WO2015012375A1 - 非水電解質二次電池用正極およびこれを用いた非水電解質二次電池 - Google Patents
非水電解質二次電池用正極およびこれを用いた非水電解質二次電池 Download PDFInfo
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- WO2015012375A1 WO2015012375A1 PCT/JP2014/069621 JP2014069621W WO2015012375A1 WO 2015012375 A1 WO2015012375 A1 WO 2015012375A1 JP 2014069621 W JP2014069621 W JP 2014069621W WO 2015012375 A1 WO2015012375 A1 WO 2015012375A1
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- Prior art keywords
- positive electrode
- active material
- electrode active
- secondary battery
- electrolyte secondary
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Images
Classifications
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Definitions
- the present invention relates to a positive electrode for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery using the same.
- a nonaqueous electrolyte secondary battery generally includes a positive electrode obtained by applying a positive electrode active material or the like to a current collector, and a negative electrode obtained by applying a negative electrode active material or the like to a current collector. It has the structure connected through the electrolyte layer holding electrolyte gel. Then, when ions such as lithium ions are occluded / released in the electrode active material, a charge / discharge reaction of the battery occurs.
- non-aqueous electrolyte secondary batteries with a low environmental load are being used not only for portable devices, but also for power supply devices for electric vehicles such as hybrid vehicles (HEV), electric vehicles (EV), and fuel cell vehicles. .
- HEV hybrid vehicles
- EV electric vehicles
- fuel cell vehicles fuel cell vehicles.
- Non-aqueous electrolyte secondary batteries intended for application to electric vehicles are required to have high output and high capacity. Research and development are underway with the aim of developing technology that satisfies these performances.
- Japanese Patent Application Laid-Open No. 7-122262 when a powdered electrode active material is used, the discharge capacity decreases when the film thickness exceeds a certain level, particularly during high output (or high current) discharge. Means are provided for solving the problem.
- Japanese Patent Application Laid-Open No. 7-122262 the above problem is solved by setting the specific surface area of the electrode in the nonaqueous electrolyte secondary battery to 4 m 2 / g or more.
- JP-A-7-122262 by setting the specific surface area to 4 m 2 / g or more, voids in the electrode increase and ion conduction is ensured. As a result, the discharge capacity is reduced even under high output conditions. Is considered to be prevented.
- an object of the present invention is to provide means capable of suppressing a decrease in discharge capacity under a high output condition while minimizing an increase in battery temperature in an overcharged state of the battery.
- the present inventor has intensively studied in view of the above problems.
- a conductive assistant is included in the positive electrode active material layer, the BET specific surface area is controlled to a predetermined value, and two or more kinds having different average particle diameters are used as the conductive assistant. It has been found that the above problem can be solved by controlling the relationship, and the present invention has been completed.
- a non-aqueous electrolyte secondary battery having a positive electrode current collector and a positive electrode active material layer formed on the surface of the positive electrode current collector and including a positive electrode active material and a conductive additive.
- a positive electrode is provided.
- the BET specific surface area of the positive electrode active material layer is 1 to 3 m 2 / g
- the conductive auxiliary agent is the first conductive auxiliary agent and the second conductive material having an average particle size larger than that of the first conductive auxiliary agent. It is characterized in that the content of the first conductive auxiliary agent in the positive electrode active material layer is greater than the content of the second conductive auxiliary agent in the positive electrode active material layer.
- FIG. 1 is a schematic cross-sectional view showing a basic configuration of a non-aqueous electrolyte lithium ion secondary battery that is not a flat (stacked) bipolar type, which is an embodiment of a nonaqueous electrolyte lithium ion secondary battery. It is a perspective view showing the appearance of a flat lithium ion secondary battery which is a typical embodiment of a secondary battery.
- a positive electrode current collector is formed on the surface of the positive electrode current collector, includes a positive electrode active material and a conductive additive, and has a BET specific surface area of 1 to 3 m 2 / g.
- a conductive layer wherein the conductive auxiliary agent includes a first conductive auxiliary agent and a second conductive auxiliary agent having an average particle size larger than that of the first conductive auxiliary agent, and the positive electrode active material layer includes the second conductive auxiliary agent.
- the BET specific surface area of the positive electrode active material layer is controlled within a predetermined range, and a conductive additive having a large average particle size is contained,
- the contact area with the constituent material of the positive electrode active material layer does not become too large. For this reason, an increase in battery temperature is suppressed even in an overcharged state of the battery.
- the conductive network in a positive electrode active material layer is ensured by containing more conductive support agents with a small average particle diameter. For this reason, a decrease in discharge capacity is prevented even under high output conditions, and excellent output characteristics are ensured.
- nonaqueous electrolyte lithium ion secondary battery will be described as a preferred embodiment of a nonaqueous electrolyte secondary battery to which the positive electrode according to the present embodiment is applied, but is not limited only to the following embodiment.
- the same elements are denoted by the same reference numerals, and redundant description is omitted.
- the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.
- FIG. 1 is a schematic cross-sectional view schematically showing a basic configuration of a non-aqueous electrolyte lithium ion secondary battery (hereinafter also simply referred to as “stacked battery”) that is not a flat (stacked) bipolar type.
- 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 battery exterior material 29 that is an exterior body.
- the power generation element 21 has a configuration in which a positive electrode, a separator 17, and a negative electrode are stacked.
- the separator 17 contains a nonaqueous electrolyte (for example, a liquid electrolyte).
- the positive electrode has a structure in which the positive electrode active material layers 15 are disposed on both surfaces of the positive electrode current collector 12.
- the negative electrode has a structure in which the negative electrode active material layer 13 is disposed on both surfaces of the negative electrode current collector 11.
- the negative electrode, the electrolyte layer, and the positive electrode are laminated in this order so that one positive electrode active material layer 15 and the negative electrode active material layer 13 adjacent thereto face each other with a separator 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 negative electrode active material layer 13 is arrange
- the arrangement of the positive electrode and the negative electrode is reversed from that in FIG. 1 so that the outermost positive electrode current collector is positioned on both outermost layers of the power generation element 21, A positive electrode active material layer may be disposed.
- the positive electrode current collector 12 and the negative electrode current collector 11 are each provided with a positive electrode current collector plate (tab) 27 and a negative electrode current collector plate (tab) 25 that are electrically connected to the respective electrodes (positive electrode and negative electrode). It has the structure led out of the battery exterior material 29 so that it may be pinched
- the positive electrode current collector plate 27 and the negative electrode current collector plate 25 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.
- FIG. 1 shows a flat battery (stacked battery) that is not a bipolar battery, but a positive electrode active material layer that is electrically coupled to one surface of the current collector and the opposite side of the current collector.
- a bipolar battery including a bipolar electrode having a negative electrode active material layer electrically coupled to the surface.
- one current collector also serves as a positive electrode current collector and a negative electrode current collector.
- the positive electrode has a positive electrode current collector and a positive electrode active material layer formed on the surface of the positive electrode current collector.
- a metal is preferably used.
- the metal include aluminum, nickel, iron, stainless steel, titanium, copper, and other alloys.
- 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, and copper are preferable from the viewpoints of electronic conductivity and battery operating potential.
- 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. There is no particular limitation on the thickness of the current collector.
- the thickness of the current collector is usually about 1 to 100 ⁇ m.
- a positive electrode active material layer contains a positive electrode active material.
- a positive electrode active material There is no restriction
- the positive electrode active material preferably contains a spinel-based lithium manganese composite oxide and / or a lithium-nickel composite oxide.
- preferred forms of these positive electrode active materials will be described.
- Spinel-based lithium manganese composite oxide is a composite oxide that typically has a composition of LiMn 2 O 4 and has a spinel structure and essentially contains lithium and manganese. Conventionally known knowledge can be appropriately referred to for the specific configuration and manufacturing method.
- Spinel-based lithium manganese composite oxide has a structure of secondary particles formed by agglomerating primary particles.
- the average particle diameter (average secondary particle diameter) of the secondary particles is preferably 5 to 50 ⁇ m, more preferably 7 to 20 ⁇ m.
- the average secondary particle diameter is measured by a laser diffraction method.
- lithium nickel complex oxide is not specifically limited as long as it is a complex oxide containing lithium and nickel.
- a typical example of a composite oxide containing lithium and nickel is lithium nickel composite oxide (LiNiO 2 ).
- a composite oxide in which some of the nickel atoms of the lithium nickel composite oxide are substituted with other metal atoms is more preferable.
- NMC composite lithium-nickel-manganese-cobalt composite oxide
- oxide (Also referred to as “oxide”) has a layered crystal structure in which a lithium atomic layer and a transition metal (Mn, Ni, and Co are arranged in order) are alternately stacked via an oxygen atomic layer.
- a lithium atomic layer Li atomic layer
- a transition metal Mn, Ni, and Co are arranged in order
- One Li atom is contained per atom, and the amount of Li that can be taken out is twice that of the spinel-type lithium manganese oxide, that is, the supply capacity is doubled, so that a high capacity can be obtained.
- LiNiO 2 since it has higher thermal stability than LiNiO 2 , it is particularly advantageous among the nickel-based composite oxides used as the positive electrode active material.
- the NMC composite oxide includes a composite oxide in which a part of the transition metal element is substituted with another metal element.
- Other elements in that case include Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr, Fe, B, Ga, In, Si, Mo, Y, Sn, V, Cu , Ag, Zn, etc., preferably Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr, more preferably Ti, Zr, P, Al, Mg, From the viewpoint of improving cycle characteristics, Ti, Zr, Al, Mg, and Cr are more preferable.
- a represents the atomic ratio of Li
- b represents the atomic ratio of Ni
- c represents the atomic ratio of Mn
- d represents the atomic ratio of Co
- x represents the atomic ratio of M. Represents. From the viewpoint of cycle characteristics, it is preferable that 0.4 ⁇ b ⁇ 0.6 in the general formula (1).
- the composition of each element can be measured by, for example, inductively coupled plasma (ICP) emission spectrometry.
- ICP inductively coupled plasma
- Ni nickel
- Co cobalt
- Mn manganese
- Ti or the like partially replaces the transition metal in the crystal lattice. From the viewpoint of cycle characteristics, it is preferable that a part of the transition element is substituted with another metal element, and it is particularly preferable that 0 ⁇ x ⁇ 0.3 in the general formula (1). Since at least one selected from the group consisting of Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, and Cr is dissolved, the crystal structure is stabilized. It is considered that the battery capacity can be prevented from decreasing even if the above is repeated, and that excellent cycle characteristics can be realized.
- the present inventors charge and discharge the above-mentioned charge and discharge when the metal composition of nickel, manganese and cobalt is not uniform, for example, LiNi 0.5 Mn 0.3 Co 0.2 O 2. It has been found that the influence of strain / cracking of the complex oxide at the time increases. This is presumably because the stress applied to the inside of the particles during expansion and contraction is distorted and cracks are more likely to occur in the composite oxide due to the non-uniform metal composition. Therefore, for example, a complex oxide having a rich Ni abundance ratio (for example, LiNi 0.8 Mn 0.1 Co 0.1 O 2 ) or a complex oxide having a uniform ratio of Ni, Mn, and Co.
- a complex oxide having a rich Ni abundance ratio for example, LiNi 0.8 Mn 0.1 Co 0.1 O 2
- a complex oxide having a uniform ratio of Ni, Mn, and Co for example, LiNi 0.8 Mn 0.1 Co 0.1 O 2
- composite oxides in which b, c and d are 0.44 ⁇ b ⁇ 0.51, 0.27 ⁇ c ⁇ 0.31, 0.19 ⁇ d ⁇ 0.26 The positive electrode active material is preferable. By adopting such a configuration, a battery having an excellent balance between capacity characteristics and output characteristics can be provided.
- the lithium nickel composite oxide also has a secondary particle structure in which primary particles are aggregated.
- the average primary particle size (average primary particle size) is preferably 0.9 ⁇ m or less, more preferably 0.20 to 0.6 ⁇ m, and even more preferably 0.25 to 0.5 ⁇ m.
- the average particle diameter of the secondary particles (average secondary particle diameter) is preferably 5 to 20 ⁇ m, more preferably 5 to 15 ⁇ m.
- the value of these ratios (average secondary particle size / average primary particle size) is preferably greater than 11, more preferably 15 to 50, and even more preferably 25 to 40.
- the primary particles constituting the lithium nickel composite oxide usually have a hexagonal crystal structure having a layered structure, but the size of the crystallite is correlated with the size of the average primary particle size.
- crystallite means the largest group that can be regarded as a single crystal, and can be measured by a method of refining the crystal structure parameters from the diffraction intensity obtained by powder X-ray diffraction measurement or the like.
- the specific value of the crystallite size of the primary particles constituting the lithium nickel composite oxide is not particularly limited, but from the viewpoint of life characteristics, it is preferably 1 ⁇ m or less, more preferably 360 nm or less, Preferably it is 310 nm or less.
- the lower limit value of the crystallite diameter is not particularly limited, but is usually 20 nm or more.
- the value of the crystallite diameter in the positive electrode active material particles is measured by the Rietveld method in which the crystallite diameter is calculated from the diffraction peak intensity obtained by powder X-ray diffraction measurement.
- the tap density of the lithium nickel composite oxide is preferably 2.3 g / cm 3 or more, more preferably 2.4 to 2.9 g / cm 3 .
- the BET specific surface area of the lithium nickel composite oxide is preferably 0.1 to 1.0 m 2 / g, more preferably 0.3 to 1.0 m 2 / g, and particularly preferably 0.00. 3 to 0.7 m 2 / g.
- the specific surface area of the active material is in such a range, the reaction area of the active material is ensured and the internal resistance of the battery is reduced, so that the occurrence of polarization during the electrode reaction can be minimized.
- the diffraction peak intensity ratio ((003) / (104)) is the diffraction peak on the (104) plane and the diffraction peak on the (003) plane obtained by powder X-ray diffraction measurement. It is preferably 1.28 or more, more preferably 1.35 to 2.1.
- the diffraction peak integrated intensity ratio ((003) / (104)) is preferably 1.08 or more, more preferably 1.10 to 1.45.
- Ni 3+ is easily reduced to Ni 2+, and because substantially equal to the Ni 2+ ion radius (0.83 ⁇ ) is Li + ion radius (0.90 ⁇ ), Ni to Li + defect occurring during active material synthesized 2+ tends to be mixed.
- Ni 2+ is mixed into the Li + site, a locally electrochemically inactive structure is formed and Li + diffusion is prevented. For this reason, when an active material with low crystallinity is used, there is a possibility that the battery charge / discharge capacity is reduced and the durability is lowered.
- the above definition is used as an index of the crystallinity.
- the ratio of the intensity of diffraction peaks of the (003) plane and the (104) plane and the ratio of the integrated intensity of the diffraction peaks by crystal structure analysis using X-ray diffraction. was used.
- these parameters satisfy the above-mentioned rules, defects in the crystal are reduced, and a decrease in battery charge / discharge capacity and a decrease in durability can be suppressed.
- Such crystallinity parameters can be controlled by the raw material, composition, firing conditions, and the like.
- the lithium nickel composite oxide such as NMC composite oxide can be prepared by selecting various known methods such as coprecipitation method and spray drying method.
- the coprecipitation method is preferably used because the complex oxide according to this embodiment is easy to prepare.
- a nickel-cobalt-manganese composite oxide is manufactured by a coprecipitation method as in the method described in JP2011-105588A, and then nickel-cobalt It can be obtained by mixing and firing a manganese composite oxide and a lithium compound.
- the positive electrode active material includes a spinel-based lithium manganese composite oxide and a lithium-nickel-based composite oxide
- the mixing ratio thereof is not particularly limited, but from the viewpoint of life characteristics and cost, the spinel-based lithium manganese composite oxide
- the content is preferably 15 to 40% by mass and more preferably 30 to 40% by mass with respect to 100% by mass of the lithium nickel composite oxide.
- a positive electrode active material layer also contains a conductive auxiliary agent essential.
- the “conducting aid” refers to an additive blended to improve the conductivity of the active material layer.
- the conductive auxiliary agent include carbon materials such as carbon black such as ketjen black and acetylene black, graphite, and carbon fiber.
- the conductive assistant contained in the positive electrode active material layer contains two or more kinds of conductive assistants having different average particle diameters.
- first conductive assistant the conductive assistant having a smaller average particle diameter than the other conductive assistants
- second conductive assistant the conductive assistant having a larger average particle diameter than the other conductive assistants
- conductive aid the conductive assistant contained in the positive electrode active material layer
- the present invention can be used as long as any two kinds of conductive assistants satisfy the above-mentioned rules. It shall be included in the technical scope of
- the specific value of the average particle diameter of the conductive auxiliary agent is not particularly limited, and conventionally known knowledge can be referred to as appropriate.
- the average particle diameter of the first conductive auxiliary agent is preferably 1.8 to The thickness is 2.5 ⁇ m, more preferably 1.3 to 4.5 ⁇ m.
- the average particle size of the second conductive assistant is preferably 2.0 to 5.8 ⁇ m, more preferably 3.1 to 3.8 ⁇ m.
- the ratio of the average particle diameter of the first conductive assistant to the average particle diameter of the second conductive assistant is not particularly limited, but the average particle diameter of the first conductive assistant / second conductive assistant.
- the ratio value of the average particle diameter is preferably 0.25 or more and less than 1, more preferably 0.47 to 0.8.
- the value of the average particle diameter of the conductive assistant is a value measured by a laser diffraction method.
- the value of the BET specific surface area of the conductive auxiliary agent is not particularly limited. However, when both the first conductive auxiliary agent and the second conductive auxiliary agent have a BET specific surface area of 25 to 80 cm 2 / g, the action of the present invention is achieved. This is preferable in that the effect can be remarkably exhibited.
- the content of the first conductive auxiliary in the positive electrode active material layer is larger than the content of the second conductive auxiliary, but the ratio value (the content of the first conductive auxiliary) / Mass ratio of the content of the second conductive auxiliary agent) is preferably 1.5 to 4.0, more preferably 2.0 to 3.0. Further, the content of the first conductive assistant in the positive electrode active material layer is preferably 2 to 4% by mass. Further, the content of the second conductive additive in the positive electrode active material layer is preferably 1 to 2% by mass.
- the positive electrode active material layer has a BET specific surface area of 1 to 3 m 2 / g.
- the value of the BET specific surface area is preferably 1.0 to 2.0 m 2 / g, more preferably 1.2 to 1.8 m 2 / g, and still more preferably 1.2 to 1.7 m 2. / G.
- the present inventor diligently searched for the cause of the temperature rise as described above.
- the cause of the temperature increase is that the decomposition reaction of the electrolyte caused by the increase in the surface potential of the positive electrode when the battery is overcharged is accelerated by the large specific surface area of the positive electrode. I found out that The configuration according to the present embodiment as described above has been found based on such knowledge.
- the BET specific surface area of the positive electrode active material layer is controlled within a predetermined range, and the conductive auxiliary agent having a large average particle size is contained,
- the contact area with the constituent material of the positive electrode active material layer does not become too large. For this reason, an increase in battery temperature is suppressed even in an overcharged state of the battery.
- the conductive network in a positive electrode active material layer is ensured by containing more conductive support agents with a small average particle diameter. For this reason, a decrease in discharge capacity is prevented even under high output conditions, and excellent output characteristics are ensured.
- the positive electrode active material layer is used to increase the binder, electrolyte (polymer matrix, ion conductive polymer, electrolyte, etc.), and ion conductivity as necessary. It further includes other additives such as lithium salts.
- the content of a material that can function as an active material in the positive electrode active material layer and the negative electrode active material layer described later is preferably 85 to 99.5% by weight.
- 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 amount of the binder contained in the positive electrode active material layer is not particularly limited as long as it is an amount capable of binding the active material, but preferably 0.5 to 15% by weight with respect to the active material layer. More preferably, it is 1 to 10% 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 compounding ratio of the components contained in the positive electrode active material layer and the negative electrode active material layer described later is not particularly limited.
- the blending ratio can be adjusted by appropriately referring to known knowledge about lithium ion secondary batteries.
- the thickness of each active material layer is not particularly limited, and conventionally known knowledge about the battery can be appropriately referred to. As an example, the thickness of each active material layer is about 2 to 100 ⁇ m.
- the negative electrode active material layer contains a negative electrode active material and, if necessary, other materials such as a conductive aid, a binder, an electrolyte (polymer matrix, ion conductive polymer, electrolyte, etc.), and a lithium salt for increasing ion conductivity. Further includes an additive. Other additives such as conductive assistants, binders, electrolytes (polymer matrix, ion conductive polymers, electrolytes, etc.) and lithium salts for improving ion conductivity are those described in the above positive electrode active material layer column. It is the same.
- the negative electrode active material examples include carbon materials such as graphite (graphite), soft carbon, and hard carbon, lithium-transition metal composite oxides (for example, Li 4 Ti 5 O 12 ), metal materials, lithium alloy negative electrode materials, and the like. Is mentioned. In some cases, two or more negative electrode active materials may be used in combination. Preferably, from the viewpoint of capacity and output characteristics, a carbon material or a lithium-transition metal composite oxide is used as the negative electrode active material. For the same reason, in the non-aqueous electrolyte secondary battery according to this embodiment, the negative electrode active material preferably includes graphite (graphite), and the negative electrode active material preferably includes graphite as a main component.
- carbon materials such as graphite (graphite), soft carbon, and hard carbon
- lithium-transition metal composite oxides for example, Li 4 Ti 5 O 12
- metal materials lithium alloy negative electrode materials, and the like. Is mentioned.
- two or more negative electrode active materials may be used in combination.
- the negative electrode active material is mainly composed of graphite” means that the proportion of graphite in the negative electrode active material is 50% by weight or more.
- the proportion of graphite in the negative electrode active material is more preferably 70% by weight or more, still more preferably 85% by weight or more, still more preferably 90% by weight or more, and particularly preferably 95% by weight or more. And most preferably 100% by weight.
- negative electrode active materials other than those described above may be used.
- the average particle diameter of the negative electrode active material is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 1 to 20 ⁇ m from the viewpoint of increasing the output.
- the negative electrode active material layer preferably contains at least an aqueous binder.
- a water-based binder has a high binding power.
- it is easy to procure water as a raw material and since steam is generated at the time of drying, the capital investment in the production line can be greatly suppressed, and the environmental load can be reduced. There is.
- the water-based binder refers to a binder using water as a solvent or a dispersion medium, and specifically includes a thermoplastic resin, a polymer having rubber elasticity, a water-soluble polymer, or a mixture thereof.
- the binder using water as a dispersion medium refers to a polymer that includes all expressed as latex or emulsion and is emulsified or suspended in water.
- kind a polymer latex that is emulsion-polymerized in a system that self-emulsifies.
- water-based binders include styrene polymers (styrene-butadiene rubber, styrene-vinyl acetate copolymer, styrene-acrylic copolymer, etc.), acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, ) Acrylic polymers (polyethyl acrylate, polyethyl methacrylate, polypropyl acrylate, polymethyl methacrylate (methyl methacrylate rubber), polypropyl methacrylate, polyisopropyl acrylate, polyisopropyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyhexyl acrylate , Polyhexyl methacrylate, polyethylhexyl acrylate, polyethylhexyl methacrylate, polylauryl acrylate, polylauryl meta Acrylate, etc.), polytyren
- the aqueous binder may contain at least one rubber binder selected from the group consisting of styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, and methyl methacrylate rubber from the viewpoint of binding properties. preferable. Furthermore, it is preferable that the water-based binder contains styrene-butadiene rubber because of good binding properties.
- Water-soluble polymers suitable for use in combination with styrene-butadiene rubber include polyvinyl alcohol and modified products thereof, starch and modified products thereof, cellulose derivatives (such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and salts thereof), polyvinyl Examples include pyrrolidone, polyacrylic acid (salt), or polyethylene glycol. Among them, it is preferable to combine styrene-butadiene rubber and carboxymethyl cellulose (salt) as a binder.
- the content of the aqueous binder is preferably 80 to 100% by weight, preferably 90 to 100% by weight, and preferably 100% 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. With the binder, 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 a 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 gaps between the inorganic particles are 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 .
- the material which comprises a current collector plate (25, 27) is not restrict
- 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.
- the same material may be used for the positive electrode current collecting plate 27 and the negative electrode current collecting plate 25, and different materials may be used.
- the battery outer case 29 a known metal can case can be used, and a bag-like case using a laminate film containing aluminum that can cover the power generation element can be used.
- a laminate film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used as the laminate film, but the laminate film is not limited thereto.
- a laminate film is desirable from the viewpoint that it is excellent in high output and cooling performance, and can be suitably used for a battery for large equipment for EV and HEV.
- the exterior body is more preferably an aluminate laminate.
- FIG. 2 is a perspective view showing the appearance of a flat lithium ion secondary battery which is a typical embodiment of the secondary battery.
- a flat laminated battery having a structure in which the power generation element is enclosed in a battery outer package made of a laminate film containing aluminum.
- the flat lithium ion secondary battery 50 has a rectangular flat shape, and a positive electrode tab 58 and a negative electrode tab 59 for taking out electric power are drawn out from both sides thereof.
- the power generation element 57 is encased by the battery outer packaging material 52 of the lithium ion secondary battery 50, and the periphery thereof is heat-sealed. The power generation element 57 is sealed with the positive electrode tab 58 and the negative electrode tab 59 pulled out to the outside.
- the power generation element 57 corresponds to the power generation element 21 of the lithium ion secondary battery 10 shown in FIG. 1 described above.
- the power generation element 57 is formed by laminating a plurality of single battery layers (single cells) 19 including a positive electrode (positive electrode active material layer) 15, an electrolyte layer 17, and a negative electrode (negative electrode active material layer) 13.
- the lithium ion secondary battery is not limited to a stacked flat shape.
- the wound lithium ion secondary battery may have a cylindrical shape, or may have a shape that is a flattened rectangular shape by deforming such a cylindrical shape.
- a laminate film may be used for the exterior material, and the conventional cylindrical can (metal can) may be used, for example, It does not restrict
- the power generation element is covered with an aluminum laminate film. With this configuration, weight reduction can be achieved.
- 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 battery storage space is about 170L. Since auxiliary devices such as cells and charge / discharge control devices are stored in this space, the storage efficiency of a normal cell is about 50%. The efficiency of loading cells into this space is a factor that governs the cruising range of electric vehicles. If the size of the single cell is reduced, the loading efficiency is impaired, so that the cruising distance cannot be secured.
- the battery structure in which the power generation element is covered with the exterior body is preferably large.
- the length of the short side of the laminated cell battery is preferably 100 mm or more. Such a large battery can be used for vehicle applications.
- the length of the short side of the laminated cell battery refers to the side having the shortest length.
- the upper limit of the short side length is not particularly limited, but is usually 400 mm or less.
- volume energy density and rated discharge capacity In a general electric vehicle, a travel distance (cruising range) by a single charge is 100 km. Considering such a cruising distance, the volume energy density of the battery is preferably 157 Wh / L or more, and the rated capacity is preferably 20 Wh or more.
- the nonaqueous electrolyte secondary battery according to this embodiment is a flat laminated battery, and the ratio of the battery area to the rated capacity (projected area of the battery including the battery outer package) is 5 cm 2 / It is preferably Ah or more and the rated capacity is 3 Ah or more.
- the aspect ratio of the rectangular electrode is preferably 1 to 3, and more preferably 1 to 2.
- the electrode aspect ratio is defined as the aspect ratio of the rectangular positive electrode active material layer.
- 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 nonaqueous electrolyte secondary battery according to this embodiment maintains a discharge capacity even when used for a long period of 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 nonaqueous electrolyte secondary battery can be suitably used as a vehicle power source, for example, 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.
- the obtained positive electrode active material slurry was applied to the surface of an aluminum foil (thickness: 20 ⁇ m) as a current collector, dried at 120 ° C. for 3 minutes, and then compression-molded with a roll press to obtain a rectangular planar shape.
- a positive electrode active material layer was prepared.
- a positive electrode active material layer was formed on the back surface to produce a positive electrode in which a positive electrode active material layer was formed on both surfaces of a positive electrode current collector (aluminum foil).
- the single-sided coating amount of the positive electrode active material layer was 20 mg / cm 2 (excluding the foil).
- a negative electrode active material slurry was prepared by dispersing 94% by mass of graphite as a negative electrode active material, 1% by mass of carbon black as a conductive additive, and 5% by mass of polyvinylidene fluoride (PVDF) as a binder. did.
- This negative electrode active material slurry was applied to a copper foil (thickness 10 ⁇ m) serving as a negative electrode current collector, dried at 120 ° C. for 3 minutes, and then compression molded with a roll press to produce a negative electrode.
- a negative electrode active material layer was formed on the back surface to prepare a negative electrode in which a negative electrode active material layer was formed on both sides of a negative electrode current collector (copper foil). The coating amount of the negative electrode active material layer was adjusted to 9 mg / cm 2 .
- the negative electrode of this comparative example was produced.
- test cell flat plate (flat) laminate battery
- Example 1 to 5 and Comparative Examples 2 to 5 Examples 1 to 5 and Comparative Example were compared in the same manner as in Comparative Example 1 except that the contents of the first conductive auxiliary and the second conductive auxiliary were changed to the values shown in Table 1 below. Test cells of Examples 2-5 were prepared.
- test cell was charged under a CC / CV condition of 150A 5.7V, and when the cell temperature did not reach 120 ° C., “ ⁇ ”, and when the cell temperature reached 120 ° C., “ ⁇ "
- test cells of Examples 1 to 5 using the positive electrode for a non-aqueous electrolyte secondary battery according to the present invention have both excellent life characteristics and overcharge characteristics.
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Abstract
Description
正極は、正極集電体と、前記正極集電体の表面に形成された正極活物質層とを有するものである。
正極集電体を構成する材料に特に制限はないが、好適には金属が用いられる。具体的には、金属としては、アルミニウム、ニッケル、鉄、ステンレス、チタン、銅、その他合金等などが挙げられる。これらのほか、ニッケルとアルミニウムとのクラッド材、銅とアルミニウムとのクラッド材、またはこれらの金属の組み合わせのめっき材などが好ましく用いられうる。また、金属表面にアルミニウムが被覆されてなる箔であってもよい。なかでも、電子伝導性や電池作動電位の観点からは、アルミニウム、ステンレス、銅が好ましい。
・正極活物質
正極活物質層は、正極活物質を含む。正極活物質の具体的な構成について特に制限はなく、従来公知の材料が用いられうる。一例として、正極活物質は、スピネル系リチウムマンガン複合酸化物および/またはリチウムニッケル系複合酸化物を含むことが好ましい。以下、これらの正極活物質の好ましい形態について、説明する。
スピネル系リチウムマンガン複合酸化物は、典型的にはLiMn2O4の組成を有し、スピネル構造を有する、リチウムおよびマンガンを必須に含有する複合酸化物であり、その具体的な構成や製造方法については、従来公知の知見が適宜参照されうる。
リチウムニッケル系複合酸化物は、リチウムとニッケルとを含有する複合酸化物である限り、その組成は具体的に限定されない。リチウムとニッケルとを含有する複合酸化物の典型的な例としては、リチウムニッケル複合酸化物(LiNiO2)が挙げられる。ただし、リチウムニッケル複合酸化物のニッケル原子の一部が他の金属原子で置換された複合酸化物がより好ましく、好ましい例として、リチウム-ニッケル-マンガン-コバルト複合酸化物(以下、単に「NMC複合酸化物」とも称する)は、リチウム原子層と遷移金属(Mn、NiおよびCoが秩序正しく配置)原子層とが酸素原子層を介して交互に積み重なった層状結晶構造を持ち、遷移金属Mの1原子あたり1個のLi原子が含まれ、取り出せるLi量が、スピネル系リチウムマンガン酸化物の2倍、つまり供給能力が2倍になり、高い容量を持つことができる。加えて、LiNiO2より高い熱安定性を有しているため、正極活物質として用いられるニッケル系複合酸化物の中でも特に有利である。
本形態に係る非水電解質二次電池において、正極活物質層は、導電助剤をも必須に含む。ここで「導電助剤」とは、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、グラファイト、炭素繊維などの炭素材料が挙げられる。正極活物質層が導電助剤を含むと、正極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。
正極活物質層は上述した正極活物質および導電助剤の他、必要に応じて、バインダー、電解質(ポリマーマトリックス、イオン伝導性ポリマー、電解液など)、イオン伝導性を高めるためのリチウム塩などのその他の添加剤をさらに含む。ただし、正極活物質層および後述の負極活物質層中、活物質として機能しうる材料の含有量は、85~99.5重量%であることが好ましい。
正極活物質層に用いられるバインダーとしては、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。これらのバインダーは、単独で用いてもよいし、2種以上を併用してもよい。
負極活物質層は負極活物質を含み、必要に応じて、導電助剤、バインダー、電解質(ポリマーマトリックス、イオン伝導性ポリマー、電解液など)、イオン伝導性を高めるためのリチウム塩などのその他の添加剤をさらに含む。導電助剤、バインダー、電解質(ポリマーマトリックス、イオン伝導性ポリマー、電解液など)、イオン伝導性を高めるためのリチウム塩などのその他の添加剤については、上記正極活物質層の欄で述べたものと同様である。
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。
集電板(25、27)を構成する材料は、特に制限されず、リチウムイオン二次電池用の集電板として従来用いられている公知の高導電性材料が用いられうる。集電板の構成材料としては、例えば、アルミニウム、銅、チタン、ニッケル、ステンレス鋼(SUS)、これらの合金等の金属材料が好ましい。軽量、耐食性、高導電性の観点から、より好ましくはアルミニウム、銅であり、特に好ましくはアルミニウムである。なお、正極集電板27と負極集電板25とでは、同一の材料が用いられてもよいし、異なる材料が用いられてもよい。
また、図示は省略するが、集電体11と集電板(25、27)との間を正極リードや負極リードを介して電気的に接続してもよい。正極および負極リードの構成材料としては、公知のリチウムイオン二次電池において用いられる材料が同様に採用されうる。なお、外装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ことが好ましい。
電池外装体29としては、公知の金属缶ケースを用いることができるほか、発電要素を覆うことができる、アルミニウムを含むラミネートフィルムを用いた袋状のケースが用いられうる。該ラミネートフィルムには、例えば、PP、アルミニウム、ナイロンをこの順に積層してなる3層構造のラミネートフィルム等を用いることができるが、これらに何ら制限されるものではない。高出力化や冷却性能に優れ、EV、HEV用の大型機器用電池に好適に利用することができるという観点から、ラミネートフィルムが望ましい。また、外部から掛かる発電要素への群圧を容易に調整することができ、所望の電解液層厚みへと調整容易であることから、外装体はアルミネートラミネートがより好ましい。
図2は、二次電池の代表的な実施形態である扁平なリチウムイオン二次電池の外観を表した斜視図である。このリチウムイオン二次電池のように、本発明における好ましい実施形態によれば、アルミニウムを含むラミネートフィルムからなる電池外装体に前記発電要素が封入されてなる構成を有する扁平積層型ラミネート電池が提供される。
一般的な電気自動車では、一回の充電による走行距離(航続距離)は100kmが市場要求である。かような航続距離を考慮すると、電池の体積エネルギー密度は157Wh/L以上であることが好ましく、かつ定格容量は20Wh以上であることが好ましい。
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。
本形態に係る非水電解質二次電池は、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、上記非水電解質二次電池は、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。
(1)正極の作製
第1の導電助剤としてカーボンブラック(平均粒径2.2μm)を1質量%、第2の導電助剤であるグラファイト(平均粒径3.4μm)を1質量%、バインダーとしてポリフッ化ビニリデン(PVDF)を4質量%、正極活物質としてリチウムニッケル複合酸化物を残部(導電助剤、バインダーおよび正極活物質の合計で100質量%)、およびスラリー粘度調整溶媒であるN-メチル-2-ピロリドン(NMP)を適量混合して正極活物質スラリーを調製した。次いで、得られた正極活物質スラリーを集電体であるアルミニウム箔(厚さ:20μm)の表面に塗布し、120℃で3分間乾燥後、ロールプレス機で圧縮成形して平面形状が矩形の正極活物質層を作製した。裏面にも同様にして正極活物質層を形成して、正極集電体(アルミニウム箔)の両面に正極活物質層が形成されてなる正極を作製した。なお、正極活物質層の片面塗工量は20mg/cm2(箔を含まない)であった。このようにして、本比較例の正極を作製した。
負極活物質としてグラファイトを94質量%、導電助剤としてカーボンブラックを1質量%、バインダーとしてポリフッ化ビニリデン(PVDF)を5質量%、を分散させて負極活物質スラリーを調製した。この負極活物質スラリーを負極集電体となる銅箔(厚さ10μm)に塗布し、120℃で3分間乾燥後、ロールプレス機で圧縮成形して負極を作製した。裏面にも同様にして負極活物質層を形成して、負極集電体(銅箔)の両面に負極活物質層が形成されてなる負極を作製した。なお、負極活物質層の塗工量については、9mg/cm2となるように調整した。このようにして、本比較例の負極を作製した。
上記(1)で作製した正極と、上記(2)で作製した負極とを、セパレータ(厚さ25μm、セルガード♯2500、ポリポア社製)を介して交互に積層(正極3層、負極4層)することによって発電要素を作製した。得られた発電要素を外装であるアルミラミネートシート製のバッグ中に載置し、電解液を注液した。電解液としては、1.0M LiPF6をエチレンカーボネート(EC)とジエチルカーボネート(DEC)との3:7(EC:DECの体積比)混合溶媒に溶解した溶液100重量%に対して、添加剤であるビニレンカーボネートを1質量%添加したものを用いた。次いで、真空条件下において、両電極に接続された電流取り出しタブが導出するようにアルミラミネートシート製バッグの開口部を封止し、ラミネート型リチウムイオン二次電池である試験用セルを完成させた。このようにして、本比較例の試験用セル(平板積層(扁平)型ラミネート電池)を作製した。
第1の導電助剤および第2の導電助剤の含有量を、下記の表1に示す値に変更したこと以外は、上述した比較例1と同様の手法により、実施例1~5および比較例2~5の試験用セルを作製した。
(正極活物質層のBET比表面積)
上記で作製した各試験用セルの作製に用いた正極の正極活物質層のBET比表面積を測定した。結果を下記の表1に示す。
上記で作製した各試験用セルについて、寿命特性を評価した。
上記で作製した各試験用セルについて、過充電特性を評価した。
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 (14)
- 正極集電体と、
前記正極集電体の表面に形成され、正極活物質および導電助剤を含み、BET比表面積が1~3m2/gである正極活物質層と、
を有し、
前記導電助剤が、第1の導電助剤および前記第1の導電助剤よりも平均粒径の大きい第2の導電助剤を含み、正極活物質層における前記第1の導電助剤の含有量が前記第2の導電助剤の含有量よりも多い、非水電解質二次電池用正極。 - 前記正極活物質層における前記第1の導電助剤の含有量が2~4質量%であり、前記正極活物質層における前記第2の導電助剤の含有量が1~2質量%である、請求項1に記載の非水電解質二次電池用正極。
- 前記正極活物質層のBET比表面積が1.2~1.8m2/g以下である、請求項1または2に記載の非水電解質二次電池用正極。
- 前記第1の導電助剤および前記第2の導電助剤のBET比表面積が、ともに25~80m2/gである、請求項1~3のいずれか1項に記載の非水電解質二次電池用正極。
- 前記正極活物質がスピネル系リチウムマンガン複合酸化物およびリチウムニッケル系複合酸化物を含み、前記スピネル系リチウムマンガン複合酸化物の含有量は、前記リチウムニッケル系複合酸化物の含有量100質量%に対して15~40質量%である、請求項1~4のいずれか1項に記載の非水電解質二次電池用正極。
- 前記正極活物質がリチウムニッケル系複合酸化物を含み、前記リチウムニッケル系複合酸化物の結晶子径が360nm以下である、請求項1~5のいずれか1項に記載の非水電解質二次電池用正極。
- 前記正極活物質がリチウムニッケル系複合酸化物を含み、
前記リチウムニッケル系複合酸化物は、一般式:LiaNibMncCodMxO2(但し、式中、a、b、c、d、xは、0.9≦a≦1.2、0<b<1、0<c≦0.5、0<d≦0.5、0≦x≦0.3、b+c+d=1を満たす。MはTi、Zr、Nb、W、P、Al、Mg、V、Ca、SrおよびCrからなる群から選ばれる少なくとも1種である)で表される組成を有する、請求項1~6のいずれか1項に記載の非水電解質二次電池用正極。 - 前記b、cおよびdが、0.44≦b≦0.51、0.27≦c≦0.31、0.19≦d≦0.26である、請求項7に記載の非水電解質二次電池用正極。
- 前記正極活物質層が矩形状であり、矩形状の前記正極活物質層の縦横比として定義される電極のアスペクト比が1~3である、請求項1~8のいずれか1項に記載の非水電解質二次電池用正極。
- 請求項1~9のいずれか1項に記載の非水電解質二次電池用正極と、
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、非水電解質二次電池。 - 定格容量に対する電池面積(電池外装体まで含めた電池の投影面積)の比の値が5cm2/Ah以上であり、定格容量が3Ah以上である、請求項10に記載の非水電解質二次電池。
- 前記負極活物質が黒鉛を主成分として含む、請求項10または11に記載の非水電解質二次電池。
- 前記セパレータが耐熱絶縁層付セパレータである、請求項10~12のいずれか1項に記載の非水電解質二次電池。
- アルミニウムを含むラミネートフィルムからなる電池外装体に前記発電要素が封入されてなる構成を有する扁平積層型ラミネート電池である、請求項10~13のいずれか1項に記載の非水電解質二次電池。
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