WO2015111188A1 - 電気デバイス - Google Patents
電気デバイス Download PDFInfo
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- WO2015111188A1 WO2015111188A1 PCT/JP2014/051528 JP2014051528W WO2015111188A1 WO 2015111188 A1 WO2015111188 A1 WO 2015111188A1 JP 2014051528 W JP2014051528 W JP 2014051528W WO 2015111188 A1 WO2015111188 A1 WO 2015111188A1
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- active material
- electrode active
- positive electrode
- negative electrode
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Images
Classifications
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- 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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- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- the present invention relates to an electrical device.
- the electric device according to the present invention is used, for example, as a secondary battery, a capacitor or the like as a driving power source or auxiliary power source for motors of vehicles such as electric vehicles, fuel cell vehicles, and hybrid electric vehicles.
- Motor drive secondary batteries are required to have extremely high output characteristics and high energy compared to consumer lithium ion secondary batteries used in mobile phones and notebook computers. Therefore, lithium ion secondary batteries having the highest theoretical energy among all the batteries are attracting attention, and are currently being developed rapidly.
- a lithium ion secondary battery includes a positive electrode in which a positive electrode active material or the like is applied to both surfaces of a positive electrode current collector using a binder, and a negative electrode in which a negative electrode active material or the like is applied to both surfaces of a negative electrode current collector using a binder.
- a positive electrode in which a positive electrode active material or the like is applied to both surfaces of a positive electrode current collector using a binder
- a negative electrode in which a negative electrode active material or the like is applied to both surfaces of a negative electrode current collector using a binder.
- it has the structure connected through an electrolyte layer and accommodated in a battery case.
- a battery using a SiO x (0 ⁇ x ⁇ 2) material that forms a compound with Li in the negative electrode has an improved energy density as compared with a conventional carbon / graphite negative electrode material.
- a SiO x (0 ⁇ x ⁇ 2) material that forms a compound with Li in the negative electrode
- SiO x a material that forms a compound with Li in the negative electrode
- a conventional carbon / graphite negative electrode material expected to bed as a material.
- SiO x single crystal nanoparticles
- amorphous SiO 2 exist in phase separation.
- Silicon oxide has a tetrahedral structure as a unit structure, and silicon oxides (intermediate oxides) other than SiO 2 correspond to the number of oxygen at the apex of the tetrahedron, 1, 2 and 3, respectively. Although they can be expressed as 2 O, SiO and Si 2 O 3 , these intermediate oxides are thermodynamically unstable and are extremely difficult to exist as single crystals. Therefore, SiO x is composed of an amorphous structure in which unit structures are irregularly arranged, and this amorphous structure is an amorphous structure in which a plurality of amorphous compounds are formed without forming an interface. The structure is mainly composed of a homogeneous amorphous structure portion. Therefore, SiO x has a structure in which Si nanoparticles are dispersed in amorphous SiO 2 .
- Li y SiO x such as Li 4 SiO 4 , Li 2 SiO 3 , Li 2 Si 2 O 5 , Li 2 Si 3 O 8 , Li 6 Si 4 O 11, etc. (0 ⁇ y, 0 ⁇ x ⁇ 2)
- Li y SiO x has extremely low electron conductivity, and furthermore, since SiO 2 does not have electron conductivity, the resistance of the negative electrode increases. There is. As a result, it is extremely difficult to desorb and insert lithium ions into the negative electrode active material.
- a lithium ion secondary battery using a material that is alloyed with Li for the negative electrode has a large expansion and contraction in the negative electrode during charge and discharge.
- the volume expansion when lithium ions are occluded is about 1.2 times in graphite materials, whereas in Si materials, when Si and Li are alloyed, the amorphous state transitions to the crystalline state, resulting in a large volume change. (Approximately 4 times), there was a problem of reducing the cycle life of the electrode.
- the Si negative electrode active material the battery capacity and the cycle durability are in a trade-off relationship, and there is a problem that it is difficult to improve the high cycle durability while exhibiting a high capacity.
- Patent Document 1 a negative electrode for a lithium ion secondary battery containing SiO x and a graphite material has been proposed (see, for example, Patent Document 1).
- paragraph “0018” describes that, by minimizing the content of SiO x , good cycle life is exhibited in addition to high capacity.
- the present invention is satisfactory in rate characteristics while fully utilizing the high capacity characteristics that are characteristic of solid solution positive electrode active materials in electrical devices such as lithium ion secondary batteries having positive electrodes using solid solution positive electrode active materials.
- the object is to provide a means to achieve the desired performance.
- the present inventors have conducted intensive research to solve the above problems. As a result, a negative electrode containing a negative electrode active material obtained by mixing a Si-containing alloy and a carbon material, and a positive electrode containing a Mn-containing solid solution positive electrode active material in which Mn is substituted with a predetermined element are used.
- the inventors have found that the above problem can be solved by controlling the coating amount (weight per unit area) of the active material layer to a predetermined value, and have completed the present invention.
- the present invention includes a positive electrode in which a positive electrode active material layer including a positive electrode active material is formed on the surface of a positive electrode current collector, and a negative electrode active material layer including a negative electrode active material on the surface of the negative electrode current collector.
- the present invention relates to an electric device having a power generation element including a negative electrode and a separator.
- the coating amount of the negative electrode active material layer is 3 to 11 mg / cm 2 .
- the said negative electrode active material layer contains the negative electrode active material represented by following formula (1).
- ⁇ and ⁇ represent the weight percent of each component in the negative electrode active material layer, and 80 ⁇ ⁇ + ⁇ ⁇ 98, 3 ⁇ ⁇ ⁇ 40, and 40 ⁇ ⁇ ⁇ 95.
- the positive electrode active material layer contains a positive electrode active material represented by the following formula (2).
- e represents weight% of each component in the positive electrode active material layer, and 80 ⁇ e ⁇ 98.
- the positive electrode active material is a solid solution material having a predetermined composition
- an effect of greatly reducing the initial discharge capacity due to the initial irreversible capacity of the negative electrode active material can be obtained.
- the electrical device according to the present invention can achieve satisfactory performance in terms of rate characteristics while fully utilizing the high capacity characteristics that are characteristic of the solid solution positive electrode active material.
- FIG. 1 is a schematic cross-sectional view showing the basic configuration of a non-aqueous electrolyte lithium ion secondary battery that is not a flat type (stacked type) bipolar type, which is an embodiment of the electrical device according to the present invention. It is a perspective view showing the appearance of a flat lithium ion secondary battery which is a typical embodiment of an electric device according to the present invention. It is a chart which shows the X-ray-diffraction pattern of the solid solution positive electrode active material C0 which does not contain Ti. 2 is a chart showing an X-ray diffraction pattern of the solid solution positive electrode active material C1 obtained in Example 1.
- a positive electrode in which a positive electrode active material layer containing a positive electrode active material is formed on the surface of a positive electrode current collector, and a negative electrode active material layer containing a negative electrode active material on the surface of the negative electrode current collector are provided.
- the negative electrode active material layer has the following formula (1):
- ⁇ and ⁇ represent the weight percentage of each component in the negative electrode active material layer, and 80 ⁇ ⁇ + ⁇ ⁇ 98, 3 ⁇ ⁇ ⁇ 40, and 40 ⁇ ⁇ ⁇ 95.
- Containing a negative electrode active material represented by The positive electrode active material layer has the following formula (2):
- e represents the weight% of each component in the positive electrode active material layer, and 80 ⁇ e ⁇ 98.
- the solid solution positive electrode active material is represented by the following formula (3):
- An electrical device having the composition represented by:
- a lithium ion secondary battery will be described as an example of an electric device.
- the lithium ion secondary battery using the electric device according to the present invention the voltage of the cell (single cell layer) is large, and high energy density and high output density can be achieved. Therefore, the lithium ion secondary battery of the present embodiment is excellent as a vehicle driving power source or an auxiliary power source. As a result, it can be suitably used as a lithium ion secondary battery for a vehicle driving power source or the like. In addition to this, the present invention can be sufficiently applied to lithium ion secondary batteries for portable devices such as mobile phones.
- the lithium ion secondary battery When the lithium ion secondary battery is distinguished by its form / structure, it can be applied to any conventionally known form / structure such as a stacked (flat) battery or a wound (cylindrical) battery. Is. By adopting a stacked (flat) battery structure, long-term reliability can be secured by a sealing technique such as simple thermocompression bonding, which is advantageous in terms of cost and workability.
- a solution electrolyte type battery using a solution electrolyte such as a nonaqueous electrolyte solution for the electrolyte layer, a polymer battery using a polymer electrolyte for the electrolyte layer, etc. It can be applied to any conventionally known electrolyte layer type.
- the polymer battery is further divided into a gel electrolyte type battery using a polymer gel electrolyte (also simply referred to as gel electrolyte) and a solid polymer (all solid) type battery using a polymer solid electrolyte (also simply referred to as polymer electrolyte). It is done.
- FIG. 1 schematically shows the overall structure of a flat (stacked) lithium ion secondary battery (hereinafter also simply referred to as “stacked battery”), which is a typical embodiment of the electrical device of the present invention.
- stacked battery a flat (stacked) lithium ion secondary battery
- the stacked battery 10 of the present embodiment has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction actually proceeds is sealed inside a laminate sheet 29 that is an exterior body.
- the positive electrode in which the positive electrode active material layer 13 is disposed on both surfaces of the positive electrode current collector 11, the electrolyte layer 17, and the negative electrode active material layer 15 is disposed on both surfaces of the negative electrode current collector 12. It has a configuration in which a negative electrode is laminated. Specifically, the negative electrode, the electrolyte layer, and the positive electrode are laminated in this order so that one positive electrode active material layer 13 and the negative electrode active material layer 15 adjacent thereto face each other with the electrolyte layer 17 therebetween. .
- the adjacent positive electrode, electrolyte layer, and negative electrode constitute one unit cell layer 19. Therefore, it can be said that the stacked battery 10 shown in FIG. 1 has a configuration in which a plurality of single battery layers 19 are stacked and electrically connected in parallel.
- the positive electrode current collector 13 on the outermost layer located on both outermost layers of the power generating element 21 is provided with the positive electrode active material layer 13 only on one side, but the active material layer may be provided on both sides. . That is, instead of using a current collector dedicated to the outermost layer provided with an active material layer only on one side, a current collector having an active material layer on both sides may be used as it is as an outermost current collector.
- the outermost negative electrode current collector is positioned on both outermost layers of the power generation element 21, and one side of the outermost negative electrode current collector or A negative electrode active material layer may be disposed on both sides.
- the positive electrode current collector 11 and the negative electrode current collector 12 are attached to a positive electrode current collector plate 25 and a negative electrode current collector plate 27 that are electrically connected to the respective electrodes (positive electrode and negative electrode), and are sandwiched between end portions of the laminate sheet 29. Thus, it has a structure led out of the laminate sheet 29.
- the positive electrode current collector plate 25 and the negative electrode current collector plate 27 are ultrasonically welded to the positive electrode current collector 11 and the negative electrode current collector 12 of each electrode via a positive electrode lead and a negative electrode lead (not shown), respectively, as necessary. Or resistance welding or the like.
- the lithium ion secondary battery according to this embodiment is characterized by the configuration of the positive electrode and the negative electrode.
- main components of the battery including the positive electrode and the negative electrode will be described.
- the active material layers (13, 15) contain an active material, and further contain other additives as necessary.
- the positive electrode active material layer 13 includes at least a positive electrode active material (also referred to as “solid solution positive electrode active material” in the present specification) made of a solid solution material.
- Solid solution positive electrode active material The solid solution positive electrode active material has a composition represented by the following formula (3).
- this solid solution positive electrode active material was measured at 20-23 °, 35-40 ° (101), 42-45 ° (104) and 64-65 (108) / 65-66 (X-ray diffraction (XRD) measurement).
- 110) preferably has a diffraction peak indicating a rock salt type layered structure. At this time, in order to surely obtain the effect of improving the cycle characteristics, those having substantially no peak attributed to other than the diffraction peak of the rock salt type layered structure are preferable. More preferably, one having three diffraction peaks at 35-40 ° (101) and one diffraction peak at 42-45 ° (104) is suitable.
- the X-ray diffraction measurement shall employ the measurement method described in the examples described later.
- the notation of 64-65 (108) / 65-66 (110) has two peaks close to 64-65 and 65-66.
- one peak is broadly separated without being clearly separated. It is meant to include.
- the solid solution positive electrode active material having the composition represented by the composition formula (3) preferably has a plurality of specific diffraction peaks in the X-ray diffraction (XRD) measurement.
- the solid solution positive electrode active material having the above composition formula is a solid solution system of Li 2 MnO 3 and LiMnO 2.
- the diffraction peak at 20-23 ° is characteristic of Li 2 MnO 3 .
- the diffraction peaks of 36.5-37.5 ° (101), 44-45 ° (104) and 64-65 (108) / 65-66 (110) are usually in the rock salt type layered structure of LiMnO 2. It is characteristic.
- the solid solution positive electrode active material of the present embodiment does not include those having a peak other than a diffraction peak showing a rock salt type layered structure, for example, other peaks derived from impurities or the like, in these angular ranges.
- a structure other than the rock salt type layered structure is included in the positive electrode active material. If the structure other than the rock salt type layered structure is not included, the effect of improving the cycle characteristics can be surely obtained.
- the solid solution positive electrode active material at least one of Ti, Zr, and Nb is dissolved in a transition metal layer made of Ni, Co, and Mn by substituting Mn 4+ to form a rock salt type It is considered that a layered structure is formed. Since at least one kind of Ti, Zr and Nb is dissolved, the crystal structure is stabilized, so that it is considered that elution of transition metals including Mn is suppressed during charging and discharging. As a result, even if charging / discharging is repeated, the capacity reduction of the battery can be prevented, and excellent cycle characteristics can be achieved. In addition, battery performance itself and durability can be improved.
- the diffraction peak showing the rock salt type layered structure in this embodiment is shifted to the low angle side. That is, the solid solution positive electrode active material according to the present embodiment is 20-23 °, 35.5-36.5 ° (101), 43.5-44.5 ° (104) in X-ray diffraction (XRD) measurement. And preferably have diffraction peaks at 64-65 (108) / 65-66 (110).
- the shift of the diffraction peak to the lower angle side indicates that Ti and the like are more solid-dissolved in the positive electrode active material and substitutes Mn, which is considered to have a greater effect of suppressing Mn elution.
- a + b + c + e satisfies 1.1 ⁇ [a + b + c + e] ⁇ 1.4.
- nickel (Ni), cobalt (Co), and manganese (Mn) are known to contribute to capacity characteristics and output characteristics from the viewpoint of improving the purity of the material and improving the electronic conductivity.
- Ti or the like partially substitutes Mn in the crystal lattice.
- a is preferably 0 ⁇ a ⁇ 1.5, and more preferably 0.1 ⁇ a ⁇ 0.75.
- a is in the above range, a secondary battery having a better capacity retention rate can be obtained.
- a is not a ⁇ 0.75, the crystal structure is not stabilized because nickel is contained in the positive electrode active material within the above range d on condition that nickel (Ni) is divalent. There is.
- a ⁇ 0.75 the crystal structure of the positive electrode active material tends to be a rock salt type layered structure.
- b is preferably 0 ⁇ b ⁇ 1.5, and more preferably 0.2 ⁇ b ⁇ 0.9.
- b is in the above range, an electric device having a better capacity retention rate can be obtained.
- b does not satisfy b ⁇ 0.9, manganese is contained in the positive electrode active material within the above range d, provided that manganese is tetravalent, and nickel (Ni ), The crystal structure may not be stabilized.
- b ⁇ 0.9 the crystal structure of the positive electrode active material tends to be a rock salt type layered structure.
- c is preferably 0 ⁇ c ⁇ 1.5.
- nickel and manganese are contained in the positive electrode active material within the above range d on condition that cobalt is trivalent.
- cobalt (Co) is contained in the positive electrode active material within the above range d on condition that nickel (Ni) is divalent and manganese (Mn) is tetravalent. Therefore, the crystal structure of the positive electrode active material may not be stabilized.
- c ⁇ 0.6 the crystal structure of the positive electrode active material tends to be a rock salt type layered structure.
- composition formula (3) 0.1 ⁇ d ⁇ 0.4.
- d is not 0.1 ⁇ d ⁇ 0.4, the crystal structure of the positive electrode active material may not be stabilized.
- the positive electrode active material tends to have a rock salt type layered structure.
- the range of d is more preferably 0.15 ⁇ d ⁇ 0.35.
- d is 0.1 or more, the composition is less likely to be close to Li 2 MnO 3 and charge / discharge is facilitated, which is preferable.
- e 0.01 ⁇ e ⁇ 0.4.
- the element cannot be uniformly dissolved in the crystal structure, and the crystal structure cannot be stabilized.
- at least one of Ti, Zr, and Nb can sufficiently substitute Mn 4+ so that elution is suppressed. More preferably, e satisfies 0.02 ⁇ e ⁇ 0.3, more preferably 0.025 ⁇ e ⁇ 0.25, and particularly preferably 0.03 ⁇ e ⁇ 0.2.
- the ionic radius of each element is Mn 4+ 0.540.5, Mn 4+ 0.54 ⁇ , Ti 4+ 0.61 ⁇ , Zr 4+ 0.72 ⁇ , Nb 5+ 0.64 ⁇ , and Ti, Zr and Nb are larger than Mn. ing. Therefore, as Mn 4+ in the positive electrode active material is replaced with Ti or the like, the crystal lattice expands, and the diffraction peak indicating the rock salt type layered structure shifts to a lower angle side. On the contrary, if the diffraction peak is shifted to a lower angle side, the substitution amount of Mn 4+ such as Ti is larger, and the crystal structure is easily stabilized. That is, elution of Mn at the time of charging / discharging is further suppressed, and the capacity reduction of the electric device can be more effectively prevented.
- the specific surface area of the positive electrode active material is preferably 0.2 to 0.6 m 2 / g, and more preferably 0.25 to 0.5 m 2 / g.
- a specific surface area of 0.2 m 2 / g or more is preferable because sufficient battery output can be obtained.
- the specific surface area is 0.6 m 2 / g or less because elution of manganese can be further suppressed.
- the value measured by the method of an Example shall be employ
- the average particle diameter of the positive electrode active material is preferably 10 to 20 ⁇ m, and more preferably 12 to 18 ⁇ m. It is preferable that the average particle size is 10 ⁇ m or more because elution of manganese can be suppressed. On the other hand, when the average particle size is 20 ⁇ m or less, it is preferable that foil breakage, clogging, and the like can be suppressed in the application step to the current collector during the production of the positive electrode.
- the average particle diameter is measured by a laser diffraction / scattering particle size distribution measuring device. The average particle diameter can be measured, for example, using a particle size distribution analyzer (model LA-920) manufactured by Horiba.
- the solid solution positive electrode active material as described above can be prepared, for example, by the following method. That is, a first step of mixing at least one citrate of Ti, Zr and Nb with an organic acid salt of a transition metal having a melting point of 100 ° C. to 350 ° C., and a mixture obtained in the first step at 100 ° C. A second step of melting at ⁇ 350 ° C., a third step of pyrolyzing the melt obtained in the second step at a temperature higher than the melting point, and a second step of firing the pyrolyzate obtained in the third step. 4 steps. Hereinafter, each step will be described.
- At least one citrate of Ti, Zr and Nb and an organic acid salt of a transition metal having a melting point of 100 ° C. to 350 ° C. are mixed.
- At least one citrate of Ti, Zr and Nb is preferably mixed in the form of an aqueous citric acid complex solution.
- the aqueous solution of at least one kind of citrate complex of Ti, Zr and Nb is not limited to the following, but it can be preferably prepared as follows.
- anhydrous citric acid is dissolved in an organic solvent such as acetone, and at least one alkoxide of Ti, Zr and Nb is added to the solution.
- the molar ratio of at least one of Ti, Zr and Nb to citric acid is preferably (at least one of Ti, Zr and Nb) / citric acid being 1/1 to 1/2.
- the amount of water is appropriately added so that the concentration of the aqueous citric acid complex is 1 to 10% by mass in terms of at least one of Ti, Zr and Nb.
- This aqueous solution is allowed to stand for one day, and the precipitate is filtered to obtain an aqueous solution of at least one citrate complex of Ti, Zr and Nb as a filtrate.
- an organic acid salt of a transition metal having a melting point of 100 ° C. to 350 ° C. is added to the obtained aqueous solution of at least one kind of citric acid complex of Ti, Zr and Nb to obtain a mixture.
- the organic acid salt of transition metal having a melting point of 100 ° C. to 350 ° C. preferably includes nickel acetate, manganese acetate, cobalt acetate, manganese citrate and the like.
- an alkali metal organic acid salt is further mixed with the above-described aqueous solution of at least one kind of citric acid complex of Ti, Zr and Nb.
- Preferred examples of the organic acid salt of alkali metal include lithium acetate and lithium citrate. It is preferable to mix an alkali metal organic acid salt at this stage because the production method is simple.
- Second Step The mixture obtained in the first step is melted at 100 to 350 ° C., preferably 200 to 300 ° C.
- the heated melt (slurry) obtained in the second step is pyrolyzed at a temperature equal to or higher than the melting point of the organic acid salt of the transition metal used in the first step to obtain a pyrolyzate that is a dry powder.
- the melting points of the organic acid salts of a plurality of transition metals are different from each other, they are thermally decomposed at a temperature higher than the highest melting point. More specifically, the melt can be heated and sprayed at 200 to 600 ° C., more preferably 200 to 400 ° C., with a spray device.
- the pyrolyzate obtained in the third step is calcined at 600 to 1200 ° C., more preferably 800 to 1100 ° C., for 5 to 20 hours, preferably 10 to 15 hours.
- Temporary baking may be performed before baking, in which case the temporary baking may be performed at 200 to 700 ° C., more preferably 300 to 600 ° C. for 1 to 10 hours, more preferably 2 to 6 hours.
- the positive electrode active material of this embodiment is obtained.
- a positive electrode active material other than the solid solution positive electrode active material described above may be used in combination.
- a lithium-transition metal composite oxide is used in combination as the positive electrode active material from the viewpoint of capacity and output characteristics.
- other positive electrode active materials may be used.
- the optimum particle size is different for expressing the unique effect of each active material, the optimum particle size may be blended and used for expressing each unique effect. It is not always necessary to make the particle diameter uniform.
- the average particle diameter of the positive electrode active material contained in the positive electrode active material layer 13 is not particularly limited, but is preferably 1 to 30 ⁇ m and more preferably 5 to 20 ⁇ m from the viewpoint of increasing the output.
- the “particle diameter” refers to the outline of the active material particles (observation surface) observed using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). It means the maximum distance among any two points.
- the value of “average particle diameter” is the value of particles observed in several to several tens of fields using observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The value calculated as the average value of the particle diameter shall be adopted.
- the particle diameters and average particle diameters of other components can be defined in the same manner.
- the positive electrode active material layer contains a positive electrode active material (solid solution positive electrode active material) represented by the following formula (2).
- e represents the weight% of each component in the positive electrode active material layer, and 80 ⁇ e ⁇ 98.
- the content of the solid solution positive electrode active material in the positive electrode active material layer is indispensable to be 80 to 98% by weight, preferably 84 to 98% by weight.
- the positive electrode active material layer preferably contains a binder and a conductive aid in addition to the solid solution positive electrode active material described above. Further, if necessary, it further contains other additives such as an electrolyte (polymer matrix, ion-conductive polymer, electrolyte solution, etc.) and a lithium salt for increasing the ion conductivity.
- a binder and a conductive aid in addition to the solid solution positive electrode active material described above. Further, if necessary, it further contains other additives such as an electrolyte (polymer matrix, ion-conductive polymer, electrolyte solution, etc.) and a lithium salt for increasing the ion conductivity.
- Binder Although it does not specifically limit as a binder used for a positive electrode active material layer, for example, the following materials are mentioned. Polyethylene, polypropylene, polyethylene terephthalate (PET), polyether nitrile, polyacrylonitrile, polyimide, polyamide, cellulose, carboxymethyl cellulose (CMC) and its salts, ethylene-vinyl acetate copolymer, polyvinyl chloride, styrene-butadiene rubber (SBR) ), Isoprene rubber, butadiene rubber, ethylene / propylene rubber, ethylene / propylene / diene copolymer, styrene / butadiene / styrene block copolymer and hydrogenated product thereof, styrene / isoprene / styrene block copolymer and hydrogenated product thereof.
- Thermoplastic polymers such as products, polyvinylidene fluoride (P
- the binder content in the positive electrode active material layer is preferably 1 to 10% by weight, more preferably 1 to 8% by weight.
- the conductive assistant refers to an additive that is blended in order to improve the conductivity of the positive electrode active material layer or the negative electrode active material layer.
- Examples of the conductive assistant include carbon black such as ketjen black and acetylene black.
- the content of the conductive auxiliary in the positive electrode active material layer is preferably 1 to 10% by weight, more preferably 1 to 8% by weight.
- electrolyte salt examples include Li (C 2 F 5 SO 2 ) 2 N, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 and the like.
- Examples of the ion conductive polymer include polyethylene oxide (PEO) and polypropylene oxide (PPO) polymers.
- the positive electrode (positive electrode active material layer) can be applied by any one of a kneading method, a sputtering method, a vapor deposition method, a CVD method, a PVD method, an ion plating method, and a thermal spraying method in addition to a method of applying (coating) a normal slurry. Can be formed.
- the negative electrode active material layer 15 essentially contains a Si-containing alloy and a carbon material as a negative electrode active material.
- Si-containing alloy is not particularly limited as long as it is an alloy with another metal containing Si, and conventionally known knowledge can be appropriately referred to.
- Si-containing alloy Si x Ti y Ge z A a , Si x Ti y Zn z A a , Si x Ti y Sn z A a , Si x Sn y Al z A a , and Si x Sn y V z A a , Si x Sn y C z A a , Si x Zn y V z A a , Si x Zn y Sn z A a , Si x Zn y Al z A a , Si x Zn y C zA a, Si x Al y C z a a and Si x Al y Nb z a a ( wherein, a is unavoidable impurities.
- the average particle size of the Si-containing alloy is not particularly limited as long as it is approximately the same as the average particle size of the negative electrode active material included in the existing negative electrode active material layer 15. From the viewpoint of higher output, it is preferably in the range of 1 to 20 ⁇ m. However, it is not limited at all to the above range, and it goes without saying that it may be outside the above range as long as the effects of the present embodiment can be effectively expressed.
- the shape of the Si-containing alloy is not particularly limited, and may be spherical, elliptical, cylindrical, polygonal, flaky, indefinite, or the like.
- the carbon material that can be used in the present invention is not particularly limited, but graphite (graphite), which is a highly crystalline carbon such as natural graphite or artificial graphite; low crystalline carbon such as soft carbon or hard carbon; ketjen black, acetylene Carbon black such as black, channel black, lamp black, oil furnace black, and thermal black; and carbon materials such as fullerene, carbon nanotube, carbon nanofiber, carbon nanohorn, and carbon fibril. Of these, graphite is preferably used.
- the average particle diameter of the carbon material is not particularly limited, but is preferably 5 to 25 ⁇ m, and more preferably 5 to 10 ⁇ m.
- the average particle size of the carbon material may be the same as or different from the average particle size of the Si-containing alloy. Is preferred.
- the average particle size of the Si-containing alloy is more preferably smaller than the average particle size of the carbon material.
- negative electrode active materials other than the two types of negative electrode active materials described above may be used in combination.
- the negative electrode active material that can be used in combination include SiO x , a lithium-transition metal composite oxide (eg, Li 4 Ti 5 O 12 ), a metal material, and a lithium alloy negative electrode material.
- SiO x SiO x
- Li 4 Ti 5 O 12 lithium-transition metal composite oxide
- metal material e.g., Li 4 Ti 5 O 12
- lithium alloy negative electrode material e.g, Li 4 Ti 5 O 12
- other negative electrode active materials may be used.
- the negative electrode active material layer contains a negative electrode active material represented by the following formula (1).
- ⁇ and ⁇ represent the weight percentage of each component in the negative electrode active material layer, and 80 ⁇ ⁇ + ⁇ ⁇ 98, 3 ⁇ ⁇ ⁇ 40, and 40 ⁇ ⁇ ⁇ 95.
- the content of the negative electrode active material made of the Si-containing alloy in the negative electrode active material layer is 3 to 40% by weight.
- the content of the carbon material negative electrode active material is 40 to 95% by weight. Furthermore, the total content thereof is 80 to 98% by weight.
- the mixing ratio of the Si-containing alloy and the carbon material of the negative electrode active material is not particularly limited as long as the above-described content specification is satisfied, and can be appropriately selected according to a desired application.
- the content of the Si-containing alloy in the negative electrode active material is preferably 3 to 40% by weight.
- the content of the Si-containing alloy in the negative electrode active material is more preferably 4 to 30% by weight.
- the content of the Si-containing alloy in the negative electrode active material is more preferably 5 to 20% by weight.
- the content of the Si-containing alloy is 3% by weight or more because a high initial capacity can be obtained.
- the content of the Si-containing alloy is 40% by weight or less, it is preferable because high cycle characteristics can be obtained.
- the negative electrode active material layer preferably contains a binder and a conductive additive in addition to the negative electrode active material described above. Further, if necessary, it further contains other additives such as an electrolyte (polymer matrix, ion conductive polymer, electrolytic solution, etc.) and a lithium salt for increasing the ion conductivity.
- an electrolyte polymer matrix, ion conductive polymer, electrolytic solution, etc.
- a lithium salt for increasing the ion conductivity.
- the present embodiment is characterized in that the coating amount (weight per unit area) of the negative electrode active material layer is 3 to 11 mg / cm 2 .
- the coating amount (weight per unit area) of the negative electrode active material layer exceeds 11 mg / cm 2 , there is a problem that the rate characteristics of the battery are remarkably deteriorated.
- the coating amount (weight per unit area) of the negative electrode active material layer is less than 3 mg / cm 2 , the content of the active material in the negative electrode active material layer is reduced in the first place. A load will be applied, and cycle durability will deteriorate.
- the coating amount (weight per unit area) of the negative electrode active material layer is a value within the above-described range, both rate characteristics and cycle characteristics can be achieved.
- a predetermined negative electrode active material is used in combination, and the content thereof is adjusted to achieve the coating amount (weight per unit area) within the above range.
- each active material layer (active material layer on one side of the current collector) is not particularly limited, and conventionally known knowledge about the battery can be appropriately referred to.
- the thickness of each active material layer is usually about 1 to 500 ⁇ m, preferably 2 to 100 ⁇ m, taking into consideration the intended use of the battery (emphasis on output, energy, etc.) and ion conductivity.
- the current collectors (11, 12) are made of a conductive material.
- the size of the current collector is determined according to the intended use of the battery. For example, if it is used for a large battery that requires a high energy density, a current collector having a large area is used.
- the thickness of the current collector is usually about 1 to 100 ⁇ m.
- the shape of the current collector is not particularly limited.
- a mesh shape (such as an expanded grid) can be used.
- the negative electrode active material is formed directly on the negative electrode current collector 12 by sputtering or the like, it is preferable to use a current collector foil.
- a metal or a resin in which a conductive filler is added to a conductive polymer material or a non-conductive polymer material can be employed.
- examples of the metal include aluminum, nickel, iron, stainless steel, titanium, and copper.
- a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plating material of a combination of these metals can be preferably used.
- covered on the metal surface may be sufficient.
- aluminum, stainless steel, copper, and nickel are preferable from the viewpoints of electronic conductivity, battery operating potential, and adhesion of the negative electrode active material by sputtering to the current collector.
- examples of the conductive polymer material include polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyphenylene vinylene, polyacrylonitrile, and polyoxadiazole. Since such a conductive polymer material has sufficient conductivity without adding a conductive filler, it is advantageous in terms of facilitating the manufacturing process or reducing the weight of the current collector.
- Non-conductive polymer materials include, for example, polyethylene (PE; high density polyethylene (HDPE), low density polyethylene (LDPE), etc.), polypropylene (PP), polyethylene terephthalate (PET), polyether nitrile (PEN), polyimide (PI), polyamideimide (PAI), polyamide (PA), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA) , Polyvinyl chloride (PVC), polyvinylidene fluoride (PVdF), or polystyrene (PS).
- PE polyethylene
- HDPE high density polyethylene
- LDPE low density polyethylene
- PP polypropylene
- PET polyethylene terephthalate
- PEN polyether nitrile
- PI polyimide
- PAI polyamideimide
- PA polyamide
- PTFE polytetraflu
- a conductive filler may be added to the conductive polymer material or the non-conductive polymer material as necessary.
- a conductive filler is inevitably necessary to impart conductivity to the resin.
- the conductive filler can be used without particular limitation as long as it has a conductivity.
- metals, conductive carbon, etc. are mentioned as a material excellent in electroconductivity, electric potential resistance, or lithium ion barrier
- the metal is not particularly limited, but at least one metal selected from the group consisting of Ni, Ti, Al, Cu, Pt, Fe, Cr, Sn, Zn, In, Sb, and K, or these metals It is preferable to contain an alloy or metal oxide containing.
- it includes at least one selected from the group consisting of acetylene black, vulcan, black pearl, carbon nanofiber, ketjen black, carbon nanotube, carbon nanohorn, carbon nanoballoon, and fullerene.
- the amount of the conductive filler added is not particularly limited as long as it is an amount capable of imparting sufficient conductivity to the current collector, and is generally about 5 to 35% by weight.
- the separator has a function of holding an electrolyte and ensuring lithium ion conductivity between the positive electrode and the negative electrode, and a function as a partition wall between the positive electrode and the negative electrode.
- separator examples include a separator made of a porous sheet made of a polymer or fiber that absorbs and holds the electrolyte and a nonwoven fabric separator.
- a microporous (microporous film) can be used as the separator of the porous sheet made of polymer or fiber.
- the porous sheet made of the polymer or fiber include polyolefins such as polyethylene (PE) and polypropylene (PP); a laminate in which a plurality of these are laminated (for example, three layers of PP / PE / PP) And a microporous (microporous membrane) separator made of a hydrocarbon resin such as polyimide, aramid, polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), glass fiber, and the like.
- PE polyethylene
- PP polypropylene
- a microporous (microporous membrane) separator made of a hydrocarbon resin such as polyimide, aramid, polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), glass fiber, and the like.
- the thickness of the microporous (microporous membrane) separator cannot be uniquely defined because it varies depending on the intended use. For example, in applications such as secondary batteries for driving motors such as electric vehicles (EV), hybrid electric vehicles (HEV), and fuel cell vehicles (FCV), it is 4 to 60 ⁇ m in a single layer or multiple layers. Is desirable.
- the fine pore diameter of the microporous (microporous membrane) separator is desirably 1 ⁇ m or less (usually a pore diameter of about several tens of nm).
- nonwoven fabric separator cotton, rayon, acetate, nylon, polyester; polyolefins such as PP and PE; conventionally known ones such as polyimide and aramid are used alone or in combination.
- the bulk density of the nonwoven fabric is not particularly limited as long as sufficient battery characteristics can be obtained by the impregnated polymer gel electrolyte.
- the thickness of the nonwoven fabric separator may be the same as that of the electrolyte layer, and is preferably 5 to 200 ⁇ m, particularly preferably 10 to 100 ⁇ m.
- the separator includes an electrolyte.
- the electrolyte is not particularly limited as long as it can exhibit such a function, but a liquid electrolyte or a gel polymer electrolyte is used.
- a gel polymer electrolyte By using the gel polymer electrolyte, the distance between the electrodes is stabilized, the occurrence of polarization is suppressed, and the durability (cycle characteristics) is improved.
- the liquid electrolyte functions as a lithium ion carrier.
- the liquid electrolyte constituting the electrolytic solution layer has a form in which a lithium salt as a supporting salt is dissolved in an organic solvent as a plasticizer.
- organic solvent include carbonates such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate.
- EC ethylene carbonate
- PC propylene carbonate
- DMC dimethyl carbonate
- DEC diethyl carbonate
- ethyl methyl carbonate ethyl methyl carbonate.
- Li (CF 3 SO 2) 2 N Li (C 2 F 5 SO 2) 2 N, LiPF 6, LiBF 4, LiClO 4, LiAsF 6, LiTaF such 6, LiCF 3 SO 3
- a compound that can be added to the active material layer of the electrode can be similarly employed.
- the liquid electrolyte may further contain additives other than the components described above.
- additives include, for example, vinylene carbonate, methyl vinylene carbonate, dimethyl vinylene carbonate, phenyl vinylene carbonate, diphenyl vinylene carbonate, ethyl vinylene carbonate, diethyl vinylene carbonate, vinyl ethylene carbonate, 1,2-divinyl ethylene carbonate.
- vinylene carbonate, methyl vinylene carbonate, and vinyl ethylene carbonate are preferable, and vinylene carbonate and vinyl ethylene carbonate are more preferable.
- These cyclic carbonates may be used alone or in combination of two or more.
- the gel polymer electrolyte has a configuration in which the above liquid electrolyte is injected into a matrix polymer (host polymer) made of an ion conductive polymer.
- a gel polymer electrolyte as the electrolyte is superior in that the fluidity of the electrolyte is lost and the ion conductivity between the layers is easily cut off.
- ion conductive polymer used as the matrix polymer (host polymer) examples include polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyacrylonitrile (PAN), polyvinylidene fluoride-hexafluoropropylene ( PVdF-HEP), poly (methyl methacrylate (PMMA), and copolymers thereof.
- PEO polyethylene oxide
- PPO polypropylene oxide
- PEG polyethylene glycol
- PAN polyacrylonitrile
- PVdF-HEP polyvinylidene fluoride-hexafluoropropylene
- PMMA methyl methacrylate
- the matrix polymer of gel electrolyte can express excellent mechanical strength by forming a crosslinked structure.
- thermal polymerization, ultraviolet polymerization, radiation polymerization, electron beam polymerization, etc. are performed on a polymerizable polymer (for example, PEO or PPO) for forming a polymer electrolyte using an appropriate polymerization initiator.
- a polymerization treatment may be performed.
- the separator is preferably a separator in which a heat-resistant insulating layer is laminated on a porous substrate (a separator with a heat-resistant insulating layer).
- the heat resistant insulating layer is a ceramic layer containing inorganic particles and a binder.
- a highly heat-resistant separator having a melting point or a heat softening point of 150 ° C. or higher, preferably 200 ° C. or higher is used.
- the separator is less likely to curl in the battery manufacturing process due to the effect of suppressing thermal shrinkage and high mechanical strength.
- the inorganic particles in the heat resistant insulating layer contribute to the mechanical strength and heat shrinkage suppressing effect of the heat resistant insulating layer.
- the material used as the inorganic particles is not particularly limited. Examples thereof include silicon, aluminum, zirconium, titanium oxides (SiO 2 , Al 2 O 3 , ZrO 2 , TiO 2 ), hydroxides and nitrides, and composites thereof. These inorganic particles may be derived from mineral resources such as boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine and mica, or may be artificially produced. Moreover, only 1 type may be used individually for these inorganic particles, and 2 or more types may be used together. Of these, silica (SiO 2 ) or alumina (Al 2 O 3 ) is preferably used, and alumina (Al 2 O 3 ) is more preferably used from the viewpoint of cost.
- the basis weight of the heat-resistant particles is not particularly limited, but is preferably 5 to 15 g / m 2 . If it is this range, sufficient ion conductivity will be acquired and it is preferable at the point which maintains heat resistant strength.
- the binder in the heat-resistant insulating layer has a role of adhering the inorganic particles and the inorganic particles to the resin porous substrate layer.
- the heat resistant insulating layer is stably formed, and peeling between the porous substrate layer and the heat resistant insulating layer is prevented.
- the binder used for the heat-resistant insulating layer is not particularly limited.
- a compound such as butadiene rubber, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), or methyl acrylate can be used as the binder.
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- PVF polyvinyl fluoride
- methyl acrylate methyl acrylate
- PVDF polyvinylidene fluoride
- these compounds only 1 type may be used independently and 2 or more types may be used together.
- the binder content in the heat-resistant insulating layer is preferably 2 to 20% by weight with respect to 100% by weight of the heat-resistant insulating layer.
- the binder content is 2% by weight or more, the peel strength between the heat-resistant insulating layer and the porous substrate layer can be increased, and the vibration resistance of the separator can be improved.
- the binder content is 20% by weight or less, the gap between the inorganic particles is appropriately maintained, so that sufficient lithium ion conductivity can be ensured.
- the thermal contraction rate of the separator with a heat-resistant insulating layer is preferably 10% or less for both MD and TD after holding for 1 hour at 150 ° C. and 2 gf / cm 2 .
- a current collector plate (tab) electrically connected to a current collector is taken out of a laminate film as an exterior material for the purpose of taking out current outside the battery.
- the material constituting the current collector plate is not particularly limited, and a known highly conductive material conventionally used as a current collector plate for a lithium ion secondary battery can be used.
- a constituent material of the current collector plate for example, metal materials such as aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof are preferable. From the viewpoint of light weight, corrosion resistance, and high conductivity, aluminum and copper are more preferable, and aluminum is particularly preferable. Note that the same material may be used for the positive electrode current collector plate (positive electrode tab) and the negative electrode current collector plate (negative electrode tab), or different materials may be used.
- the tabs 58 and 59 shown in FIG. 2 are not particularly limited.
- the positive electrode tab 58 and the negative electrode tab 59 may be drawn out from the same side, or the positive electrode tab 58 and the negative electrode tab 59 may be divided into a plurality of parts and taken out from each side, as shown in FIG. It is not limited to.
- a terminal may be formed using a cylindrical can (metal can).
- the seal portion is a member unique to the serially stacked battery and has a function of preventing leakage of the electrolyte layer. In addition to this, it is possible to prevent current collectors adjacent in the battery from coming into contact with each other and a short circuit due to a slight unevenness at the end of the laminated electrode.
- the constituent material of the seal part is not particularly limited, but polyolefin resin such as polyethylene and polypropylene, epoxy resin, rubber, polyimide and the like can be used. Among these, it is preferable to use a polyolefin resin from the viewpoints of corrosion resistance, chemical resistance, film-forming property, economy, and the like.
- ⁇ Positive terminal lead and negative terminal lead> As a material for the negative electrode and the positive electrode terminal lead, a lead used in a known laminated secondary battery can be used.
- the parts removed from the battery exterior material should be heat-insulating so that they do not affect products (for example, automobile parts, especially electronic devices) by touching peripheral devices or wiring and causing leakage. It is preferable to coat with a heat shrinkable tube or the like.
- Laminate film A conventionally known metal can case can be used as the exterior material.
- the power generation element 17 may be packed using a laminate film 22 as shown in FIG.
- the laminate film can be configured as a three-layer structure in which, for example, polypropylene, aluminum, and nylon are laminated in this order.
- the manufacturing method in particular of a lithium ion secondary battery is not restrict
- a lithium ion secondary battery is not limited to this.
- the electrode (positive electrode and negative electrode) is prepared, for example, by preparing an active material slurry (positive electrode active material slurry or negative electrode active material slurry) and applying the active material slurry onto a current collector. It can be made by drying, then pressing.
- the active material slurry includes the above-described active material (positive electrode active material or negative electrode active material), a binder, a conductive additive, and a solvent.
- the solvent is not particularly limited, and N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide, cyclohexane, hexane, water and the like can be used.
- NMP N-methyl-2-pyrrolidone
- the method for applying the active material slurry to the current collector is not particularly limited, and examples thereof include a screen printing method, a spray coating method, an electrostatic spray coating method, an ink jet method, and a doctor blade method.
- the method for drying the coating film formed on the surface of the current collector is not particularly limited as long as at least a part of the solvent in the coating film is removed.
- An example of the drying method is heating. Drying conditions (drying time, drying temperature, etc.) can be appropriately set according to the volatilization rate of the solvent contained in the applied active material slurry, the coating amount of the active material slurry, and the like. A part of the solvent may remain. The remaining solvent can be removed by a press process described later.
- the pressing means is not particularly limited, and for example, a calendar roll, a flat plate press, or the like can be used.
- the single cell layer can be produced by laminating the electrodes (positive electrode and negative electrode) produced in (1) via an electrolyte layer.
- the power generation element can be produced by laminating the single cell layers in consideration of the output and capacity of the single cell layer, the output and capacity required for the battery, and the like.
- the structure of the battery various shapes such as a square, a paper, a laminated, a cylindrical, and a coin can be adopted.
- the current collector and insulating plate of the component parts are not particularly limited, and may be selected according to the above shape.
- a stacked battery is preferable.
- a lead is joined to the current collector of the power generation element obtained above, and the positive electrode lead or the negative electrode lead is joined to the positive electrode tab or the negative electrode tab.
- a power generation element is placed in a laminate sheet so that the positive electrode tab and the negative electrode tab are exposed to the outside of the battery, and an electrolytic solution is injected with a liquid injector and then sealed in a vacuum to produce a stacked battery. sell.
- the initial charge treatment, gas removal treatment and activation treatment are further performed under the following conditions.
- it is done (see Example 1).
- the three sides of the laminate sheet (exterior material) are completely sealed in a rectangular shape by thermocompression when sealing in the production of the laminated battery of (4) so that the gas removal treatment can be performed. Stop (main sealing), and the remaining one side is temporarily sealed by thermocompression bonding.
- the remaining one side may be freely opened and closed by, for example, clip fastening, but from the viewpoint of mass production (production efficiency), it is preferable to temporarily seal the side by thermocompression bonding.
- thermocompression it is only necessary to adjust the temperature and pressure for pressure bonding.
- it can be opened by lightly applying force, and after degassing, it may be sealed again by thermocompression, or finally completely sealed by thermocompression ( Main sealing).
- the battery aging treatment is preferably performed as follows. At 25 ° C., a constant current charging method is used for 0.05 C for 4 hours (SOC approximately 20%). Next, after charging to 4.45 V at a 0.1 C rate at 25 ° C., the charging is stopped, and the state (SOC is about 70%) is maintained for about 2 days (48 hours).
- thermocompression bonding Next, the following process is performed as the first (first) gas removal process. First, one side temporarily sealed by thermocompression bonding is opened, gas is removed at 10 ⁇ 3 hPa for 5 minutes, and then thermocompression bonding is performed again to perform temporary sealing. Further, pressurization with a roller (surface pressure 0.5 ⁇ 0.1 MPa) is performed, and the electrode and the separator are sufficiently adhered.
- the battery is charged at 25 ° C. by a constant current charging method until the voltage reaches 4.45 V at 0.1 C, and then discharged twice to 2.0 V at 0.1 C.
- a cycle of discharging to 2.0 V at 0.1 C once is 4.65 V at 0.1 C.
- the battery is charged until it reaches 0, and then discharged once at 0.1 C to 2.0 V.
- a cycle of charging at 0.1 C to 4.75 V by a constant current charging method at 25 ° C. and then discharging to 0.1 V at 0.1 C may be performed once.
- the constant current charging method is used as the activation processing method, and the electrochemical pretreatment method when the voltage is set as the termination condition is described as an example, but the charging method is a constant current constant voltage charging method. You may use. Further, as the termination condition, a charge amount or time may be used in addition to the voltage.
- thermocompression bonding Next, the following process is performed as the first (first) gas removal process. First, one side temporarily sealed by thermocompression bonding is opened, gas is removed at 10 ⁇ 3 hPa for 5 minutes, and then thermocompression bonding is performed again to perform main sealing. Further, pressurization with a roller (surface pressure 0.5 ⁇ 0.1 MPa) is performed, and the electrode and the separator are sufficiently adhered.
- the performance and durability of the obtained battery can be improved by performing the initial charging process, the gas removal process, and the activation process described above.
- the assembled battery is configured by connecting a plurality of batteries. Specifically, at least two or more are used, and are configured by serialization, parallelization, or both. Capacitance and voltage can be freely adjusted by paralleling in series.
- a small assembled battery that can be attached and detached by connecting a plurality of batteries in series or in parallel. Then, a plurality of small assembled batteries that can be attached and detached are connected in series or in parallel to provide a large capacity and large capacity suitable for vehicle drive power supplies and auxiliary power supplies that require high volume energy density and high volume output density.
- An assembled battery having an output can also be formed. How many batteries are connected to make an assembled battery, and how many small assembled batteries are stacked to make a large-capacity assembled battery depends on the battery capacity of the mounted vehicle (electric vehicle) It may be determined according to the output.
- the electric device of the present invention including the lithium ion secondary battery according to the present embodiment maintains a discharge capacity even when used for a long time, and has good cycle characteristics. Furthermore, the volume energy density is high. Vehicle applications such as electric vehicles, hybrid electric vehicles, fuel cell vehicles, and hybrid fuel cell vehicles require higher capacity, larger size, and longer life than electric and portable electronic devices. . Therefore, the lithium ion secondary battery (electric device) can be suitably used as a vehicle power source, for example, as a vehicle driving power source or an auxiliary power source.
- a battery or an assembled battery formed by combining a plurality of these batteries can be mounted on the vehicle.
- a plug-in hybrid electric vehicle having a long EV mileage or an electric vehicle having a long charge mileage can be formed by mounting such a battery.
- a car a hybrid car, a fuel cell car, an electric car (four-wheeled vehicles (passenger cars, trucks, buses, commercial vehicles, light cars, etc.) This is because it can be used for motorcycles (including motorcycles) and tricycles) to provide a long-life and highly reliable automobile.
- the application is not limited to automobiles.
- it can be applied to various power sources for moving vehicles such as other vehicles, for example, trains, and power sources for mounting such as uninterruptible power supplies. It is also possible to use as.
- Example 1 Solid solution positive electrode active material C1 (Preparation of aqueous solution of titanium citrate complex) 60 g (0.3 mol) of anhydrous citric acid (molecular weight 192.12 g / mol) was added to 400 ml of acetone and heated to 60 ° C. to dissolve. Next, 56 g (0.2 mol) of titanium tetraisopropoxide (molecular weight 284.22 g / mol) was added to form a precipitate. This liquid was subjected to suction filtration to obtain a precipitate (light yellow).
- Ti concentration was 5.0% by weight as TiO 2 (molecular weight 79.87 g / mol).
- the obtained melted solution (slurry) was sprayed by heating at 200 ° C. to 400 ° C. and dried.
- the obtained dry powder was vacuum-dried at 140 ° C. to 250 ° C. for 12 hours and then calcined at 450 ° C. for 12 hours. Thereafter, the main baking was performed at 900 ° C. for 12 hours.
- Cu-K ⁇ rays were used as the X-ray source, and the measurement conditions were a tube voltage of 40 KV, a tube current of 20 mA, a scanning speed of 2 ° / min, a divergence slit width of 0.5 °, and a light receiving slit width of 0.15 °.
- FIG. 3 shows a positive electrode active material C0 having the following composition that does not contain Ti for comparison.
- the X-ray diffraction pattern of is shown.
- FIG. 4 shows an X-ray diffraction pattern of the solid solution positive electrode active material C1.
- 3 and 4 show a peak attributed to the superlattice structure characteristic of the solid solution system at 20-23 °. Furthermore, in FIG. 4, the peaks at 36.5-37.5 (101) and 44-45 ° (104) and 64-65 ° (108) / 65-66 (110) are slightly shifted to the lower angle side. It was observed. Further, no diffraction peak attributed to the spinel phase was observed in any sample.
- composition of slurry for positive electrode had the following composition.
- Cathode active material Ti-substituted solid solution cathode active material C1 obtained above 9.4 parts by weight
- Conductive aid flake graphite 0.15 parts by weight
- Acetylene black 0.15 parts by weight
- Binder Polyvinylidene fluoride (PVDF) 0 .3 parts by weight
- Solvent 8.2 parts by weight of N-methyl-2-pyrrolidone (NMP).
- a positive electrode slurry having the above composition was prepared as follows. First, 4.0 parts by weight of a solvent (NMP) is added to 2.0 parts by weight of a 20% binder solution obtained by dissolving a binder in a solvent (NMP) into a 50 ml disposable cup, and a stirring defoaming machine (spinning revolving mixer: Awatori) A binder diluted solution was prepared by stirring for 1 minute with Rentaro AR-100).
- NMP solvent
- NMP spinning revolving mixer
- the positive electrode slurry was applied to one side of an aluminum current collector with a thickness of 20 ⁇ m using an automatic coating apparatus (Doctor blade manufactured by Tester Sangyo: PI-1210 automatic coating apparatus). Subsequently, the current collector coated with the positive electrode slurry was dried on a hot plate (100 ° C. to 110 ° C., drying time 30 minutes), and the amount of NMP remaining in the positive electrode active material layer was 0.02 wt%.
- a sheet-like positive electrode was formed as follows.
- the sheet-like positive electrode was compression-molded by applying a roller press and cut to prepare a positive electrode having a weight of about 17.0 mg / cm 2 and a density of 2.65 g / cm 3 of the positive electrode active material layer on one side.
- Si 29 Ti 62 Ge 9 was used as the Si-containing alloy as the negative electrode active material.
- the Si-containing alloy was produced by a mechanical alloy method. Specifically, using a planetary ball mill device P-6 manufactured by Fricht, Germany, zirconia pulverized balls and alloy raw material powders were charged into a zirconia pulverized pot and alloyed at 600 rpm for 48 hours.
- Si-containing alloy Si 29 Ti 62 Ge 9
- other alloys that can be used in the present invention Si x Ti y Ge z A a , Si x Ti y Zn z A a , and Si this of x Ti y Sn z a, Si 29 Ti 62 Ge 9 except one
- Si x Ti y Ge z A a Si x Ti y Zn z A a
- Si this of x Ti y Sn z a, Si 29 Ti 62 Ge 9 except one also, since those having the same characteristics as Si 29 Ti 62 Ge 9, using Si 29 Ti 62 Ge 9 The same or similar results as in the examples are obtained.
- composition of slurry for negative electrode The negative electrode slurry had the following composition.
- Negative electrode active material Si-containing alloy (Si 29 Ti 62 Ge 9 ) 1.38 parts by weight Carbon material (manufactured by Hitachi Chemical, graphite) 7.82 parts by weight
- Conductive auxiliary agent SuperP 0.40 part by weight
- Binder Polyvinylidene fluoride ( PVDF) 0.40 parts by weight
- Solvent N-methyl-2-pyrrolidone (NMP) 10.0 parts by weight.
- a negative electrode slurry having the above composition was prepared as follows. First, 5.0 parts by weight of a solvent (NMP) was added to 2.0 parts by weight of a 20% binder solution obtained by dissolving a binder in a solvent (NMP), and the mixture was stirred for 1 minute with a stirring deaerator to prepare a diluted binder solution. To this binder diluted solution, 0.4 parts by weight of conductive additive, 9.2 parts by weight of negative electrode active material powder, and 5.0 parts by weight of solvent (NMP) are added and stirred for 3 minutes with a stirring defoamer for the negative electrode. A slurry (solid content concentration 50 wt%) was obtained.
- NMP solvent
- the negative electrode slurry was applied to one side of a 10 ⁇ m thick electrolytic copper current collector using an automatic coating apparatus. Subsequently, the current collector coated with the negative electrode slurry was dried on a hot plate (100 ° C. to 110 ° C., drying time 30 minutes), and the amount of NMP remaining in the negative electrode active material layer was 0.02 wt% or less. A sheet-like negative electrode was formed.
- the obtained sheet-like negative electrode was compression-molded by a roller press and cut to prepare a negative electrode having a weight of about 8.54 mg / cm 2 and a density of 1.45 g / cm 3 of the negative electrode active material layer on one side. When the surface of this negative electrode was observed, no cracks were observed.
- ethylene carbonate (EC) and diethyl carbonate (DEC) 1 in a mixed nonaqueous solvent were mixed at a volume ratio, the concentration of LiPF 6 a (lithium hexafluorophosphate) 1M What was dissolved so that it might become was used.
- LiPF 6 a lithium hexafluorophosphate
- the battery is evaluated by the constant current constant voltage charging method in which the battery is charged at a 0.1 C rate until the maximum voltage reaches 4.5 V and then held for about 1 to 1.5 hours.
- the constant current discharge method was used in which discharge was performed at a 0.1 C rate until the minimum voltage reached 2.0V.
- the discharge capacity at the 0.1 C rate at this time was defined as “0.1 C discharge capacity (mAh / g)”.
- the discharge capacity per active material of the positive electrode C1 was 221 mAh / g, and the discharge capacity per electrode unit area was 3.61 mAh / cm 2 .
- ethylene carbonate (EC) and diethyl carbonate (DEC) 1 in a mixed nonaqueous solvent were mixed at a volume ratio, the concentration of LiPF 6 a (lithium hexafluorophosphate) 1M What was dissolved so that it might become was used.
- LiPF 6 a lithium hexafluorophosphate
- the battery is evaluated by a constant current / constant voltage charging method in which charging (the Li insertion process into the negative electrode to be evaluated) is charged from 2 V to 10 mV at a 0.1 C rate and then held for about 1 to 1.5 hours.
- the constant current mode was used, and a constant current discharge method was performed in which discharge was performed from 10 mV to 2 V at a 0.1 C rate.
- the discharge capacity at the 0.1 C rate at this time was defined as “0.1 C discharge capacity (mAh / g)”.
- the discharge capacity per active material of the negative electrode A1 was 570 mAh / g, and the discharge capacity per electrode unit area was 4.08 mAh / cm 2 .
- the positive electrode C1 obtained above was cut out so as to have an active material layer area of 2.5 cm in length and 2.0 cm in width, and the two current collectors faced each other, so that the uncoated surface (aluminum current collector)
- the current collector portion was spot welded together with the surface not coated with the foil slurry.
- an aluminum positive electrode tab positive electrode current collector plate
- the negative electrode A1 obtained above was cut out so as to have an active material layer area of 2.7 cm in length and 2.2 cm in width, and then a negative electrode tab of electrolytic copper was further welded to the current collector portion to form a negative electrode A11.
- the negative electrode A11 has a structure in which a negative electrode active material layer is formed on one surface of a current collector.
- a porous polypropylene separator (S) (length 3.0 cm ⁇ width 2.5 cm, thickness 25 ⁇ m, porosity 55%) is sandwiched between the negative electrode A11 to which these tabs are welded and the positive electrode C11.
- a laminated power generation element was produced.
- the structure of the stacked type power generation element is the structure of negative electrode (single side) / separator / positive electrode (both sides) / separator / negative electrode (single side), that is, A11- (S) -C11- (S) -A11. The configuration.
- both sides of the power generation element were sandwiched with an aluminum laminate film exterior material (length 3.5 cm ⁇ width 3.5 cm), and the above power generation element was accommodated by thermocompression sealing at three sides.
- LiPF 6 electrolyzed ethylene carbonate
- DEC diethyl carbonate
- lithium lithium fluorophosphate LiPO 2 F 2
- MMDS methylenemethane disulfonic acid
- Example 1 a positive electrode and a negative electrode were produced according to Example 1. That is, a positive electrode and a negative electrode were produced in the same manner as in Example 1 described above except as otherwise noted below.
- positive electrodes C2 to C13 were produced in the same manner as the positive electrode C1, except that the composition of the solid solution positive electrode active material was changed as shown in Table 1 below.
- Table 1 charge / discharge capacity per unit active material weight (mAh / g), positive electrode coating amount (mg / cm 2 ), and charge / discharge capacity per unit area of the positive electrode active material layer are shown. The value of (mAh / cm 2 ) is also shown.
- negative electrodes A2 to A14 were prepared in the same manner as the negative electrode A1, except that the composition of the negative electrode active material comprising the Si-containing alloy and the composition of the negative electrode active material layer were changed as shown in Table 2 below. (Si-containing alloy is not used in the negative electrode A13). Table 2 shows the charge / discharge capacity (mAh / g) per active material weight of the Si-containing alloy used, the weight ratio (% by weight) of the Si-containing alloy in the negative electrode active material, and the active material weight of the negative electrode active material.
- Table 2 shows the charge / discharge capacity (mAh / g) per active material weight of the Si-containing alloy used, the weight ratio (% by weight) of the Si-containing alloy in the negative electrode active material, and the active material weight of the negative electrode active material.
- the charge / discharge capacity per unit area (mAh / g), the coating amount of the negative electrode (mg / cm 2 ), and the charge / discharge capacity per unit area of the negative electrode active material layer (mAh / cm 2 ) are also shown.
- the power generation element of each battery obtained above was set on an evaluation cell mounting jig, and a positive electrode lead and a negative electrode lead were attached to each tab end of the power generation element, and a test was performed.
- the battery aging treatment was performed as follows. At 25 ° C., the battery was charged at a constant current charging method of 0.05 C for 4 hours (SOC approximately 20%). Next, after charging to 4.45 V at a 0.1 C rate at 25 ° C., the charging was stopped and the state (SOC about 70%) was maintained for about 2 days (48 hours).
- thermocompression bonding One side temporarily sealed by thermocompression bonding was opened, gas was removed at 10 ⁇ 3 hPa for 5 minutes, and then thermocompression bonding was performed again to perform temporary sealing. Further, pressurization with a roller (surface pressure 0.5 ⁇ 0.1 MPa) was performed, and the electrode and the separator were sufficiently adhered.
- thermocompression bonding One side temporarily sealed by thermocompression bonding was opened, gas was removed at 10 ⁇ 3 hPa for 5 minutes, and then thermocompression bonding was performed again to perform main sealing. Further, pressurization with a roller (surface pressure 0.5 ⁇ 0.1 MPa) was performed, and the electrode and the separator were sufficiently adhered.
- Rate performance evaluation The rate performance of the battery is evaluated by a constant current / constant voltage charging method in which the battery is charged at a 0.1 C rate until the maximum voltage reaches 4.5 V and then held for about 1 hour to 1.5 hours. This was carried out by a constant current discharge method in which discharge was performed at a 0.1 C rate or a 2.5 C rate until the minimum voltage of 2.0 V became 2.0 V. All were performed at room temperature. The rate characteristics were evaluated as the ratio of the capacity at 2.5 C discharge to the capacity at 0.1 C discharge. The results are shown in Table 3 below.
- the ratio of the discharge capacity at the 100th cycle to the discharge capacity at the 1st cycle was evaluated as “capacity maintenance rate (%)”. The results are shown in Table 3 below.
- Capacity retention rate (%) 100th cycle discharge capacity / 1st cycle discharge capacity ⁇ 100
- the lithium ion secondary batteries of Examples 1 to 27, which are electrical devices according to the present invention have cycle characteristics (capacity maintenance at the 100th cycle) as compared with Comparative Examples 1 to 5. Rate) and rate characteristics (2.5C / 0.1C capacity retention ratio) showed excellent characteristics.
- Comparative Example 1 and Comparative Example 4 using the negative electrode A13 sufficient rate characteristics cannot be achieved as the amount of application of the negative electrode active material layer becomes too large.
- Comparative Example 2 and Comparative Example 5 using the negative electrode A14 sufficient application of the negative electrode active material layer was too small and an excessive load was applied to the negative electrode active material, so that sufficient cycle durability was achieved. Absent.
- Comparative Example 3 using the positive electrode C13 containing a solid solution positive electrode active material in which Mn is not substituted with another metal sufficient cycle durability could not be achieved even when the negative electrode A1 was used.
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Abstract
Description
前記負極活物質層の塗布量が3~11mg/cm2であり、
前記負極活物質層が、下記式(1):
で表される負極活物質を含有し、
前記正極活物質層が、下記式(2):
で表される正極活物質を含有し、この際、前記固溶体正極活物質は、下記式(3):
で表される組成を有する、電気デバイスが提供される。
図1は、本発明の電気デバイスの代表的な一実施形態である、扁平型(積層型)のリチウムイオン二次電池(以下、単に「積層型電池」ともいう)の全体構造を模式的に表した断面概略図である。
活物質層(13、15)は活物質を含み、必要に応じてその他の添加剤をさらに含む。
正極活物質層13は、少なくとも固溶体材料からなる正極活物質(本明細書中、「固溶体正極活物質」とも称する)を含む。
固溶体正極活物質は、下記式(3)で表される組成を有する。
第1工程では、Ti、ZrおよびNbの少なくとも一種のクエン酸塩および融点が100℃~350℃の遷移金属の有機酸塩とを混合する。Ti、ZrおよびNbの少なくとも一種のクエン酸塩は、好ましくは、クエン酸錯体水溶液の形態で混合する。Ti、ZrおよびNbの少なくとも一種のクエン酸錯体水溶液は、以下に限定はされないが、好ましくは以下のように調製できる。
第1工程で得られた混合物を、100℃~350℃、好ましくは200~300℃で融解する。
第2工程で得られた加熱溶融物(スラリー)を、第1工程で使用した遷移金属の有機酸塩の融点以上の温度で熱分解し、乾燥粉末である熱分解物を得る。複数の遷移金属の有機酸塩の融点がそれぞれ異なる場合には、最も高い融点以上の温度で熱分解する。より詳細には、溶融物をスプレー装置で、200~600℃、より好ましくは200~400℃で加熱噴霧することができる。
第3工程で得られた熱分解物を、600~1200℃、より好ましくは800~1100℃で、5~20時間、好ましくは10~15時間焼成する。焼成の前に仮焼成を行ってもよく、その場合は、200~700℃、より好ましくは300~600℃で、1~10時間、より好ましくは2~6時間仮焼成することができる。このようにして、本実施形態の正極活物質が得られる。
正極活物質層に用いられるバインダとしては、特に限定されないが、例えば、以下の材料が挙げられる。ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート(PET)、ポリエーテルニトリル、ポリアクリロニトリル、ポリイミド、ポリアミド、セルロース、カルボキシメチルセルロース(CMC)およびその塩、エチレン-酢酸ビニル共重合体、ポリ塩化ビニル、スチレン・ブタジエンゴム(SBR)、イソプレンゴム、ブタジエンゴム、エチレン・プロピレンゴム、エチレン・プロピレン・ジエン共重合体、スチレン・ブタジエン・スチレンブロック共重合体およびその水素添加物、スチレン・イソプレン・スチレンブロック共重合体およびその水素添加物などの熱可塑性高分子、ポリフッ化ビニリデン(PVdF)、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・ヘキサフルオロプロピレン共重合体(FEP)、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合体(PFA)、エチレン・テトラフルオロエチレン共重合体(ETFE)、ポリクロロトリフルオロエチレン(PCTFE)、エチレン・クロロトリフルオロエチレン共重合体(ECTFE)、ポリフッ化ビニル(PVF)等のフッ素樹脂、ビニリデンフルオライド-ヘキサフルオロプロピレン系フッ素ゴム(VDF-HFP系フッ素ゴム)、ビニリデンフルオライド-ヘキサフルオロプロピレン-テトラフルオロエチレン系フッ素ゴム(VDF-HFP-TFE系フッ素ゴム)、ビニリデンフルオライド-ペンタフルオロプロピレン系フッ素ゴム(VDF-PFP系フッ素ゴム)、ビニリデンフルオライド-ペンタフルオロプロピレン-テトラフルオロエチレン系フッ素ゴム(VDF-PFP-TFE系フッ素ゴム)、ビニリデンフルオライド-パーフルオロメチルビニルエーテル-テトラフルオロエチレン系フッ素ゴム(VDF-PFMVE-TFE系フッ素ゴム)、ビニリデンフルオライド-クロロトリフルオロエチレン系フッ素ゴム(VDF-CTFE系フッ素ゴム)等のビニリデンフルオライド系フッ素ゴム、エポキシ樹脂等が挙げられる。これらのバインダは、単独で用いてもよいし、2種以上を併用してもよい。
導電助剤とは、正極活物質層または負極活物質層の導電性を向上させるために配合される添加物をいう。導電助剤としては、ケッチェンブラック、アセチレンブラック等のカーボンブラックが挙げられる。活物質層が導電助剤を含むと、活物質層の内部における電子ネットワークが効果的に形成され、電池の出力特性の向上に寄与しうる。
電解質塩(リチウム塩)としては、Li(C2F5SO2)2N、LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3等が挙げられる。
負極活物質層15は、負極活物質として、Si含有合金および炭素材料を必須に含む。
Si含有合金は、Siを含有する他の金属との合金であれば特に制限されず、従来公知の知見が適宜参照されうる。ここでは、Si含有合金の好ましい実施形態として、SixTiyGezAa、SixTiyZnzAa、SixTiySnzAa、SixSnyAlzAa、SixSnyVzAa、SixSnyCzAa、SixZnyVzAa、SixZnySnzAa、SixZnyAlzAa、SixZnyCzAa、SixAlyCzAaおよびSixAlyNbzAa(式中、Aは、不可避不純物である。さらに、x、y、z、およびaは、重量%の値を表し、0<x<100、0<y<100、0<z<100、および0≦a<0.5であり、x+y+z+a=100である)が挙げられる。これらのSi含有合金を負極活物質として用いることで、所定の第1添加元素および所定の第2添加元素を適切に選択することによって、Li合金化の際に、アモルファス-結晶の相転移を抑制してサイクル寿命を向上させることができる。また、これによって、従来の負極活物質、例えば炭素系負極活物質よりも高容量のものとなる。
本発明に用いられうる炭素材料は、特に制限されないが、天然黒鉛、人造黒鉛等の高結晶性カーボンである黒鉛(グラファイト);ソフトカーボン、ハードカーボン等の低結晶性カーボン;ケッチェンブラック、アセチレンブラック、チャンネルブラック、ランプブラック、オイルファーネスブラック、サーマルブラック等のカーボンブラック;フラーレン、カーボンナノチューブ、カーボンナノファイバー、カーボンナノホーン、カーボンフィブリル等の炭素材料が挙げられる。これらのうち、黒鉛を用いることが好ましい。
集電体(11、12)は導電性材料から構成される。集電体の大きさは、電池の使用用途に応じて決定される。例えば、高エネルギー密度が要求される大型の電池に用いられるのであれば、面積の大きな集電体が用いられる。
セパレータは、電解質を保持して正極と負極との間のリチウムイオン伝導性を確保する機能、および正極と負極との間の隔壁としての機能を有する。
リチウムイオン二次電池においては、電池外部に電流を取り出す目的で、集電体に電気的に接続された集電板(タブ)が外装材であるラミネートフィルムの外部に取り出されている。
シール部は、直列積層型電池に特有の部材であり、電解質層の漏れを防止する機能を有する。このほかにも、電池内で隣り合う集電体同士が接触したり、積層電極の端部の僅かな不ぞろいなどによる短絡が起こったりするのを防止することもできる。
負極および正極端子リードの材料は、公知の積層型二次電池で用いられるリードを用いることができる。なお、電池外装材から取り出された部分は、周辺機器や配線などに接触して漏電したりして製品(例えば、自動車部品、特に電子機器等)に影響を与えないように、耐熱絶縁性の熱収縮チューブなどにより被覆するのが好ましい。
外装材としては、従来公知の金属缶ケースを用いることができる。そのほか、図1に示すようなラミネートフィルム22を外装材として用いて、発電要素17をパックしてもよい。ラミネートフィルムは、例えば、ポリプロピレン、アルミニウム、ナイロンがこの順に積層されてなる3層構造として構成されうる。このようなラミネートフィルムを用いることにより、外装材の開封、容量回復材の添加、外装材の再封止を容易に行うことができる。
リチウムイオン二次電池の製造方法は特に制限されず、公知の方法により製造されうる。具体的には、(1)電極の作製、(2)単電池層の作製、(3)発電要素の作製、および(4)積層型電池の製造を含む。以下、リチウムイオン二次電池の製造方法について一例を挙げて説明するが、これに限定されるものではない。
電極(正極または負極)は、例えば、活物質スラリー(正極活物質スラリーまたは負極活物質スラリー)を調製し、当該活物質スラリーを集電体上に塗布、乾燥し、次いでプレスすることにより作製されうる。前記活物質スラリーは、上述した活物質(正極活物質または負極活物質)、バインダ、導電助剤および溶媒を含む。
単電池層は、(1)で作製した電極(正極および負極)を、電解質層を介して積層させることにより作製されうる。
発電要素は、単電池層の出力および容量、電池として必要とする出力および容量等を適宜考慮し、前記単電池層を積層して作製されうる。
電池の構成としては、角形、ペーパー型、積層型、円筒型、コイン型等、種々の形状を採用することができる。また構成部品の集電体や絶縁板等は特に限定されるものではなく、上記の形状に応じて選定すればよい。しかし、本実施形態では積層型電池が好ましい。積層型電池は、上記で得られた発電要素の集電体にリードを接合し、これらの正極リードまたは負極リードを、正極タブまたは負極タブに接合する。そして、正極タブおよび負極タブが電池外部に露出するように、発電要素をラミネートシート中に入れ、注液機により電解液を注液してから真空に封止することにより積層型電池が製造されうる。
さらに、本実施形態では、上記により得られた積層型電池の性能および耐久性を高める観点から、さらに、以下の条件で初充電処理、ガス除去処理および活性化処理を行うことが好ましい(実施例1参照)。この場合には、ガス除去処理ができるように、上記(4)の積層型電池の製造において、封止する際に、矩形形状にラミネートシート(外装材)の3辺を熱圧着により完全に封止(本封止)し、残る1辺は、熱圧着で仮封止しておく。残る1辺は、例えば、クリップ留め等により開閉自在にしてもよいが、量産化(生産効率)の観点からは、熱圧着で仮封止するのがよい。この場合には、圧着する温度、圧力を調整するだけでよいためである。熱圧着で仮封止した場合には、軽く力を加えることで開封でき、ガス抜き後、再度、熱圧着で仮封止してもよいし、最後的には熱圧着で完全に封止(本封止)すればよい。
電池のエージング処理は、以下のように実施することが好ましい。25℃にて、定電流充電法で0.05C、4時間の充電(SOC約20%)を行う。次いで、25℃にて0.1Cレートで4.45Vまで充電した後、充電を止め、その状態(SOC約70%)で約2日間(48時間)保持する。
次に、最初(1回目)のガス除去処理として、以下の処理を行う。まず、熱圧着で仮封止した1辺を開封し、10±3hPaで5分間ガス除去を行った後、再度、熱圧着を行って仮封止を行う。さらに、ローラーで加圧(面圧0.5±0.1MPa)整形し電極とセパレータとを十分に密着させる。
次に、活性化処理法として、以下の電気化学前処理法を行う。
次に、最初(1回目)のガス除去処理として、以下の処理を行う。まず、熱圧着で仮封止した一辺を開封し、10±3hPaで5分間ガス除去を行った後、再度、熱圧着を行って本封止を行う。さらに、ローラーで加圧(面圧0.5±0.1MPa)整形し電極とセパレータとを十分に密着させる。
組電池は、電池を複数個接続して構成した物である。詳しくは少なくとも2つ以上用いて、直列化あるいは並列化あるいはその両方で構成されるものである。直列、並列化することで容量および電圧を自由に調節することが可能になる。
本実施形態に係るリチウムイオン二次電池をはじめとした本発明の電気デバイスは、長期使用しても放電容量が維持され、サイクル特性が良好である。さらに、体積エネルギー密度が高い。電気自動車やハイブリッド電気自動車や燃料電池車やハイブリッド燃料電池自動車などの車両用途においては、電気・携帯電子機器用途と比較して、高容量、大型化が求められるとともに、長寿命化が必要となる。したがって、上記リチウムイオン二次電池(電気デバイス)は、車両用の電源として、例えば、車両駆動用電源や補助電源に好適に利用することができる。
(固溶体正極活物質C1)
(チタンクエン酸錯体水溶液の調製)
無水クエン酸(分子量192.12g/mol)60g(0.3mol)をアセトン400mlに加え、60℃に加温し溶解した。次いで、チタンテトライソプロポキシド(分子量284.22g/mol)56g(0.2mol)を加え、沈殿を形成させた。この液を吸引濾過し沈殿物(薄黄色)を得た。
Li1.5[Ni0.450Mn0.750[Li]0.20Ti0.10]Oz
チタンクエン酸錯体水溶液(TiO2として5.0重量%)15.97gに、酢酸マンガン・4水和物(分子量245.09g/mol)14.71g、酢酸ニッケル・4水和物(分子量248.84g/mol)7.47g、酢酸リチウム・2水和物(分子量102.02g/mol)14.57gを順に加えた。得られた混合物を、200℃~300℃に加熱し溶融溶解した。次に、スプレードライ装置を用い、得られた溶融溶解液(スラリー)を200℃~400℃で加熱噴霧し、乾燥した。得られた乾燥粉末を、140℃~250℃で12時間真空乾燥した後、450℃で12時間仮焼成した。その後、900℃で12時間本焼成した。
組成式: Li1.5[Ni0.450Mn0.750[Li]0.20Ti0.10]Oz
a+b+c+d+e=1.5、d=0.20、a+b+c+e=1.30、e=0.10
(X線回折測定)
得られた固溶体正極活物質について、X線回折により、結晶構造および結晶性の評価をした。X線源にはCu-Kα線を用い、測定条件は管電圧40KV、管電流20mA、走査速度2°/分、発散スリット幅0.5°、受光スリット幅0.15°で行った。
組成式: Li1.5[Ni0.450Mn0.850[Li]0.20Ti0.00]Oz
のX線回折パターンを示す。さらに、図4に固溶体正極活物質C1のX線回折パターンを示す。
(正極用スラリーの組成)
正極用スラリーは下記組成とした。
導電助剤: 燐片状黒鉛 0.15重量部
アセチレンブラック 0.15重量部
バインダ: ポリフッ化ビニリデン(PVDF) 0.3重量部
溶媒: N-メチル-2-ピロリドン(NMP) 8.2重量部。
上記組成の正極用スラリーを次のように調製した。まず、50mlのディスポカップに、溶媒(NMP)にバインダを溶解した20%バインダ溶液2.0重量部に溶媒(NMP)4.0重量部を加え、攪拌脱泡機(自転公転ミキサー:あわとり錬太郎AR-100)で1分間攪拌してバインダ希釈溶液を作製した。次に、このバインダ希釈液に、導電助剤0.4重量部と固溶体正極活物質C1 9.2重量部、および溶媒(NMP)2.6重量部を加え、攪拌脱泡機で3分間攪拌して正極用スラリー(固形分濃度55重量%)とした。
20μm厚のアルミニウム集電体の片面に、上記正極用スラリーを自動塗工装置(テスター産業製ドクターブレード:PI-1210自動塗工装置)により塗布した。続いて、この正極用スラリーを塗布した集電体について、ホットプレートにて乾燥(100℃~110℃、乾燥時間30分)を行い、正極活物質層に残留するNMP量を0.02重量%以下として、シート状正極を形成した。
上記シート状正極を、ローラープレスをかけて圧縮成形し、切断して、片面の正極活物質層の重量約17.0mg/cm2、密度2.65g/cm3の正極を作製した。
次に、上記手順で作製した正極を用い真空乾燥炉にて乾燥処理を行った。乾燥炉内部に正極を設置した後、室温(25℃)にて減圧(100mmHg(1.33×104Pa))し乾燥炉内の空気を除去した。続いて、窒素ガスを流通(100cm3/分)しながら、10℃/分で120℃まで昇温し、120℃で再度減圧して炉内の窒素を排気したまま12時間保持した後、室温まで降温した。こうして正極表面の水分を除去した正極C1を得た。
負極活物質であるSi含有合金として、Si29Ti62Ge9を用いた。なお、上記Si含有合金は、メカニカルアロイ法により製造した。具体的には、ドイツ フリッチュ社製遊星ボールミル装置P-6を用いて、ジルコニア製粉砕ポットにジルコニア製粉砕ボールおよび合金の各原料粉末を投入し、600rpmで48時間かけて合金化させた。
負極用スラリーは下記組成とした。
炭素材料(日立化成製、黒鉛) 7.82重量部
導電助剤: SuperP 0.40重量部
バインダ: ポリフッ化ビニリデン(PVDF) 0.40重量部
溶媒: N-メチル-2-ピロリドン(NMP) 10.0重量部。
上記組成の負極用スラリーを次のように調製した。まず、溶媒(NMP)にバインダを溶解した20%バインダ溶液2.0重量部に溶媒(NMP)5.0重量部を加えて、攪拌脱泡機1分間攪拌してバインダ希釈溶液を作製した。このバインダ希釈液に、導電助剤0.4重量部、負極活物質粉末9.2重量部、および溶媒(NMP)5.0重量部を加え、攪拌脱泡機で3分間攪拌して負極用スラリー(固形分濃度50重量%)とした。
10μm厚の電解銅集電体の片面に、上記負極用スラリーを自動塗工装置により塗布した。続いて、この負極スラリーを塗布した集電体について、ホットプレートにて乾燥(100℃~110℃、乾燥時間30分)を行い、負極活物質層に残留するNMP量を0.02重量%以下として、シート状負極を形成した。
得られたシート状負極を、ローラープレスをかけて圧縮成形し、切断して、片面の負極活物質層の重量約8.54mg/cm2、密度1.45g/cm3の負極を作製した。この負極の表面を観察したところ、クラックの発生は見られなかった。
次に、上記手順で作製した負極を用い真空乾燥炉にて乾燥処理を行った。乾燥炉内部に負極を設置した後、室温(25℃)にて減圧(100mmHg(1.33×104Pa))し乾燥炉内の空気を除去した。続いて、窒素ガスを流通(100cm3/分)しながら、10℃/分で135℃まで昇温し、135で再度減圧して炉内の窒素を排気したまま12時間保持した後、室温まで降温した。こうして負極表面の水分を除去して、負極A1を得た。
[コインセルの作製]
上記により得られた正極C1(直径15mmに打抜き)とリチウム箔(本城金属株式会社製、直径16mm、厚さ200μm)からなる対極とをセパレータ(直径17mm、セルガード社製セルガード2400)を介して対向させたのち、電解液を注入することによってCR2032型コインセルを作製した。
25℃にて、定電流充電法で0.1Cで電圧が4.45Vとなるまで充電した後、0.1Cで2.0Vまで放電するサイクルを2回行った。同様に、25℃にて、定電流充電法で0.1Cで4.55Vとなるまで充電した後、0.1Cで2.0Vまで放電するサイクルを1回、0.1Cで4.65Vとなるまで充電した後、0.1Cで2.0Vまで放電するサイクルを1回行った。更に、25℃にて、定電流充電法で、0.1Cで4.75Vとなるまで充電した後、0.1Cで2.0Vまで放電するサイクルを1回行った。
電池の評価は、充電は、0.1Cレートにて最高電圧が4.5Vとなるまで充電した後、約1時間~1.5時間保持する定電流定電圧充電法とし、放電は、電池の最低電圧が2.0Vとなるまで0.1Cレートで放電する定電流放電法で行った。このときの0.1Cレートでの放電容量を「0.1C放電容量(mAh/g)」とした。
[コインセルの作製]
上記により得られた負極A1(直径15mmに打抜き)とリチウム箔(本城金属株式会社製、直径16mm、厚さ200μm)からなる対極とをセパレータ(直径17mm、セルガード社製セルガード2400)を介して対向させたのち、電解液を注入することによってCR2032型コインセルを作製した。
電池の評価は、充電(評価対象である負極へのLi挿入過程)は、0.1Cレートにて2Vから10mVまで充電した後、約1時間~1.5時間保持する定電流定電圧充電法とし、放電過程(上記負極からのLi脱離過程)では、定電流モードとし、0.1Cレートにて、10mVから2Vまで放電する定電流放電法で行った。このときの0.1Cレートでの放電容量を「0.1C放電容量(mAh/g)」とした。
上記で得られた正極C1を、活物質層面積;縦2.5cm×横2.0cmになるように切り出し、これら2枚を集電体同士が向き合うようにして、未塗工面(アルミニウム集電箔のスラリーを塗工していない面)を合わせて集電体部分をスポット溶接した。これにより、外周部をスポット溶接により一体化された2枚重ねの集電箔の両面に正極活物質層を有する正極を形成した。その後、さらに集電体部分にアルミニウムの正極タブ(正極集電板)を溶接して正極C11を形成した。すなわち、正極C11は、集電箔の両面に正極活物質層が形成された構成である。
上記で作製したラミネート型電池に対して、以下の条件で初充電処理および活性化処理を行い、性能を評価した。
電池のエージング処理は、以下のように実施した。25℃にて、定電流充電法で0.05C、4時間の充電(SOC約20%)を行った。次いで、25℃にて0.1Cレートで4.45Vまで充電した後、充電を止め、その状態(SOC約70%)で約2日間(48時間)保持した。
熱圧着で仮封止した一辺を開封し、10±3hPaで5分間ガス除去を行った後、再度、熱圧着を行い仮封止を行った。さらに、ローラーで加圧(面圧0.5±0.1MPa)成形し電極とセパレータとを十分に密着させた。
25℃にて、定電流充電法で0.1Cで電圧が4.45Vとなるまで充電した後、0.1Cで2.0Vまで放電するサイクルを2回行った。同様に、25℃にて、定電流充電法で0.1Cで4.55Vとなるまで充電した後、0.1Cで2.0Vまで放電するサイクルを1回、0.1Cで4.65Vとなるまで充電した後、0.1Cで2.0Vまで放電するサイクルを1回行った。更に、25℃にて、定電流充電法で、0.1Cで4.75Vとなるまで充電した後、0.1Cで2.0Vまで放電するサイクルを1回行った。
熱圧着で仮封止した一辺を開封し、10±3hPaで5分間ガス除去を行った後、再度、熱圧着を行い本封止を行った。さらに、ローラーで加圧(面圧0.5±0.1MPa)成形し電極とセパレータとを十分に密着させた。
電池のレート性能評価は、充電は0.1Cレートにて最高電圧が4.5Vとなるまで充電した後、約1時間~1.5時間保持する定電流定電圧充電法とし、放電は、電池の最低電圧が2.0Vとなるまで0.1Cレートまたは2.5Cレートで放電する定電流放電法で行った。いずれも、室温下で行った。レート特性は0.1C放電時の容量に対する2.5C放電時の容量の比率として評価した。結果を下記の表3に示す。
電池の寿命試験は、上記1.0Cレートでの充放電を、25℃で100サイクルを繰り返した。電池の評価は、充電は、0.1Cレートにて最高電圧が4.5Vとなるまで充電した後、約1時間~1.5時間保持する定電流定電圧充電法とし、放電は、電池の最低電圧が2.0Vとなるまで0.1Cレートで放電する定電流放電法で行った。いずれも、室温下で行った。
11 負極集電体、
12 正極集電体、
13 負極活物質層、
15 正極活物質層、
17 セパレータ、
19 単電池層、
21、57 発電要素、
25 負極集電板、
27 正極集電板、
29、52 電池外装材、
58 正極タブ、
59 負極タブ。
Claims (6)
- 正極集電体の表面に正極活物質を含む正極活物質層が形成されてなる正極と、
負極集電体の表面に負極活物質を含む負極活物質層が形成されてなる負極と、
セパレータと、
を含む発電要素を有する電気デバイスであって、
前記負極活物質層の塗布量が3~11mg/cm2であり、
前記負極活物質層が、下記式(1):
で表される負極活物質を含有し、
前記正極活物質層が、下記式(2):
で表される正極活物質を含有し、この際、前記固溶体正極活物質は、下記式(3):
で表される組成を有する、電気デバイス。 - 前記固溶体正極活物質は、X線回折(XRD)測定において、20-23°、35-40°(101)、42-45°(104)および64-65(108)/65-66(110)に、岩塩型層状構造を示す回折ピークを有する、請求項1に記載の電気デバイス。
- 前記固溶体正極活物質は、X線回折(XRD)測定において、岩塩型層状構造の回折ピーク以外に帰属されるピークを実質的に有していない、請求項1または2に記載の電気デバイス。
- 前記固溶体正極活物質が、X線回折(XRD)測定において、35-40°(101)に3つの回折ピークを有し、42-45°(104)に1つの回折ピークを有する、請求項1~3のいずれか1項に記載の電気デバイス。
- 前記固溶体正極活物質が、X線回折(XRD)測定において、20-23°、35.5-36.5°(101)、43.5-44.5°(104)および64-65(108)/65-66(110)に回折ピークを有する、請求項1~4のいずれか1項に記載の電気デバイス。
- リチウムイオン二次電池である、請求項1~5のいずれか1項に記載の電気デバイス。
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JP2017045651A (ja) * | 2015-08-27 | 2017-03-02 | 日産自動車株式会社 | リチウムイオン二次電池用正極活物質、リチウムイオン二次電池用正極及びリチウムイオン二次電池 |
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JP6123807B2 (ja) | 2012-11-22 | 2017-05-10 | 日産自動車株式会社 | リチウムイオン二次電池用負極、及びこれを用いたリチウムイオン二次電池 |
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JP2016018654A (ja) * | 2014-07-08 | 2016-02-01 | 株式会社日立製作所 | リチウムイオン二次電池 |
JP2017045651A (ja) * | 2015-08-27 | 2017-03-02 | 日産自動車株式会社 | リチウムイオン二次電池用正極活物質、リチウムイオン二次電池用正極及びリチウムイオン二次電池 |
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EP3098883A4 (en) | 2016-12-28 |
CN105934840B (zh) | 2019-03-15 |
JP6252600B2 (ja) | 2017-12-27 |
KR20160102054A (ko) | 2016-08-26 |
EP3098883A1 (en) | 2016-11-30 |
US20170012287A1 (en) | 2017-01-12 |
CN105934840A (zh) | 2016-09-07 |
KR101910721B1 (ko) | 2018-10-22 |
US9680150B2 (en) | 2017-06-13 |
EP3098883B1 (en) | 2017-11-22 |
JPWO2015111188A1 (ja) | 2017-03-23 |
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