positive electrode including a lithium iron manganese-based composite oxide as a positive electrode active material and a negative electrode including a material capable of occluding and releasing lithium ions as a negative electrode active material is expected as a high energy density secondary battery.
- Patent Document 1 discloses a lithium ion secondary battery using a lithium iron manganese composite oxide as a positive electrode active material.
- Patent Documents 2 to 6 disclose techniques related to surface coating.
- the lithium ion secondary battery disclosed in the patent document has a problem in that the capacity of the secondary battery decreases with a charge / discharge cycle.
- An object of the present embodiment is to provide a lithium iron manganese based composite oxide that can provide a lithium ion secondary battery that has a high capacity retention rate in a charge / discharge cycle and that suppresses gas generation due to the charge / discharge cycle. To do.
- the lithium iron manganese-based composite oxide according to the present embodiment has a layered rock salt structure, and has the following formula (1): Li x M 1 (yp) Mn p M 2 (zq) Fe q O (2- ⁇ ) (1) (In the above formula (1), 1.05 ⁇ x ⁇ 1.32, 0.33 ⁇ y ⁇ 0.63, 0.06 ⁇ z ⁇ 0.50, 0 ⁇ p ⁇ 0.63, 0.06 ⁇ q ⁇ 0.50, 0 ⁇ ⁇ ⁇ 0.80, y ⁇ p, z ⁇ q, M 1 is at least one element of Ti and Zr, and M 2 is selected from the group consisting of Co, Ni, and Mn. At least a part of the surface of the lithium iron-manganese composite oxide represented by (which is at least one element selected) is coated with an inorganic substance.
- the positive electrode active material for a lithium ion secondary battery according to this embodiment includes the lithium iron manganese based composite oxide.
- the positive electrode for a lithium ion secondary battery according to this embodiment includes the positive electrode active material for a lithium ion secondary battery.
- the lithium ion secondary battery according to the present embodiment includes the positive electrode for a lithium ion secondary battery and a negative electrode.
- a lithium iron manganese-based composite oxide that can provide a lithium ion secondary battery that has a high capacity retention rate in a charge / discharge cycle and that suppresses gas generation due to the charge / discharge cycle. it can.
- FIG. 1 Mapping of SEM image and EDX
- FIG. 1 Mapping of SEM image and EDX
- the lithium iron manganese-based composite oxide according to the present embodiment has a layered rock salt structure, and has the following formula (1): Li x M 1 (yp) Mn p M 2 (zq) Fe q O (2- ⁇ ) (1) (In the above formula (1), 1.05 ⁇ x ⁇ 1.32, 0.33 ⁇ y ⁇ 0.63, 0.06 ⁇ z ⁇ 0.50, 0 ⁇ p ⁇ 0.63, 0.06 ⁇ q ⁇ 0.50, 0 ⁇ ⁇ ⁇ 0.80, y ⁇ p, z ⁇ q, M 1 is at least one element of Ti and Zr, and M 2 is selected from the group consisting of Co, Ni, and Mn. At least a part of the surface of the lithium iron-manganese composite oxide represented by (which is at least one element selected) is coated with an inorganic substance.
- the structure of the positive electrode active material changes from a layered rock salt structure to a spinel structure, and thus the capacity of the secondary battery decreases. Further, since Li 2 O is generated on the negative electrode by the desorbed oxygen, the capacity of the secondary battery is reduced. Furthermore, since the secondary battery swells due to the desorption of oxygen and the resistance increases, the capacity of the secondary battery decreases.
- the lithium iron manganese complex oxide (hereinafter also referred to as complex oxide) according to this embodiment is a complex oxide having a specific composition represented by the formula (1), and at least a part of the surface is an inorganic substance. It is covered with. Since at least a part of the surface of the lithium iron manganese composite oxide is coated with an inorganic substance, it is possible to physically suppress the desorption of oxygen from the lithium iron manganese composite oxide inside the charge / discharge cycle. . Moreover, it becomes possible to suppress generation
- the composite oxide according to the present embodiment when used, the capacity of the secondary battery is maintained even in the charge / discharge cycle, and not only a high capacity retention rate is obtained, but also the generation of gas during the charge / discharge cycle. It is suppressed. Details of this embodiment will be described below.
- the composite oxide represented by the formula (1) contains at least Mn.
- the composition p of Mn is 0 ⁇ p ⁇ 0.63. When 0 ⁇ p, lithium can be included excessively. Further, by satisfying p ⁇ 0.63, Li 2 Me 1 O 3 (Me 1 contains at least Mn) and LiMe 2 O 2 (Me 2 contains at least Fe) take a solid solution state. Can do.
- p is preferably 0.10 ⁇ p ⁇ 0.60, more preferably 0.20 ⁇ p ⁇ 0.55, and still more preferably 0.30 ⁇ p ⁇ 0.50.
- M 1 is at least one element of Ti and Zr.
- the y of the composition yp of M 1 is 0.33 ⁇ y ⁇ 0.63. When 0.33 ⁇ y, excess lithium can be contained. Further, by satisfying y ⁇ 0.63, Li 2 Me 1 O 3 (Me 1 contains at least Mn) and LiMe 2 O 2 (Me 2 contains at least Fe) take a solid solution state. Can do.
- y is preferably 0.35 ⁇ y ⁇ 0.60, more preferably 0.40 ⁇ y ⁇ 0.55, and still more preferably 0.45 ⁇ y ⁇ 0.50.
- the formula (1) satisfies y ⁇ p. Further, the composition yp of M 1 may be zero. That is, the complex oxide represented by the formula (1) may not contain M 1 . Mn and M 1 in the formula (1) correspond to Me 1 of the Li 2 Me 1 O 3 .
- the composite oxide represented by the formula (1) contains at least Fe.
- the composition q of Fe is 0.06 ⁇ q ⁇ 0.50.
- a lithium iron manganese system complex oxide can be activated.
- q is preferably 0.10 ⁇ q ⁇ 0.45, more preferably 0.13 ⁇ q ⁇ 0.40, and still more preferably 0.16 ⁇ q ⁇ 0.30.
- M 2 is at least one element selected from the group consisting of Co, Ni and Mn.
- z is preferably 0.08 ⁇ z ⁇ 0.45, more preferably 0.10 ⁇ z ⁇ 0.40, and further preferably 0.12 ⁇ z ⁇ 0.30.
- the formula (1) satisfies z ⁇ q. Further, the composition zq of M 2 may be zero. That is, the complex oxide represented by the formula (1) may not contain M 2 . Fe and M 2 in the formula (1) correspond to Me 2 of the LiMe 2 O 2 .
- the composition x of Li is 1.05 ⁇ x ⁇ 1.32.
- the capacity can be increased.
- Li 2 Me 1 O 3 (Me 1 contains at least Mn) and LiMe 2 O 2 (Me 2 contains at least Fe) are in a solid solution state.
- x is preferably 1.08 ⁇ x ⁇ 1.30, more preferably 1.12 ⁇ x ⁇ 1.28, and still more preferably 1.16 ⁇ x ⁇ 1.26.
- ⁇ in the composition 2- ⁇ of oxygen atoms is a parameter indicating oxygen deficiency, and 0 ⁇ ⁇ ⁇ 0.80.
- the capacity can be increased.
- ⁇ ⁇ 0.80 the crystal structure can be stabilized.
- ⁇ is preferably 0.02 ⁇ ⁇ ⁇ 0.50, more preferably 0.04 ⁇ ⁇ ⁇ 0.30, and further preferably 0.06 ⁇ ⁇ ⁇ 0.20. Note that ⁇ varies depending not only on the mixing ratio of Me 1 and Me 2 but also on the method of synthesizing the composite oxide.
- composition of each element in the formula (1) is a value measured by inductively coupled plasma emission spectrometry for Li and by inductively coupled plasma mass spectrometry for other elements. Moreover, the composition of each element in the formula (1) does not include an inorganic substance used for surface coating.
- the composite oxide represented by the formula (1) has a layered rock salt structure. Since the composite oxide has a layered rock salt structure, charge and discharge can be stably repeated. Whether or not it has a layered rock salt structure can be determined by X-ray diffraction analysis. Further, it is not necessary that the entire complex oxide has a layered rock salt type structure, and it is sufficient that at least a part of the complex oxide has a layered rock salt type structure.
- the lithium iron manganese composite oxide according to this embodiment has at least a part of the surface covered with an inorganic substance. That is, the lithium iron manganese complex oxide according to the present embodiment has an inorganic substance other than the lithium iron manganese complex oxide on the surface. Since at least a part of the surface of the lithium iron manganese composite oxide is physically covered with an inorganic substance, oxygen can be retained inside the lithium iron manganese composite oxide even in a charge / discharge cycle, Desorption can be suppressed. Moreover, it becomes possible to suppress generation
- Whether or not at least a part of the surface of the lithium iron manganese composite oxide is coated with an inorganic substance is determined by scanning electron microscope observation (energy dispersive X-ray analysis), transmission electron microscope observation, X-ray photoelectron spectroscopy. It can be judged by analysis.
- the inorganic substance examples include germanium oxide, tin oxide, silicon oxide, molybdenum oxide, cerium oxide, gadolinium oxide, erbium oxide, aluminum oxide, aluminum fluoride, titanium oxide, and zirconium oxide.
- the inorganic material is preferably aluminum oxide, aluminum fluoride, or titanium oxide.
- germanium oxide, cerium oxide, gadolinium oxide, and erbium oxide are effective for suppressing the generation of gas, and the effect can be further improved by mixing a plurality of these.
- These inorganic materials may be used alone or in combination of two or more.
- the content of the inorganic substance relative to the lithium iron manganese-based composite oxide containing the inorganic substance is preferably 0.1% by mass or more and 15% by mass or less.
- the content is more preferably 0.2% by mass or more and 10% by mass or less, further preferably 0.3% by mass or more and 2% by mass or less, and 0.5% by mass or more and 1% by mass. It is particularly preferred that
- the shape of the inorganic substance is not particularly limited as long as the inorganic substance covers at least a part of the surface of the lithium iron manganese composite oxide, and may be layered or particulate.
- the method for producing a lithium iron manganese composite oxide according to this embodiment has a layered rock salt structure, and at least a part of the surface of the lithium iron manganese composite oxide satisfying the formula (1) is coated with an inorganic substance. If it is, it will not be specifically limited.
- a lithium iron manganese composite oxide having a layered rock salt structure and satisfying the above formula (1) and a hydrolyzable compound that is an inorganic raw material are mixed and reacted in a solution, followed by heat treatment. By doing so, at least a part of the surface of the lithium iron manganese composite oxide can be coated with an inorganic substance.
- the method shown below is mentioned.
- the method for producing lithium iron manganese-based composite oxide before coating with an inorganic substance is not particularly limited, and it is produced by performing heat treatment such as firing or hydrothermal treatment on a metal raw material containing at least lithium, manganese, iron, etc. Can do.
- heat treatment such as firing or hydrothermal treatment
- a lithium iron manganese-based composite oxide having more excellent electrochemical characteristics it is preferable to mix constituent metal elements other than lithium more uniformly.
- a method of obtaining a composite hydroxide such as iron or manganese from the liquid phase and firing it with a lithium compound is preferable.
- This method can be broadly divided into a composite hydroxide production process for producing a composite hydroxide containing a constituent metal other than lithium and a firing process for firing the composite hydroxide in the presence of lithium.
- the composite hydroxide can be prepared by dropping a water-soluble salt of a constituent metal into an alkaline aqueous solution, performing air oxidation as necessary, and aging the hydroxide.
- the water-soluble salt of the constituent metal is not particularly limited, and examples thereof include anhydrous salts and hydrates such as nitrate, sulfate, chloride, and acetate of the constituent metal.
- the alkali source is not particularly limited, and examples thereof include lithium hydroxide and hydrates thereof, sodium hydroxide, potassium hydroxide, and aqueous ammonia. These may use 1 type and may use 2 or more types together.
- the composite hydroxide can be obtained by gradually dropping a water-soluble salt of a constituent metal into an alkaline aqueous solution over several hours.
- the temperature at which the water-soluble salt of the constituent metal is dropped is preferably 60 ° C. or less from the viewpoint of suppressing the generation of impurities such as spinel ferrite.
- the water-soluble salt of the constituent metal is dropped at 0 ° C. or lower, it is preferable to prevent the solution from solidifying by adding ethanol or the like as an antifreeze to the alkaline aqueous solution. It is preferable to ripen the hydroxide by wet-oxidizing the hydroxide obtained after the dropwise addition by blowing air at room temperature for several hours or more. The resulting mature product is washed with water and filtered to obtain the desired composite hydroxide.
- a predetermined lithium compound is added to the composite hydroxide according to the composition formula and mixed, and then fired in a predetermined atmosphere. Then, in order to remove an excess lithium compound as needed, a lithium iron manganese system complex oxide which has the target composition formula is obtained by performing washing processing, filtration, and drying.
- the lithium compound is not particularly limited, and an anhydride or hydrate such as lithium carbonate, lithium hydroxide, lithium nitrate, or lithium acetate can be used. These may use 1 type and may use 2 or more types together.
- the firing temperature is preferably 1000 ° C. or less from the viewpoint of preventing Li volatilization.
- an air atmosphere an inert gas atmosphere, a nitrogen atmosphere, an oxygen atmosphere, or the like can be used.
- a lithium iron manganese based composite oxide before coating with an inorganic substance having a target composition can be produced.
- germanium, tin, silicon, molybdenum, cerium, gadolinium, erbium, aluminum, titanium, zirconium, and other chlorides, hydroxides, carbonates, nitrates, acetates, alcoholates and the like are preferable. . These may use 1 type and may use 2 or more types together.
- the concentration of each of these aqueous solutions or these alcohol solutions is not particularly limited, but is preferably 0.002 to 0.05% by mass. When the concentration is 0.002% by mass or more, the time required for evaporation of water or alcohol is shortened, so that the production efficiency is improved. Further, when the concentration is 0.05% by mass or less, the raw material is sufficiently dissolved, and a homogeneous mixed solution is obtained.
- a dried product obtained by evaporating water or alcohol and then drying can be fired at 400 to 800 ° C. in an oxygen-containing gas.
- the firing temperature is 400 ° C. or higher, the reaction is completed and no propoxide or the like remains.
- the firing temperature is 800 ° C. or lower, the reaction with lithium in the lithium iron-manganese composite oxide can be suppressed, and mixing of lithium compounds as impurities can be prevented.
- the drying method is not particularly limited, and examples thereof include a drying method using a rotary evaporator, a spray dryer and the like in addition to a normal drying method.
- the oxygen-containing gas is preferably air.
- the positive electrode active material for a lithium ion secondary battery according to the present embodiment includes the lithium iron manganese based composite oxide according to the present embodiment.
- the positive electrode active material includes the lithium iron manganese composite oxide according to the present embodiment, desorption of oxygen is suppressed even in the charge / discharge cycle, and the capacity of the secondary battery is maintained.
- the proportion of the lithium iron manganese based composite oxide according to this embodiment contained in the positive electrode active material for a lithium ion secondary battery according to this embodiment is preferably 80% by mass or more, and 90% by mass or more. Is more preferably 95% by mass or more. In addition, this ratio is 100 mass%, ie, the positive electrode active material for lithium ion secondary batteries which concerns on this embodiment may consist of the lithium iron manganese system complex oxide which concerns on this embodiment.
- the positive electrode for lithium ion secondary batteries according to the present embodiment includes the positive electrode active material for lithium ion secondary batteries according to the present embodiment.
- the positive electrode can be produced by applying the positive electrode active material according to the present embodiment on a positive electrode current collector.
- a positive electrode current collector For example, it can be produced by mixing the positive electrode active material according to this embodiment, a conductivity imparting agent, a binder, and a solvent, applying the mixture onto the positive electrode current collector, and drying.
- a conductivity imparting agent a carbon material such as ketjen black, a metal material such as Al, a conductive oxide, or the like can be used.
- the binder polyvinylidene fluoride, acrylic resin, polytetrafluoroethylene resin, or the like can be used.
- the solvent N-methylpyrrolidone or the like can be used.
- the positive electrode current collector a metal thin film mainly containing aluminum or the like can be used. The thickness of the positive electrode current collector is not particularly limited, but can be, for example, 5 to 50 ⁇ m.
- the addition amount of the conductivity imparting agent may be 1 to 10% by mass, and preferably 2 to 7% by mass. When the addition amount is 1% by mass or more, sufficient conductivity can be maintained. Moreover, since the ratio of positive electrode active material mass can be enlarged because this addition amount is 10 mass% or less, the capacity
- the addition amount of the binder may be 1 to 10% by mass, and preferably 2 to 7% by mass. When the addition amount is 1% by mass or more, generation of positive electrode peeling can be prevented. Moreover, since the ratio of positive electrode active material mass can be enlarged because this addition amount is 10 mass% or less, the capacity
- the thickness of the positive electrode is not particularly limited, but can be, for example, 50 to 500 ⁇ m, and preferably 100 to 400 ⁇ m.
- the lithium ion secondary battery according to the present embodiment includes the positive electrode for a lithium ion secondary battery according to the present embodiment and a negative electrode.
- FIG. 1 shows an example of the secondary battery according to this embodiment.
- a positive electrode is configured by forming a positive electrode active material layer 1 containing a positive electrode active material according to the present embodiment on a positive electrode current collector 1A.
- the negative electrode is comprised by forming the negative electrode active material layer 2 on the negative electrode collector 2A.
- These positive electrode and negative electrode are disposed so as to face each other through the separator 3 while being immersed in an electrolytic solution.
- the positive electrode is connected to the positive electrode tab 1B, and the negative electrode is connected to the negative electrode tab 2B.
- This power generation element is accommodated in the exterior body 4, and the positive electrode tab 1B and the negative electrode tab 2B are exposed to the outside.
- a solution in which a lithium salt as a supporting salt is dissolved in a solvent can be used.
- the solvent include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate ( DEC), chain carbonates such as dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate and ethyl propionate, ⁇ -lactones such as ⁇ -butyrolactone, 1,2-diethoxy Chain ethers such as ethane (DEE) and ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-diox
- lithium salt examples include LiPF 6 , LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiB 10 Cl 10 , lower aliphatic lithium lithium carboxylate, lithium chloroborane, lithium tetraphenylborate, LiBr, LiI, LiSCN, LiCl, imides, etc. . These may use 1 type and may use 2 or more types together.
- the concentration of the lithium salt as the supporting salt can be, for example, 0.5 to 1.5 mol / L, and preferably 0.7 to 1.3 mol / L. Sufficient electric conductivity can be obtained when the concentration of the lithium salt is 0.5 mol / L or more. Moreover, when the density
- a polymer electrolyte obtained by adding a polymer or the like to the solvent of the electrolytic solution and solidifying the electrolytic solution into a gel may be used.
- the negative electrode active material a material capable of inserting and extracting lithium can be used.
- the negative electrode active material include carbon materials such as graphite, hard carbon, soft carbon, and amorphous carbon, Li metal, Si oxide such as Si, Sn, Al, and SiO, Sn oxide, and Li 4 Ti 5 O. 12 , Ti oxide such as TiO 2 , V-containing oxide, Sb-containing oxide, Fe-containing oxide, Co-containing oxide and the like can be used. These negative electrode active materials may be used alone or in combination of two or more.
- SiO as the negative electrode active material from the viewpoint that the irreversible capacity is offset by the relationship with the positive electrode active material according to the present embodiment.
- the negative electrode can be produced, for example, by mixing the negative electrode active material, a conductivity imparting agent, a binder, and a solvent, applying the mixture onto the negative electrode current collector, and drying.
- a conductivity imparting agent for example, a carbon material, a conductive oxide, or the like can be used.
- the binder polyvinylidene fluoride, acrylic resin, styrene butadiene rubber, imide resin, imidoamide resin, polytetrafluoroethylene resin, polyamic acid, or the like can be used.
- the solvent N-methylpyrrolidone or the like can be used.
- As the negative electrode current collector a metal thin film mainly containing aluminum, copper, or the like can be used.
- the thickness of the negative electrode current collector is not particularly limited, but can be, for example, 5 to 50 ⁇ m, and preferably 10 to 40 ⁇ m.
- the thickness of the negative electrode is not particularly limited, but can be, for example, 10 to 100 ⁇ m, and preferably 20 to 70 ⁇ m.
- the secondary battery according to the present embodiment can be manufactured by assembling using the positive electrode according to the present embodiment.
- the positive electrode and the negative electrode according to the present embodiment are arranged to face each other with no electrical contact through the separator.
- a porous film containing polyethylene, polypropylene (PP), polyimide, polyamide, or the like can be used.
- the one in which the positive electrode and the negative electrode are arranged opposite to each other with a separator interposed between them is cylindrical or laminated and accommodated in the exterior body.
- a battery can, a laminate film that is a laminate of a synthetic resin and a metal foil, or the like can be used.
- a positive electrode tab is connected to the positive electrode, and a negative electrode tab is connected to the negative electrode, so that these electrode tabs are exposed to the outside of the outer package.
- the secondary battery can be manufactured by sealing the exterior body while leaving a part, injecting an electrolyte from the part, and sealing the exterior body. Moreover, you may perform an activation process before use of this secondary battery.
- the shape of the positive electrode and the negative electrode arranged opposite to each other with a separator interposed therebetween is not particularly limited, and may be a wound type, a laminated type, or the like. Further, the secondary battery may be a coin type, a laminate type, or the like. The shape of the secondary battery can be a square shape, a cylindrical shape, or the like.
- Example 1 ⁇ Synthesis of lithium iron manganese complex oxide> Iron nitrate (III), manganese chloride (II), and nickel nitrate (II) weighed so as to have a predetermined atomic ratio were dissolved in distilled water to prepare an aqueous metal salt solution (total amount 0.25 mol / batch). Separately, a 1.25 mol / L aqueous solution of lithium hydroxide was prepared, ethanol was added to make it antifreeze, and then cooled to ⁇ 10 ° C. in a thermostatic bath. A composite hydroxide was prepared by gradually dropping the metal salt aqueous solution into the alkaline solution over 2 hours or more. The alkali solution containing the composite hydroxide after the dropping was taken out from the thermostatic bath, air was blown into the solution to perform wet oxidation for 2 days, and then the composite hydroxide was aged at room temperature.
- the composite hydroxide after aging was washed with water and filtered, and then added with an equimolar amount of lithium carbonate as compared with the molar amount charged, and calcined at 850 ° C. for 5 hours in the air. After firing, the product was pulverized, washed several times with distilled water, filtered, and dried at 100 ° C. to obtain lithium iron manganese composite oxide Li 1.20 Mn 0.47 Ni 0.16 Fe 0.16 O 1.89 .
- a slurry containing 85% by mass of SiO having an average particle size of 15 ⁇ m and 15% by mass of polyamic acid was mixed with a solvent to prepare a slurry.
- the slurry was applied onto a negative electrode current collector which was a copper foil having a thickness of 10 ⁇ m, and the slurry was dried to prepare a negative electrode having a thickness of 46 ⁇ m.
- the produced negative electrode was annealed at 350 ° C. for 3 hours in a nitrogen atmosphere to cure the polyamic acid.
- the lithium ion secondary battery is charged to 4.5 V at a constant current of 40 mA / g per positive electrode active material in a constant temperature bath at 45 ° C., and further at a constant voltage of 4.8 V until a current of 5 mA / g is reached. Charged. Thereafter, the lithium ion secondary battery was discharged to 1.5 V at a current of 10 mA / g. The lithium ion secondary battery is charged to 4.5 V at a constant current of 40 mA / g per positive electrode active material in a constant temperature bath at 45 ° C., and at a constant voltage of 4.5 V until a current of 5 mA / g is reached.
- Example 1 After charging, a charge / discharge cycle of discharging to 1.5 V with a current of 40 mA / g was repeated 100 times. From the ratio of the discharge capacity obtained in the first cycle and the discharge capacity obtained in the 100th cycle, the capacity retention rate after 100 cycles was determined. In Example 1, the capacity retention rate after 100 cycles was 80%.
- Comparative Example 1 A lithium ion secondary battery was prepared and evaluated in the same manner as in Example 1 except that the surface was not coated with lithium iron manganese-based composite oxide Li 1.19 Mn 0.47 Ni 0.16 Fe 0.17 O 1.99. did. The capacity retention rate after 100 cycles in this Comparative Example 1 was 56%.
- Example 2 ⁇ Synthesis of lithium iron manganese complex oxide> 0.2 g of germanium oxide and 0.048 g of lithium hydroxide were dissolved in 10 ml of water. The obtained solution was spray-coated on 20 g of the lithium iron manganese composite oxide before coating with aluminum oxide synthesized in Example 1. The resulting slurry mixture was dried overnight in a 110 ° C. air constant temperature bath. The powder was heat-treated at 400 ° C. for 10 hours in an air atmosphere to obtain a composite oxide in which part of the surface of the lithium iron manganese composite oxide was covered with germanium oxide. The content of germanium oxide was 1% by mass.
- FIG. 3A shows the result of SEM image (scanning electron microscope image) and EDX (energy dispersive X-ray spectroscopy) analysis.
- the left side is a mapping of germanium on the SEM image
- the center is a mapping of nickel and germanium
- the right side is a mapping of manganese and germanium.
- FIG. 3B shows a spot analysis performed on the SEM image by EDX. From these results, it was found that a part of the surface of the lithium iron manganese composite oxide was covered with germanium oxide.
- ⁇ Production of negative electrode> A mixture containing 92% by mass of graphite having an average particle size of 15 ⁇ m, 4% by mass of PVDF (polyvinylidene fluoride) and 4% by mass of ketjen black was mixed with a solvent to prepare a slurry. The slurry was applied onto a negative electrode current collector which was a copper foil having a thickness of 10 ⁇ m, and the slurry was dried to prepare a negative electrode having a thickness of 100 ⁇ m.
- PVDF polyvinylidene fluoride
- ⁇ Activation processing> The lithium ion secondary battery before the activation treatment is repeatedly charged and discharged by increasing the upper limit voltage by 0.1 V in a charge / discharge range of 4.0 V to 1.5 V at a current of 20 mA / g per positive electrode active material.
- stepwise activation treatment was performed in which the potential was raised stepwise (4.0 to 4.5 V).
- the lithium ion secondary battery is charged to 4.5 V at a constant current of 40 mA / g per positive electrode active material in a 45 ° C. constant temperature bath, and further at a constant voltage of 4.5 V until a current of 10 mA / g is reached. Charged. Thereafter, the lithium ion secondary battery was discharged to 1.5 V at a current of 40 mA / g. This charge / discharge cycle was repeated nine times. Then, it charged to 4.5V with the constant current of 10 mA / g per positive electrode active material, and also charged with the constant voltage of 4.5V until it became the electric current of 2.5 mA / g.
- the lithium ion secondary battery was discharged to 1.5 V at a current of 10 mA / g.
- the above 9 cycles and 1 cycle were set to 10 cycles, and 30 cycles were performed by performing the 10 cycles three times. From the ratio of the discharge capacity obtained in the first cycle and the discharge capacity obtained in the 30th cycle, the capacity retention rate after 30 cycles was determined. Moreover, the volume of the secondary battery before charging / discharging and the secondary battery after 30 cycles was evaluated by the Archimedes method, and the difference between them was defined as a gas generation amount. The results are shown in Table 1.
- Example 3 A composite oxide in which part of the surface of the lithium iron manganese composite oxide was covered with germanium oxide was synthesized in the same manner as in Example 2 except that the content of germanium oxide was changed to 2% by mass. From the same X-ray diffraction measurement and EDX analysis as in Example 2, it was confirmed that the composite oxide was a composite oxide having a layered rock salt structure in which a part of the surface was covered with germanium oxide. A lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 4 A composite oxide in which a part of the surface of the lithium iron manganese composite oxide was coated with germanium was synthesized in the same manner as in Example 2 except that the content of germanium oxide was changed to 3% by mass. From the same X-ray diffraction measurement and EDX analysis as in Example 2, it was confirmed that the composite oxide was a composite oxide having a layered rock salt structure in which a part of the surface was covered with germanium oxide. A lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 5 A composite oxide in which part of the surface of the lithium iron manganese composite oxide was covered with germanium oxide was synthesized in the same manner as in Example 2 except that the content of germanium oxide was changed to 9% by mass. From the same X-ray diffraction measurement and EDX analysis as in Example 2, it was confirmed that the composite oxide was a composite oxide having a layered rock salt structure in which a part of the surface was covered with germanium oxide. A lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 6 A lithium ion secondary battery was produced in the same manner as in Example 2 except that the lithium iron manganese composite oxide synthesized in Example 1 and having a part of the surface covered with aluminum oxide was used as the positive electrode active material. ,evaluated. The results are shown in Table 1.
- Example 7 Titanium tetraisopropoxide 0.02g was dissolved in ethanol 15ml at 50 ° C. 30 minutes later, 0.5 g of lithium iron manganese composite oxide before coating with aluminum oxide synthesized in Example 1 was dispersed in the ethanol solution and stirred at 50 ° C. for 1 hour, whereby the lithium iron manganese composite was mixed. A slurry-like mixture was obtained in which a part of the oxide surface was coated with a hydrolysis product of titanium tetraisopropoxide. The slurry-like mixture was dried overnight in a 110 ° C. air constant temperature bath, and then heat-treated at 400 ° C. for 10 hours in an air atmosphere.
- Example 2 a composite oxide in which a part of the surface of the lithium iron manganese composite oxide was coated with titanium oxide was synthesized.
- the titanium oxide content was 1% by mass.
- the same X-ray diffraction measurement and EDX analysis as in Example 2 confirmed that the complex oxide was a complex oxide having a layered rock salt structure in which a part of the surface was coated with titanium oxide.
- a lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 8 A composite oxide in which part of the surface of the lithium iron manganese composite oxide was coated with titanium oxide was synthesized in the same manner as in Example 7 except that the content of titanium oxide was changed to 9% by mass. The same X-ray diffraction measurement and EDX analysis as in Example 2 confirmed that the complex oxide was a complex oxide having a layered rock salt structure in which a part of the surface was coated with titanium oxide. A lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 9 A composite oxide in which a part of the surface of the lithium iron manganese composite oxide was coated with silicon oxide was synthesized by the same method as in Example 7 except that tetraethyl orthosilicate was used instead of titanium tetraisopropoxide. .
- the silicon oxide content was 9% by mass.
- the same X-ray diffraction measurement and EDX analysis as in Example 2 confirmed that the complex oxide was a complex oxide having a layered rock salt structure in which a part of the surface was coated with silicon oxide.
- a lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 10 A composite oxide in which a part of the surface of the lithium iron manganese composite oxide was coated with tin oxide was synthesized in the same manner as in Example 7 except that tetraethoxytin was used instead of titanium tetraisopropoxide. .
- the tin oxide content was 9% by mass.
- the same X-ray diffraction measurement and EDX analysis as in Example 2 confirmed that the composite oxide was a composite oxide having a layered rock salt structure in which a part of the surface was coated with tin oxide.
- a lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 11 Cerium acetate was dissolved in 10 ml of water, and this was spray-coated on the composite oxide in which a part of the surface of the lithium iron manganese composite oxide obtained in Example 2 was covered with germanium oxide. The resulting slurry mixture was dried overnight in a 110 ° C. air constant temperature bath. The powder was heat-treated at 400 ° C. for 10 hours in an air atmosphere to synthesize a composite oxide in which part of the surface of the lithium iron manganese composite oxide was coated with cerium oxide and germanium oxide. The cerium oxide content was 1% by mass, and the germanium oxide content was 2% by mass.
- Example 2 The same X-ray diffraction measurement and EDX analysis as in Example 2 confirmed that the composite oxide was a composite oxide having a layered rock salt structure in which a part of the surface was coated with cerium oxide and germanium oxide. It was. A lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 12 A composite oxide in which part of the surface of the lithium iron manganese composite oxide was coated with gadolinium oxide and germanium oxide was synthesized in the same manner as in Example 11 except that gadolinium acetate was used instead of cerium acetate. The content of gadolinium oxide was 1% by mass, and the content of germanium oxide was 2% by mass. The same X-ray diffraction measurement and EDX analysis as in Example 2 confirmed that the composite oxide was a composite oxide having a layered rock salt structure in which a part of the surface was coated with gadolinium oxide and germanium oxide. It was. A lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 13 A composite oxide in which part of the surface of the lithium iron manganese composite oxide was coated with erbium oxide and germanium oxide was synthesized by the same method as in Example 11 except that erbium acetate was used instead of cerium acetate. The erbium oxide content was 1% by mass, and the germanium oxide content was 2% by mass. The same X-ray diffraction measurement and EDX analysis as in Example 2 confirmed that the composite oxide was a composite oxide having a layered rock salt structure in which a part of the surface was covered with erbium oxide and germanium oxide. It was. A lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 14 0.1 g of gadolinium acetate was dissolved in 10 ml of water, and this was spray-coated on the composite oxide in which a part of the surface of the lithium iron manganese composite oxide obtained in Example 2 was coated with germanium oxide, and dried. By firing, a composite oxide in which a part of the surface of the lithium iron manganese composite oxide was coated with gadolinium oxide was synthesized. In addition, content of the gadolinium oxide was 1 mass%. From the same X-ray diffraction measurement and EDX analysis as in Example 2, it was confirmed that the complex oxide was a complex oxide having a layered rock salt structure in which a part of the surface was coated with gadolinium oxide. A lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 15 A composite oxide in which a part of the surface of the lithium iron manganese composite oxide was coated with molybdenum oxide was synthesized in the same manner as in Example 2 except that molybdenum oxide was used instead of germanium oxide. The molybdenum oxide content was 2% by mass. The same X-ray diffraction measurement and EDX analysis as in Example 2 confirmed that the complex oxide was a complex oxide having a layered rock salt structure in which a part of the surface was coated with molybdenum oxide. A lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 16 0.4 g of germanium oxide, 0.2 g of molybdenum oxide and 0.048 g of lithium hydroxide were dissolved in 10 ml of water. This was spray-coated on 20 g of the lithium iron manganese composite oxide before coating with aluminum oxide synthesized in Example 1, dried and fired, so that a part of the surface of the lithium iron manganese composite oxide was molybdenum oxide, A composite oxide coated with germanium oxide was synthesized. The molybdenum oxide content was 1% by mass, and the germanium oxide content was 2% by mass.
- Example 2 The same X-ray diffraction measurement and EDX analysis as in Example 2 confirmed that the composite oxide was a composite oxide having a layered rock salt structure in which a part of the surface was coated with molybdenum oxide and germanium oxide. It was. A lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 17 A composite oxide in which part of the surface of the lithium iron manganese composite oxide was coated with aluminum oxide and germanium was synthesized in the same manner as in Example 11 except that aluminum acetate was used instead of cerium acetate. The aluminum oxide content was 1% by mass, and the germanium oxide content was 2% by mass. The same X-ray diffraction measurement and EDX analysis as in Example 2 confirmed that the composite oxide was a composite oxide having a layered rock salt structure in which a part of the surface was coated with aluminum oxide and germanium oxide. It was. A lithium ion secondary battery was produced and evaluated in the same manner as in Example 2 using the composite oxide. The results are shown in Table 1.
- Example 2 A lithium ion secondary battery was prepared and evaluated in the same manner as in Example 2 except that the lithium iron manganese-based composite oxide before coating with aluminum oxide synthesized in Example 1 was used as the positive electrode active material. The results are shown in Table 1.
- FIG. 4 is a diagram showing the capacity retention ratio with respect to the number of cycles in Comparative Example 2 and Example 2.
- the initial discharge capacities were 249 mAh / g and 247 mAh / g, respectively.
- the capacity retention ratios after 30 cycles in Comparative Example 2 and Example 2 were 89% and 92%, respectively.
- the gas generation amount per positive electrode active material was 15 ml / g and 10 ml / g, respectively, and gas generation was suppressed by covering the surface with germanium oxide.
- germanium oxide, cerium oxide, gadolinium oxide, erbium oxide, and molybdenum oxide as the inorganic substances from the capacity retention rate and gas generation amount shown in Table 1.
- the initial discharge capacities are 247 mAh / g, 247 mAh / g, 244 mAh / g, and 218 mAh / respectively. From the viewpoint of increasing the capacity, 3% by mass or less is effective.
- the lithium ion secondary battery according to the present embodiment has a high energy density and is excellent in cycle characteristics. Therefore, the lithium ion secondary battery can be widely used as an electronic device, an electric vehicle, a storage battery for power storage in general households and facilities, and the like. it can.
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Abstract
Description
LixM1 (y-p)MnpM2 (z-q)FeqO(2-δ) (1)
(前記式(1)において、1.05≦x≦1.32、0.33≦y≦0.63、0.06≦z≦0.50、0<p≦0.63、0.06≦q≦0.50、0≦δ≦0.80、y≧p、z≧qであり、M1はTiおよびZrの少なくとも一方の元素であり、M2はCo、NiおよびMnからなる群から選択される少なくとも一種の元素である)で示されるリチウム鉄マンガン系複合酸化物の表面の少なくとも一部が無機物により被覆されている。
本実施形態に係るリチウム鉄マンガン系複合酸化物は、層状岩塩型構造を有し、下記式(1)
LixM1 (y-p)MnpM2 (z-q)FeqO(2-δ) (1)
(前記式(1)において、1.05≦x≦1.32、0.33≦y≦0.63、0.06≦z≦0.50、0<p≦0.63、0.06≦q≦0.50、0≦δ≦0.80、y≧p、z≧qであり、M1はTiおよびZrの少なくとも一方の元素であり、M2はCo、NiおよびMnからなる群から選択される少なくとも一種の元素である)で示されるリチウム鉄マンガン系複合酸化物の表面の少なくとも一部が無機物により被覆されている。
本実施形態に係るリチウム鉄マンガン系複合酸化物の製造方法は、層状岩塩型構造を有し、前記式(1)を満たすリチウム鉄マンガン系複合酸化物の表面の少なくとも一部が無機物により被覆されていれば特に限定されない。例えば、層状岩塩型構造を有し、前記式(1)を満たすリチウム鉄マンガン系複合酸化物と、無機物の原料である加水分解性の化合物とを溶液中で混合し、反応させた後、熱処理することにより該リチウム鉄マンガン系複合酸化物の表面の少なくとも一部に無機物を被覆させることができる。具体的には、以下に示す方法が挙げられる。
複合水酸化物は、構成金属の水溶性塩をアルカリ水溶液中に滴下することにより析出させ、必要に応じて空気酸化を行い、水酸化物を熟成することによって作製することができる。構成金属の水溶性塩としては、特に限定されず、構成金属の硝酸塩、硫酸塩、塩化物、酢酸塩などの無水塩や水和物等が挙げられる。アルカリ源も特に限定されず、水酸化リチウムおよびその水和物、水酸化ナトリウム、水酸化カリウム、アンモニア水等が挙げられる。これらは一種を用いてもよく、二種以上を併用してもよい。複合水酸化物は、アルカリ水溶液に対して、構成金属の水溶性塩を数時間程度かけて徐々に滴下することで得られる。構成金属の水溶性塩を滴下する温度は、スピネルフェライトなどの不純物生成を抑制する観点から、60℃以下で行うことが好ましい。また0℃以下で構成金属の水溶性塩の滴下を行う場合には、アルカリ水溶液に不凍液としてエタノール等を加えて溶液の固化を防ぐことが好ましい。滴下後得られる水酸化物に対して、室温で数時間以上空気を吹き込むことにより水酸化物を湿式酸化して熟成することが好ましい。得られた熟成物を水洗、濾過することにより、目的の複合水酸化物が得られる。
前記複合水酸化物に対して、組成式に従い所定のリチウム化合物を加えて混合した後、所定の雰囲気下で焼成を行う。その後、必要に応じて余剰のリチウム化合物を除去するために水洗処理、濾過、乾燥を行うことにより、目的の組成式を有するリチウム鉄マンガン系複合酸化物が得られる。リチウム化合物は特に限定されず、炭酸リチウム、水酸化リチウム、硝酸リチウム、酢酸リチウム等の無水物または水和物を用いることができる。これらは一種を用いてもよく、二種以上を併用してもよい。焼成温度はLiの揮発を防ぐ観点から1000℃以下が好ましい。焼成雰囲気としては、空気雰囲気、不活性ガス雰囲気、窒素雰囲気、酸素雰囲気などを用いることができる。このような工程を経て、目的の組成を有する無機物による被覆前のリチウム鉄マンガン系複合酸化物が作製できる。
本実施形態に係るリチウムイオン二次電池用正極活物質は、本実施形態に係るリチウム鉄マンガン系複合酸化物を含む。正極活物質が本実施形態に係るリチウム鉄マンガン系複合酸化物を含むことにより、充放電サイクルにおいても酸素の脱離が抑制され、二次電池の容量が維持される。
本実施形態に係るリチウムイオン二次電池用正極(以下、正極とも示す)は、本実施形態に係るリチウムイオン二次電池用正極活物質を含む。
本実施形態に係るリチウムイオン二次電池は、本実施形態に係るリチウムイオン二次電池用正極と、負極とを備える。
<リチウム鉄マンガン系複合酸化物の合成>
所定原子比となるように秤量した硝酸鉄(III)、塩化マンガン(II)、および硝酸ニッケル(II)を蒸留水に溶解させ、金属塩水溶液(全量0.25mol/バッチ)を作製した。これとは別に、1.25mol/Lの水酸化リチウム水溶液を調製し、エタノールを加えて不凍化した後、恒温槽にて-10℃に冷却した。このアルカリ溶液に前記金属塩水溶液を2時間以上かけて徐々に滴下することにより、複合水酸化物を作製した。滴下後の複合水酸化物を含むアルカリ溶液を恒温槽より取り出し、該溶液に空気を吹き込んで2日間湿式酸化を行った後、複合水酸化物を室温にて熟成させた。
正極活物質である、リチウム鉄マンガン系複合酸化物Li1.20Mn0.47Ni0.16Fe0.16O1.89の表面の一部が酸化アルミニウムで被覆されたリチウム鉄マンガン系複合酸化物を92質量%、ケッチェンブラックを4質量%、ポリフッ化ビニリデンを4質量%含む混合物を、溶媒に混合してスラリーを調製した。該スラリーを厚み20μmのアルミニウム箔である正極集電体上に塗布し、該スラリーを乾燥させて、厚み175μmの正極を作製した。なお、前記リチウム鉄マンガン系複合酸化物全体に対する酸化アルミニウムの含有量は1質量%であった。
平均粒子径が15μmのSiOを85質量%、ポリアミック酸を15質量%含む混合物を、溶媒に混合してスラリーを調製した。該スラリーを厚み10μmの銅箔である負極集電体上に塗布し、該スラリーを乾燥させて、厚み46μmの負極を作製した。作製した負極を窒素雰囲気下350℃で3時間アニールし、ポリアミック酸を硬化させた。
前記正極および前記負極を成形した後、多孔質のフィルムセパレータを挟んで積層した。その後、該正極および該負極にそれぞれ正極タブおよび負極タブを溶接し、発電要素を作製した。該発電要素をアルミニウムラミネートフィルムである外装体で包み、該外装体の3辺を熱融着により封止した。その後、適度な真空度にて、該外装体内に1mol/LのLiPF6を含むEC/DEC電解液を注入した。その後、減圧下にて該外装体の残りの1辺を熱融着して封止し、活性化処理前のリチウムイオン二次電池を作製した。
前記活性化処理前のリチウムイオン二次電池について、正極活物質あたり20mA/gの電流で4.5Vまで充電した後、正極活物質あたり20mA/gの電流で1.5Vまで放電するサイクルを2回繰り返した。その後、一旦外装体の封止部を破り、減圧することで二次電池内部のガスを抜き、再封止することによりリチウムイオン二次電池を作製した。
前記リチウムイオン二次電池を、45℃の恒温槽中で、正極活物質あたり40mA/gの定電流で4.5Vまで充電し、さらに5mA/gの電流になるまで4.8Vの定電圧で充電した。その後、該リチウムイオン二次電池を10mA/gの電流で1.5Vまで放電した。該リチウムイオン二次電池を、45℃の恒温槽中で、正極活物質あたり40mA/gの定電流で4.5Vまで充電し、さらに5mA/gの電流になるまで4.5Vの定電圧で充電した後、40mA/gの電流で1.5Vまで放電する充放電サイクルを100回繰り返した。1サイクル目に得られた放電容量と、100サイクル目に得られた放電容量との比から、100サイクル後の容量維持率を求めた。本実施例1における100サイクル後の容量維持率は80%であった。
正極活物質として、表面が被覆されていないリチウム鉄マンガン系複合酸化物Li1.19Mn0.47Ni0.16Fe0.17O1.99を用いた以外は、実施例1と同様にリチウムイオン二次電池を作製し、評価した。本比較例1における100サイクル後の容量維持率は56%であった。
<リチウム鉄マンガン系複合酸化物の合成>
酸化ゲルマニウム0.2gと水酸化リチウム0.048gを水10mlに溶解させた。得られた溶液を、実施例1で合成した酸化アルミニウムによる被覆前のリチウム鉄マンガン系複合酸化物20gへスプレー塗布を行った。得られたスラリー状の混合物を110℃の空気恒温槽で1晩乾燥させた。その粉末を空気雰囲気下、400℃で10時間熱処理することにより、前記リチウム鉄マンガン系複合酸化物の表面の一部が酸化ゲルマニウムにより被覆された複合酸化物を得た。なお、酸化ゲルマニウムの含有量は1質量%であった。また、X線回折測定(XRD)の回折パターンから、この物質が層状岩塩型構造を有することが確認された(図2)。また、酸化ゲルマニウムの被覆によるピークシフトが観察されず、母材のリチウム鉄マンガン系複合酸化物の構造にほとんど変化はなかった(図2)。図3(a)は、SEM像(走査型電子顕微鏡像)とEDX(エネルギー分散型X線分光法)分析の結果である。左側がSEM像上にゲルマニウムをマッピングしたものであり、中央がニッケルとゲルマニウムをマッピングしたものであり、右側がマンガンとゲルマニウムをマッピングしたものである。図3(b)は、SEM像上をEDXでスポット分析したものである。これらの結果から、リチウム鉄マンガン系複合酸化物の表面の一部が酸化ゲルマニウムにより被覆されていることが分かった。
正極活物質である、リチウム鉄マンガン系複合酸化物Li1.20Mn0.47Ni0.16Fe0.16O1.89の表面の一部が酸化アルミニウムで被覆されたリチウム鉄マンガン系複合酸化物を92質量%、ケッチェンブラックを4質量%、ポリフッ化ビニリデンを4質量%含む混合物を、溶媒に混合してスラリーを調製した。該スラリーを厚み20μmのアルミニウム箔である正極集電体上に塗布し、該スラリーを乾燥させて、厚み130μmの正極を作製した。
平均粒子径が15μmの黒鉛を92質量%、PVDF(ポリフッ化ビニリデン)を4質量%、ケッチェンブラックを4質量%含む混合物を、溶媒に混合してスラリーを調製した。該スラリーを厚み10μmの銅箔である負極集電体上に塗布し、該スラリーを乾燥させて、厚み100μmの負極を作製した。
前記正極および前記負極を成形した後、多孔質のフィルムセパレータを挟んで積層した。その後、該正極および該負極にそれぞれ正極タブおよび負極タブを溶接し、発電要素を作製した。該発電要素をアルミニウムラミネートフィルムである外装体で包み、該外装体の3辺を熱融着により封止した。その後、適度な真空度にて、該外装体内に1mol/LのLiPF6を含むEC/DEC電解液を注入した。その後、減圧下にて該外装体の残りの1辺を熱融着して封止し、活性化処理前のリチウムイオン二次電池を作製した。
前記活性化処理前のリチウムイオン二次電池について、正極活物質あたり20mA/gの電流で、4.0Vから1.5Vの充放電範囲を、0.1Vずつ上限電圧を上げて充放電を繰り返しながら、段階的に電位を上げていく段階的活性化処理を行った(4.0~4.5V)。
前記リチウムイオン二次電池を、45℃の恒温槽中で、正極活物質あたり40mA/gの定電流で4.5Vまで充電し、さらに10mA/gの電流になるまで4.5Vの定電圧で充電した。その後、該リチウムイオン二次電池を40mA/gの電流で1.5Vまで放電した。この充放電サイクルを9回繰り返した。その後、正極活物質あたり10mA/gの定電流で4.5Vまで充電し、さらに2.5mA/gの電流になるまで4.5Vの定電圧で充電した。その後、該リチウムイオン二次電池を10mA/gの電流で1.5Vまで放電した。上記9サイクルと1サイクルで10サイクルとし、該10サイクルを3回行うことで30サイクルを実施した。1サイクル目に得られた放電容量と、30サイクル目に得られた放電容量との比から、30サイクル後の容量維持率を求めた。また、充放電前の二次電池と30サイクル後の二次電池の体積をアルキメデス法により評価し、それらの差をガス発生量とした。結果を表1に示す。
酸化ゲルマニウムの含有量を2質量%に変更した以外は、実施例2と同様にリチウム鉄マンガン系複合酸化物の表面の一部が酸化ゲルマニウムにより被覆された複合酸化物を合成した。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化ゲルマニウムにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
酸化ゲルマニウムの含有量を3質量%に変更した以外は、実施例2と同様にリチウム鉄マンガン系複合酸化物の表面の一部が酸化ゲルマニウムにより被覆された複合酸化物を合成した。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化ゲルマニウムにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
酸化ゲルマニウムの含有量を9質量%に変更した以外は、実施例2と同様にリチウム鉄マンガン系複合酸化物の表面の一部が酸化ゲルマニウムにより被覆された複合酸化物を合成した。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化ゲルマニウムにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
正極活物質として、実施例1において合成した、表面の一部が酸化アルミニウムにより被覆されたリチウム鉄マンガン系複合酸化物を用いた以外は、実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
チタンテトライソプロポキシド0.02gをエタノール15mlに50℃で溶解させた。30分後、実施例1で合成した酸化アルミニウムによる被覆前のリチウム鉄マンガン系複合酸化物0.5gを前記エタノール溶液に分散させ、50℃で1時間攪拌することで、前記リチウム鉄マンガン系複合酸化物の表面の一部がチタンテトライソプロポキシドの加水分解生成物により被覆されたスラリー状の混合物を得た。該スラリー状の混合物を110℃の空気恒温槽で1晩乾燥し、その後空気雰囲気下、400℃で10時間熱処理を行った。これにより、リチウム鉄マンガン系複合酸化物の表面の一部が酸化チタンにより被覆された複合酸化物を合成した。なお、酸化チタンの含有量は1質量%であった。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化チタンにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
酸化チタンの含有量を9質量%に変更した以外は、実施例7と同様にリチウム鉄マンガン系複合酸化物の表面の一部が酸化チタンにより被覆された複合酸化物を合成した。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化チタンにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
チタンテトライソプロポキシドの代わりにオルトケイ酸テトラエチルを用いた以外は、実施例7と同様の方法によりリチウム鉄マンガン系複合酸化物の表面の一部が酸化ケイ素により被覆された複合酸化物を合成した。なお、酸化ケイ素の含有量は9質量%であった。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化ケイ素により被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
チタンテトライソプロポキシドの代わりにテトラエトキシスズを用いた以外は、実施例7と同様の方法によりリチウム鉄マンガン系複合酸化物の表面の一部が酸化スズにより被覆された複合酸化物を合成した。なお、酸化スズの含有量は9質量%であった。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化スズにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
酢酸セリウムを水10mlに溶解させ、これを実施例2で得られたリチウム鉄マンガン系複合酸化物の表面の一部が酸化ゲルマニウムにより被覆された複合酸化物にスプレー塗布した。得られたスラリー状の混合物を110℃の空気恒温槽で1晩乾燥させた。その粉末を空気雰囲気下、400℃で10時間熱処理することにより、リチウム鉄マンガン系複合酸化物の表面の一部が酸化セリウムと酸化ゲルマニウムにより被覆された複合酸化物を合成した。なお、酸化セリウムの含有量は1質量%、酸化ゲルマニウムの含有量は2質量%であった。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化セリウムと酸化ゲルマニウムにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
酢酸セリウムの代わりに酢酸ガドリニウムを用いた以外は、実施例11と同様の方法によりリチウム鉄マンガン系複合酸化物の表面の一部が酸化ガドリニウムと酸化ゲルマニウムにより被覆された複合酸化物を合成した。なお、酸化ガドリニウムの含有量は1質量%、酸化ゲルマニウムの含有量は2質量%であった。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化ガドリニウムと酸化ゲルマニウムにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
酢酸セリウムの代わりに酢酸エルビウムを用いた以外は、実施例11と同様の方法によりリチウム鉄マンガン系複合酸化物の表面の一部が酸化エルビウムと酸化ゲルマニウムにより被覆された複合酸化物を合成した。なお、酸化エルビウムの含有量は1質量%、酸化ゲルマニウムの含有量は2質量%であった。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化エルビウムと酸化ゲルマニウムにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
酢酸ガドリニウム0.1gを水10mlに溶解させ、これを実施例2で得られたリチウム鉄マンガン系複合酸化物の表面の一部が酸化ゲルマニウムにより被覆された複合酸化物にスプレー塗布し、乾燥、焼成することで、リチウム鉄マンガン系複合酸化物の表面の一部が酸化ガドリニウムにより被覆された複合酸化物を合成した。なお、酸化ガドリニウムの含有量は1質量%であった。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化ガドリニウムにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
酸化ゲルマニウムの代わりに酸化モリブデンを用いた以外は、実施例2と同様の方法によりリチウム鉄マンガン系複合酸化物の表面の一部が酸化モリブデンにより被覆された複合酸化物を合成した。なお、酸化モリブデンの含有量は2質量%であった。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化モリブデンにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
酸化ゲルマニウム0.4g、酸化モリブデン0.2g、水酸化リチウム0.048gを水10mlに溶解させた。これを実施例1で合成した酸化アルミニウムによる被覆前のリチウム鉄マンガン系複合酸化物20gへスプレー塗布し、乾燥、焼成することで、リチウム鉄マンガン系複合酸化物の表面の一部が酸化モリブデン、酸化ゲルマニウムにより被覆された複合酸化物を合成した。なお、酸化モリブデンの含有量は1質量%、酸化ゲルマニウムの含有量は2質量%であった。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化モリブデン、酸化ゲルマニウムにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
酢酸セリウムの代わりに酢酸アルミニウムを用いた以外は、実施例11と同様の方法によりリチウム鉄マンガン系複合酸化物の表面の一部が酸化アルミニウムと酸化ゲルマニウムにより被覆された複合酸化物を合成した。なお、酸化アルミニウムの含有量は1質量%、酸化ゲルマニウムの含有量は2質量%であった。実施例2と同様のX線回折測定とEDX分析により、該複合酸化物は表面の一部が酸化アルミニウムと酸化ゲルマニウムにより被覆された、層状岩塩型構造を有する複合酸化物であることが確認された。該複合酸化物を用いて実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
正極活物質として、実施例1において合成した、酸化アルミニウムによる被覆前のリチウム鉄マンガン系複合酸化物を用いた以外は、実施例2と同様にリチウムイオン二次電池を作製し、評価した。結果を表1に示す。
1A 正極集電体
1B 正極タブ
2 負極活物質層
2A 負極集電体
2B 負極タブ
3 セパレータ
4 外装体
Claims (9)
- 層状岩塩型構造を有し、下記式(1)
LixM1 (y-p)MnpM2 (z-q)FeqO(2-δ) (1)
(前記式(1)において、1.05≦x≦1.32、0.33≦y≦0.63、0.06≦z≦0.50、0<p≦0.63、0.06≦q≦0.50、0≦δ≦0.80、y≧p、z≧qであり、M1はTiおよびZrの少なくとも一方の元素であり、M2はCo、NiおよびMnからなる群から選択される少なくとも一種の元素である)
で示されるリチウム鉄マンガン系複合酸化物の表面の少なくとも一部が無機物により被覆されたリチウム鉄マンガン系複合酸化物。 - 前記無機物が、酸化ゲルマニウム、酸化スズ、酸化ケイ素、酸化モリブデン、酸化セリウム、酸化ガドリニウム、酸化エルビウム、酸化アルミニウム、フッ化アルミニウムおよび酸化チタンからなる群から選択される少なくとも一種である請求項1に記載のリチウム鉄マンガン系複合酸化物。
- 前記無機物の含有量が、0.1質量%以上、15質量%以下である請求項1または2に記載のリチウム鉄マンガン系複合酸化物。
- 前記式(1)において、qが0.16≦q≦0.45を満たす請求項1から3のいずれか1項に記載のリチウム鉄マンガン系複合酸化物。
- 前記式(1)において、δが0.02≦δ≦0.50を満たす請求項1から4のいずれか1項に記載のリチウム鉄マンガン系複合酸化物。
- 請求項1から5のいずれか1項に記載のリチウム鉄マンガン系複合酸化物を含むリチウムイオン二次電池用正極活物質。
- 請求項6に記載のリチウムイオン二次電池用正極活物質を含むリチウムイオン二次電池用正極。
- 請求項7に記載のリチウムイオン二次電池用正極と、負極とを備えるリチウムイオン二次電池。
- 前記負極が、負極活物質としてSiOを含む請求項8に記載のリチウムイオン二次電池。
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JP2018063835A (ja) * | 2016-10-12 | 2018-04-19 | 日本電気株式会社 | リチウムイオン二次電池用正極材料、リチウムイオン二次電池用正極およびリチウムイオン二次電池 |
JP2020087612A (ja) * | 2018-11-20 | 2020-06-04 | 株式会社豊田自動織機 | 表面にアルミニウム含有被膜が形成された金属酸化物とアルミニウム含有針状物質とを含有する正極材料、及び、その製造方法 |
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