Patent Application
20190355969
The present invention relates to a non-aqueous electrolyte secondary battery.
Currently, a non-aqueous electrolyte secondary battery including a lithium ion secondary battery that is utilized for a mobile device such as a mobile phone is available as a commercial product. The non-aqueous electrolyte secondary battery generally has a configuration in which a positive electrode having a positive electrode active material or the like applied to a current collector and a negative electrode having a negative electrode active material or the like applied to a current collector are connected to each other via an electrolyte layer in which a non-aqueous electrolyte solution or a non-aqueous electrolyte gel is held in a separator. Further, charge and discharge reactions of a battery occur as ions such as lithium ions are absorbed into and desorbed from an electrode active material.
Incidentally, in recent years, it has been desired to reduce the amount of carbon dioxide in order to cope with global warming. Hence, a non-aqueous electrolyte secondary battery having a small environmental burden has been used not only in a mobile device or the like but also in a power source device of an electrically driven vehicle such as a hybrid vehicle (HEV), an electric vehicle (EV), or a fuel cell vehicle.
A non-aqueous electrolyte secondary battery directed to the application to electrically driven vehicles is desired to have a high output and a high capacity. Further, the non-aqueous electrolyte secondary battery directed to the application to electrically driven vehicles is desired to have cycle characteristics that the capacity can be maintained even when the charge and discharge cycle is repeated for a long period of time.
However, with an increase in capacity of the battery, the density of the positive electrode active material layer increases, and permeation of the non-aqueous electrolyte into the active material layer is inhibited by the porosity of the active material layer decreasing. Thus, the exchange of lithium ions becomes partially difficult, and reaction in the active material layer becomes non-uniform in some cases. Due to such a local reaction, a part of the active material is in an overcharge or overdischarge state and positive electrode active material particles are easily cracked. Due to such particle cracks of the positive electrode active material, cycle characteristics deteriorate in some cases.
Patent Literature 1 discloses a lithium ion secondary battery having an active material density of a positive electrode active material layer of 3.65 g/cm3 or more, in which large diameter particles having a crushing strength of 85 MPa or more and small diameter particles are mixed for use as a positive electrode active material. With such a configuration, even in a case where a positive electrode having a high active material density of the positive electrode active material layer is provided, the cracks of the positive electrode active material are suppressed so that a battery having excellent cycle characteristics can be obtained.
Patent Literature 1: JP 2013-65468 A
Incidentally, particularly in a non-aqueous electrolyte secondary battery for an electrically driven vehicle, a high capacity and a high output are demanded in order to lengthen a cruising distance per one charge. In addition to the above description, an improvement in durability (cycle characteristics in repetitive charging and discharging) of the battery is demanded such that a sufficient cruising distance can be secured even in repetitive charging and discharging. However, in the lithium ion secondary battery described in Patent Literature 1, the cycle characteristics cannot be said to be sufficient, and thus further improvement is demanded.
In this regard, an object of the present invention is to provide a non-aqueous electrolyte secondary battery having improved battery durability in the battery having a high capacity, a high density, and a large area.
The present invention is characterized in that in a battery having a high capacity, a high density, and a large area, a variation in porosity in a positive electrode active material layer is 6.0% or less.
According to a first embodiment of the present invention, there is provided a non-aqueous electrolyte secondary battery which includes a power generating element including a positive electrode in which a positive electrode active material layer containing a positive electrode active material is formed on a surface of a positive electrode current collector, a negative electrode in which a negative electrode active material layer containing a negative electrode active material is formed on a surface of a negative electrode current collector, and a separator, a ratio of a rated capacity to a pore volume of the positive electrode active material layer being 1.40 Ah/cc or more, a ratio of a battery area to a rated capacity being 4.0 cm2/Ah or more, and a rated capacity being 30 Ah or more, in which a variation in porosity in the positive electrode active material layer is 6.0% or less. In the first embodiment, by setting the variation in porosity in the positive electrode active material layer to 6.0% or less, a non-aqueous electrolyte secondary battery having significantly improved durability is obtained.
In recent years, an electric vehicle is attracting attention in view of being environmentally friendly, but as compared to a gasoline vehicle, the cruising distance is short and the shortness of the cruising distance is particularly significant at the time of air conditioning (cooling and heating), particularly. For this reason, a non-aqueous electrolyte secondary battery, particularly, a non-aqueous electrolyte secondary battery for an electrically driven vehicle is required to have a high output and a high capacity in order to extend the cruising distance per one charge. Further, improvement in durability (cycle characteristics) such that a high output and a high capacity are not decreased even by repetitive charging and discharging in a short time at a large current is important in a battery mounted in an electrically driven vehicle. For example, in Patent Literature 1, a capacity retention rate after the 500th cycle is about 80 to 83% (Patent Literature 1: Table 1), but a longer service life is demanded for widespread use of an electrically driven vehicle.
The present inventors have found that cycle characteristics are significantly improved by setting a variation in pore distribution in the positive electrode active material layer to 6.0% or less in view of the fact that cycle characteristics are not sufficient in a non-aqueous electrolyte secondary battery which has a high capacity density, a large area, and a high capacity and in which a ratio of a capacity to a pore volume of the positive electrode active material layer is 1.40 Ah/cc (Ah/cm3) or more, a ratio of a battery area to a rated capacity is 4.0 cm2/Ah or more, and a rated capacity is 30 Ah or more.
The detailed mechanisms for the effect being exhibited are not clear, but are speculated as follows. Incidentally, the technical scope of the present invention is not limited to the following mechanisms.
In a non-aqueous electrolyte secondary battery having a large area, pressure distribution occurs in the plane of the positive electrode, and overvoltages in the positive electrode active material layer are different due to such pressure distribution.
Under such a circumstance, a load is likely to be applied to the positive electrode active material at the time of charging and discharging, and the lifetime easily deteriorates. In addition, in a cell having a large capacity with respect to the pore volume of the positive electrode active material layer and a high capacity density, in a case where charging and discharging are repeated in a short time at a large current like use in a vehicle, diffusibility of Li ions is poor, and thus degradation of the battery lifetime easily occurs due to particle cracks of the positive electrode active material.
By setting the variation in pore distribution in the positive electrode active material layer to 6.0% or less, it is considered that the electro-current constriction in the positive electrode active material layer is alleviated, deterioration accompanied by side reaction caused by overvoltage variation is suppressed, and thus durability can be improved. In other words, the variation in porosity of the positive electrode active material layer can be allowed to be 6.0%. On the other hand, when the variation in porosity in the positive electrode active material layer is more than 6.0%, the capacity retention rate after charging and discharging are repeated is significantly decreased (see Comparative Examples 1 to 3 described later). A significant effect that such a variation in pore distribution is 6.0% or less is not recognized in a small-sized battery or a battery having a low capacity density (in the small-sized battery or the battery having a low capacity density, even when the variation in porosity in the positive electrode active material layer is more than 6.0%, the capacity retention rate becomes high; see Comparative Examples 4 to 6 described later). Therefore, the present invention can be said to be a means for solving a problem dedicated to a non-aqueous electrolyte secondary battery having a high capacity density, a large area, and a high capacity.
Incidentally, as the structure of the electrode, other than a winding type, there is a flat rectangular structure. In particular, in a winding type battery, the pressure distribution hardly occurs in the plane of the positive electrode as described above because of the structure thereof. On the other hand, as compared to a winding type electrode, a flat rectangular electrode has a large surface area, and a distance between the battery surface and a center portion is short. Therefore, heat generated inside the battery can be easily released outside, and it is possible to suppress heat remaining at the center portion of the battery. Since charging and discharging are performed at a large current, in an electrically driven vehicle, high heat releasing properties are required, but by using the flat rectangular electrode, an increase in temperature of the battery can be suppressed, and deterioration in battery performance can be suppressed. Meanwhile, in order to increase the capacity of the battery by using the flat rectangular electrode, the area of the non-aqueous electrolyte secondary battery used in an electrically driven vehicle is extremely larger than that of a consumer battery. In addition, in order to secure a living space, the volume of a battery to be mounted in an electrically driven vehicle is also required to be small, and thus the capacity density of a battery having a small volume and a high capacity is tried to be increased. In such a flat rectangular battery having a high capacity, a high capacity density, and a large area, further improvement in battery durability is demanded. As described above, in the flat rectangular battery, because of the size of the area thereof, problems of pressure distribution in the plane of the positive electrode and degradation in cycle characteristics become evident. However, according to the present invention, even in a non-aqueous electrolyte secondary battery with a flat rectangular shape, cycle characteristics at the time of repetition of charging and discharging in a short time at a large current can be improved. Therefore, the non-aqueous electrolyte secondary battery of the present invention can be particularly suitably used in a flat type non-aqueous electrolyte secondary battery.
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. Incidentally, the same elements are given with the same symbols for the descriptions of the drawings, and overlapped descriptions are omitted. Further, dimensional ratios in the drawings are exaggerated for the sake of description, and are different from actual ratios in some cases.
[Non-Aqueous Electrolyte Secondary Battery]
Incidentally, the lithium ion secondary battery is not limited to those having a flat shape of a laminate type, but a flat shape is preferable since the pressure in the plane direction is easily to be non-uniform and the effect of the present invention is further easily exerted, and a laminate type is more preferable since increasing of capacity is easy to achieve. A winding type lithium ion secondary battery may be those having a barrel shape or those having a rectangular flat shape obtained by modifying those having a barrel shape, and it is not particularly limited. A laminate film may be used as the outer casing material of those having a barrel shape, and a barrel can (metal can) of the related art may be used, and it is not particularly limited. Preferably, the power generating element is encased with an aluminum laminate film. Weight saving can be attained by such a form.
First, the overall structure of the non-aqueous electrolyte secondary battery of the present invention will be described using the drawings.
[Overall Structure of Battery]
Incidentally, the negative electrode active material layer 13 is disposed only on one surface of both the outermost layer negative electrode current collectors positioned on both outermost layers of the power generating element 21. However, an active material layer may be formed on both surfaces thereof. That is, not a current collector exclusive for an outermost layer in which an active material layer is formed on only one surface is used but a current collector having an active material layer on both surfaces may be directly used as the current collector of the outermost layer. Further, a positive electrode active material layer may be disposed on one surface of the outermost layer positive electrode current collector by reversing the disposition of the positive electrode and negative electrode in
The positive electrode current collector 12 and the negative electrode current collector 11 have a structure in which a positive electrode current collecting plate (tab) 27 and a negative electrode current collecting plate (tab) 25, which conductively communicate with each electrode (positive electrode and negative electrode), are attached to the positive electrode current collector 12 and the negative electrode current collector 11 and led to the outside of the battery outer casing material 29 so as to be inserted between the end parts of the battery outer casing material 29. If necessary, each of the positive electrode current collecting plate 27 and the negative electrode current collecting plate 25 may be attached to the positive electrode current collector 12 and the negative electrode current collector 11 of each electrode via a positive electrode lead and a negative electrode lead (not illustrated) by ultrasonic welding, resistance welding, or the like.
Incidentally, although a laminate type battery that is a flat laminate type but not a bipolar type is illustrated in
Hereinafter, respective members constituting the non-aqueous electrolyte lithium ion secondary battery according to an embodiment of the present invention will be described.
[Positive Electrode]
The positive electrode is one which includes a positive electrode current collector and a positive electrode active material layer containing a positive electrode active material formed on the surface of the positive electrode current collector.
(Positive Electrode Current Collector)
The material constituting the positive electrode current collector is not particularly limited, but a metal is suitably used. Specific examples of the metal include aluminum, nickel, iron, stainless steel, titanium, copper, and an alloy. In addition to these, a clad material of nickel and aluminum, a clad material of copper and aluminum, a plating material of a combination of these metals, or the like can be preferably used. Further, the material may be a foil obtained by coating a metal surface with aluminum. Among them, from the viewpoint of the electron conductivity and the potential for operating the battery, aluminum, stainless steel, and copper are preferable.
The size of the current collector is determined depending on the use of application of the battery. A current collector having a large area is used, for example, when the current collector is used in a large-sized battery which requires a high energy density. The thickness of the current collector is not particularly limited as well. The thickness of the current collector is generally about 1 to 100 μm.
Further, in the negative electrode described later, also in the case of using the negative electrode current collector, the same materials as described above can be used.
(Positive Electrode Active Material Layer)
The positive electrode active material layer 15 contains a positive electrode active material, and if necessary, further contains other additives such as a binder, a conductive aid, an electrolyte (a polymer matrix, an ion conductive polymer, an electrolyte solution, and the like), and a lithium salt for enhancing ion conductivity.
(Positive Electrode Active Material)
Examples of the positive electrode active material include lithium-transition metal composite oxides such as LiMn2O4, LiCoO2, LiNiO2, Li(Ni—Mn—Co)O2, and those in which a part of these transition metals are substituted with other elements, lithium-transition metal phosphate compounds, and lithium-transition metal sulfate compounds. A lithium-transition metal composite oxide is preferably used as the positive electrode active material from the viewpoint of capacity and output characteristics. Depending on the cases, two or more kinds of positive electrode active materials may be used concurrently.
Li(Ni—Mn—Co)O2 and those in which a part of these transition metals are substituted with other elements (hereinafter, also simply referred to as the “NMC composite oxide”) are more preferably used. The NMC composite oxide has a layered crystal structure in which a lithium atom layer and a transition metal (Mn, Ni, and Co are orderly disposed) atom layer are alternately laminated via an oxygen atom layer. In addition, one Li atom is contained per one atom of the transition metal, the amount of Li that can be taken out is twofold that of spinel type lithium manganese oxide, that is, the supply ability is twofold, and the NMC composite oxide can thus have a high capacity.
As described above, the NMC composite oxide also includes a composite oxide in which a part of the transition metal elements is substituted with other metal elements. Examples of the 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, and Zn. The other elements are preferably Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, and Cr. The other elements are more preferably Ti, Zr, P, Al, Mg, and Cr. From the viewpoint of improving the cycle characteristics, the other elements are further preferably Ti, Zr, Al, Mg, and Cr.
The NMC composite oxide preferably has a composition represented by General Formula (1): LiaNibMncCodMxO2 (provided that, in the formula, a, b, c, d, and x satisfy 0.9≤a≤1.2, 0<b<1, 0<c≤0.5, 0<d≤0.5, and 0≤x≤0.3; and M is at least one kind selected from Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, and Cr) since the theoretical discharge capacity is high. Herein, 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, and x represents the atomic ratio of M. In the above General Formula (1), the relation among b, c, and d is not particularly limited and varies depending on the valence of M, or the like, but it is preferable that b+c+d=1 is satisfied. Incidentally, the composition of the respective elements can be measured by, for example, inductively coupled plasma (ICP) emission spectrometry.
In general, it is known that nickel (Ni), cobalt (Co), and manganese (Mn) contribute to the capacity and output characteristics from the viewpoint of improving purity of the material and improving electron conductivity. Ti or the like partially substitutes the transition metal in the crystal lattice. From the viewpoint of cycle characteristics, a part of the transition element may be substituted with another metal element. In this case, it is preferable that 0<x≤0.3 in General Formula (1) is satisfied. It is considered that the crystal structure is stabilized by a solid solution formed by at least one kind selected from the group consisting of Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, and Cr, and as a result, a decrease in capacity of the battery can be prevented even when charge and discharge are repeated and excellent cycle characteristics can be realized.
The NMC composite oxide can be produced by selecting various known methods such as a co-precipitation method and a spray drying method. It is preferable to use a co-precipitation method since the production of the composite oxide is easy. Specifically, for example, as the method described in JP 2011-105588 A, a nickel-cobalt-manganese composite hydroxide is produced by a co-precipitation method. Thereafter, the nickel-cobalt-manganese composite hydroxide is mixed with a lithium compound, and the mixture is calcined so that the NMC composite oxide can be obtained.
Incidentally, it is needless to say that a positive electrode active material other than those described above may be used.
The average particle diameter of the positive electrode active material contained in the positive electrode active material layer is not particularly limited, but is preferably 1 to 100 μm and more preferably 1 to 25 μm from the viewpoint of increasing the output. Incidentally, in the present specification, as the average particle diameter, a value measured by a particle size distribution measuring apparatus for a laser diffraction and scattering method is employed.
The content of the positive electrode active material in the positive electrode active material layer (in terms of solid content) is preferably 80 to 99.5% by weight and more preferably 85 to 99.5% by weight.
The density of the positive electrode active material layer is preferably 2.5 to 3.8 g/cm3, more preferably 2.6 to 3.7 g/cm3, and further preferably 2.8 to 3.7 g/cm3 from the viewpoint of increasing the density.
(Binder)
The binder used in the positive electrode active material layer is not particularly limited, and examples thereof include thermoplastic polymers such as polyethylene, polypropylene, polyethylene terephthalate (PET), polyether nitrile, polyacrylonitrile, polyimide, polyamide, cellulose, carboxymethyl cellulose (CMC) and a salt thereof, an ethylene-vinyl acetate copolymer, polyvinylidene chloride, styrene-butadiene rubber (SBR), isoprene rubber, butadiene rubber, ethylene-propylene rubber, an ethylene-propylene-diene copolymer, a styrene-butadiene-styrene block copolymer and a hydrogenated product thereof, and a styrene-isoprene-styrene block copolymer and a hydrogenated product thereof; fluorine resins such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), a tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), an ethylene-tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), an ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF); vinylidene fluoride-based fluorine rubber such as vinylidene fluoride-hexafluoropropylene-based fluorine rubber (VDF-HFP-based fluorine rubber), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-based fluorine rubber (VDF-HFP-TFE-based fluorine rubber), vinylidene fluoride-pentafluoropropylene-based fluorine rubber (VDF-PFP-based fluorine rubber), vinylidene fluoride-pentafluoropropylene-tetrafluoroethylene-based fluorine rubber (VDF-PFP-TFE-based fluorine rubber), vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene-based fluorine rubber (VDF-PFMVE-TFE-based fluorine rubber), and vinylidene fluoride-chlorotrifluoroethylene-based fluorine rubber (VDF-CTFE-based fluorine rubber); and an epoxy resin. These binders may be used singly or two or more kinds thereof may be used concurrently.
The amount of the binder contained in the positive electrode active material layer is not particularly limited as long as it is such an amount that the active material can be bound, but the amount of the binder is preferably 0.5 to 15% by weight and more preferably 1 to 10% by weight with respect to the active material layer.
(Other Additives)
The conductive aid 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 aid include carbon materials such as carbon black including ketjen black, acetylene black, and the like, graphite, and a carbon fiber. When the active material layer contains the conductive aid, the electron network in the inside of the active material layer is effectively formed, thereby contributing to the improvement of output characteristics of the battery.
The amount of the conductive aid contained in the positive electrode active material layer is not particularly limited, but is preferably 0.5 to 15% by weight and more preferably 1 to 10% by weight with respect to the active material layer.
Examples of the electrolyte salt (lithium salt) include Li(C2F5SO2)2N, LiPF6, LiBF4, LiClO4, LiAsF6, and LiCF3SO3.
Examples of the ion conductive polymer include a polyethylene oxide (PEO)-based polymer and a polypropylene oxide (PPO)-based polymer.
The blending ratio of the components that are 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 the known knowledge on a lithium ion secondary battery. The thickness of each active material layer is not particularly limited as well, and the known knowledge on a battery can be appropriately referred to. As an example, the thickness of each active material layer is about 2 to 100 μm.
[Variation in Porosity in Positive Electrode Active Material Layer]
In the first embodiment, the variation in porosity in the positive electrode active material layer is 6.0% or less.
In a more preferred embodiment, the ratio of the rated capacity to the pore volume of the positive electrode active material layer is 2.20 Ah/cc or more, and the variation in porosity in the positive electrode active material layer is 5.0% or less. In a non-aqueous electrolyte secondary battery in which the ratio of the capacity to the pore volume of the positive electrode is 2.20 Ah/cc or more and the capacity density is further higher, by setting the variation in porosity in the positive electrode active material layer to 5.0% or less, the capacity retention rate is significantly improved. The reason for this is considered that, in a battery having a high capacity density, the influence of the variation in porosity on cycle characteristics becomes further significant so that uniformity of porosity of one layer is further demanded, and in a case where the variation in porosity in the positive electrode active material layer is 5.0% or less, a battery having a high capacity retention rate of more than 90% can be obtained (Example 9 or the like described later). Further, in another preferred embodiment, the variation in porosity in the positive electrode active material layer is 4.0% or less. When the variation in porosity in the positive electrode active material layer is 4.0% or less, cycle characteristics are further improved (comparison between Examples 1 to 6 and Examples 7 to 12 described later).
A lower variation in porosity in the positive electrode active material layer is preferable from the viewpoint of improving cycle characteristics, but the variation in porosity in the positive electrode active material layer is usually 0.5% or more.
When the variation in porosity in the positive electrode active material layer is decreased, the yield of the battery is decreased. On the other hand, with reference to
The variation in porosity in the positive electrode active material layer is calculated by the following equation.
Variation in porosity in the positive electrode active material layer=(Maximum porosity−Minimum porosity)/Average porosity×100 (%) [Math. 1]
Regarding the variation in porosity in the positive electrode active material layer, after respective positive electrode active material layers are separated, the porosity in five regions (=2 cm×5 cm) selected in the plane direction of each active material layer as illustrated in
As a method of measuring the porosity, first, the pore volume of a sample is measured. The pore volume of the sample is measured as follows. The volume of pores (micropores) existing in the sample is measured by a mercury intrusion method using a mercury intrusion porosimeter according to micropore distribution measurement. In a case where a capillary tube is set upright in a liquid, a liquid wetting a wall ascends in the capillary; on the other hand, a liquid not wetting a wall descends. It is needless to say that, in this capillary phenomenon, pressure acts in meniscus due to surface tension so that a material not wetted by a general substance, such as mercury, does not enter the inside of the capillary until pressure is applied. Since a mercury porosimeter uses the above-described matter, mercury is press-inserted to micropores, and then the diameter of micropores is obtained from a necessary pressure and the micropore volume (sample pore volume) is obtained from the press-inserted amount. The porosity can be calculated from the sample volume and the sample pore volume (porosity=(sample pore volume/sample volume)×100 (%)).
[Negative Electrode]
The negative electrode includes a negative electrode current collector and a negative electrode active material layer formed on the surface of the negative electrode current collector.
(Negative Electrode Active Material Layer)
The negative electrode active material layer contains a negative electrode active material, and if necessary, further contains other additives such as a conductive aid, a binder, an electrolyte (a polymer matrix, an ion conductive polymer, an electrolyte solution, and the like), and a lithium salt for enhancing ion conductivity. The other additives such as a conductive aid, a binder, an electrolyte (a polymer matrix, an ion conductive polymer, an electrolyte solution, and the like), and a lithium salt for enhancing ion conductivity are the same as those described above in the section of the positive electrode active material layer.
Examples of the negative electrode active material include graphite such as artificial graphite, coated natural graphite, or natural graphite, a carbon material such as soft carbon or hard carbon, a lithium-transition metal composite oxide (for example, Li4Ti5O12), a metal material, and a lithium alloy-based negative electrode material. Depending on the cases, two or more kinds of negative electrode active materials may be used concurrently. Preferably, a carbon material or a lithium-transition metal composite oxide is used as the negative electrode active material from the viewpoint of the capacity and output characteristics. Incidentally, it is needless to say that a negative electrode active material 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 μm and more preferably 1 to 30 μm from the viewpoint of increasing the output.
The negative electrode active material layer preferably contains at least an aqueous binder. The aqueous binder exhibits a high binding force. In addition, procurement of water as a raw material is easy and also only water vapor is generated during drying, and thus there is an advantage that the investment on facilities of a production line can be greatly cut down and a decrease in environmental burden can be achieved.
The aqueous binder refers to a binder which uses water as a solvent or a dispersion medium, and specific examples thereof include a thermoplastic resin, a polymer exhibiting rubber elasticity, a water-soluble polymer, and a mixture thereof. Herein, the binder which uses water as a dispersion medium includes all which are regarded as latex or an emulsion, and refers to a polymer that is emulsified in water or suspended in water. Examples thereof include a polymer latex obtained by emulsion polymerization in a self-emulsifying system.
Specific examples of the aqueous binder include a styrene polymer (styrene-butadiene rubber (SBR), a styrene-vinyl acetate copolymer, a styrene-acrylic copolymer, or the like), acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, a (meth)acrylic polymer (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 methacrylate, or the like), polytetrafluoroethylene, polyethylene, polypropylene, an ethylene-propylene copolymer, polybutadiene, butyl rubber, fluorine rubber, polyethylene oxide, polyepichlorohydrin, polyphosphagen, polyacrylonitrile, polystyrene, an ethylene-propylene-diene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, a polyester resin, a phenolic resin, an epoxy resin; polyvinyl alcohol (the average polymerization degree is suitably 200 to 4000 and more suitably 1000 to 3000, and the saponification degree is suitably 80% by mol or more and more suitably 90% by mol or more) and a modified product thereof (a product obtained by saponifying 1 to 80% by mol of the vinyl acetate units in a copolymer of ethylene/vinyl acetate=2/98 to 30/70 (molar ratio), a product obtained by partially acetalizing polyvinyl alcohol at 1 to 50% by mol, or the like), starch and a modified product thereof (oxidized starch, phosphoric acid esterified starch, cationized starch, or the like), cellulose derivatives (carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, a salt thereof, or the like), polyvinylpyrrolidone, polyacrylic acid (salt), polyethylene glycol, a copolymer of (meth)acrylamide and/or a (meth)acrylate salt [a (meth)acrylamide polymer, a (meth)acrylamide-(meth)acrylate salt copolymer, a (meth)acrylic acid alkyl (having 1 to 4 carbon atoms) ester-(meth)acrylate salt copolymer, or the like], a styrene-maleate salt copolymer, a mannich modified product of polyacrylamide, a formalin condensation type resin (a urea-formalin resin, a melamin-formalin resin, or the like), a polyamide polyamine or dialkylamine-epichlorohydrin copolymer, polyethyleneimine, casein, soybean protein, synthetic protein, and a water-soluble polymer such as a mannan galactan derivative. These aqueous binders may be used singly or two or more kinds thereof may be used concurrently.
From the viewpoint of binding property, the aqueous binder preferably contains at least one rubber-based binder selected from the group consisting of styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, and methyl methacrylate rubber. Further, the aqueous binder preferably contains styrene-butadiene rubber (SBR) since the binding property thereof is favorable.
In the case of using styrene-butadiene rubber as the aqueous binder, it is preferable to concurrently use the above-described water-soluble polymer from the viewpoint of the improvement in coating property. Examples of the water-soluble polymer which is suitably concurrently used with styrene-butadiene rubber include polyvinyl alcohol and a modified product thereof, starch and a modified product thereof, cellulose derivatives (carboxymethyl cellulose (CMC), methylcellulose, hydroxyethyl cellulose, a salt thereof, or the like), polyvinylpyrrolidone, polyacrylic acid (salt), and polyethylene glycol. Among them, styrene-butadiene rubber and carboxymethyl cellulose (CMC) (salt) are preferably combined as a binder. The weight content ratio of the styrene-butadiene rubber to the water-soluble polymer is not particularly limited, but it is preferable that the ratio of the styrene-butadiene rubber:the water-soluble polymer is 1:0.1 to 10 and more preferably 1:0.3 to 2.
The amount of the binder contained in the negative electrode active material layer is not particularly limited as long as it is such an amount that the active material can be bound, but the amount of the binder is preferably 0.5 to 15% by weight and more preferably 1 to 10% by weight with respect to the active material layer.
Further, the content of the aqueous binder of the binder used in the negative electrode active material layer is preferably 80 to 100% by weight, preferably 90 to 100% by weight, and preferably 100% by weight.
The density of the negative electrode active material layer is preferably 1.2 to 1.8 g/cm3 from the viewpoint of increasing the capacity.
Further, the weight per unit area (coating amount on one surface) of the negative electrode active material layer is preferably 6.0 to 15.0 mg/cm2 from the viewpoint of increasing the capacity.
[Separator (Electrolyte Layer)]
The separator has a function to hold the electrolyte so as to secure the lithium ion conductivity between the positive electrode and the negative electrode and also a function as a partition wall between the positive electrode and the negative electrode.
Examples of the separator shape include a porous sheet separator or a non-woven separator composed of a polymer or a fiber which absorbs and holds the electrolyte.
As the porous sheet separator composed of a polymer or a fiber, a microporous (microporous membrane) separator can be used, for example. Specific examples of the porous sheet composed of a polymer or a fiber include a microporous (microporous membrane) separator which is composed of a polyolefin such as polyethylene (PE) or polypropylene (PP); a laminate in which a plurality of these are laminated (for example, a laminate having a three-layer structure of PP/PE/PP), a hydrocarbon-based resin such as polyimide, aramid, or polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), or a glass fiber.
The thickness of the microporous (microporous membrane) separator cannot be uniformly defined as it varies depending on the use. For example, for use in a secondary battery for driving a motor of an electric vehicle (EV), a hybrid electric vehicle (HEV), a fuel cell vehicle (FCV), and the like, the thickness thereof is desirably 4 to 60 μm as a monolayer or a multilayer. The fine pore diameter of the microporous (microporous membrane) separator is desirably 1 μm or less at most (usually, the pore diameter is about several tens of nanometers).
As the non-woven separator, those known in the related art, such as cotton, rayon, acetate, nylon, polyester; a polyolefin such as PP or PE; polyimide, and aramid are used singly or as a mixture. In addition, the bulk density of the non-woven fabric is not particularly limited as long as sufficient battery characteristics are obtained by a polymer gel electrolyte impregnated into the non-woven fabric. Further, it is sufficient that the thickness of the non-woven separator is the same as that of the electrolyte layer. The thickness thereof is preferably 5 to 200 μm and particularly preferably 10 to 100 μm.
In addition, as described above, the separator also contains an electrolyte. The electrolyte is not particularly limited as long as it can exhibit such functions, but a liquid electrolyte or a gel polymer electrolyte may be used. The distance between electrodes is stabilized, an occurrence of polarization is suppressed, and the durability (cycle characteristics) is improved as a gel polymer electrolyte is used.
The liquid electrolyte has a function as a carrier of lithium ion. The liquid electrolyte constituting the electrolyte solution layer has a form in which a lithium salt as a supporting salt is dissolved in an organic solvent as a plasticizer. Examples of the organic solvent which can be used include carbonates such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethylmethyl carbonate (EMC). Further, as the lithium salt, a compound which may be added to an active material layer of an electrode, such as Li(CF3SO2)2N, Li(C2F5SO2)2N, LiPF6, LiBF4, LiClO4, LiAsF6, LiTaF6, and LiCF3SO3, can be adopted in the same manner. The liquid electrolyte may further contain an additive in addition to the components described above. Specific examples of such a compound include 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, 1-methyl-1-vinyl ethylene carbonate, 1-methyl-2-vinyl ethylene carbonate, 1-ethyl-1-vinyl ethylene carbonate, 1-ethyl-2-vinyl ethylene carbonate, vinyl vinylene carbonate, allyl ethylene carbonate, vinyloxymethyl ethylene carbonate, allyloxymethyl ethylene carbonate, acryloxymethyl ethylene carbonate, methacryloxymethyl ethylene carbonate, ethynyl ethylene carbonate, propargyl ethylene carbonate, ethynyloxymethyl ethylene carbonate, propargyloxyethylene carbonate, methylene ethylene carbonate, and 1,1-dimethyl-2-methylene ethylene carbonate. Among them, 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 singly or two or more kinds thereof may be used concurrently.
The gel polymer electrolyte has a configuration in which the above-described liquid electrolyte is injected into a matrix polymer (host polymer) consisting of an ion conductive polymer. Using a gel polymer electrolyte as an electrolyte is excellent in that the fluidity of the electrolyte disappears and ion conductivity between the respective layers is blocked. Examples of the ion conductive polymer which is used as the matrix polymer (host polymer) include polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyacrylonitrile (PAN), polyvinylidene fluoride-hexafluoropropylene (PVdF-HEP), polymethyl methacrylate (PMMA), and a copolymer thereof.
The matrix polymer of the gel electrolyte can exhibit an excellent mechanical strength as it forms a cross-linked structure. In order to forma cross-linked structure, it is sufficient to conduct a polymerization treatment, such as thermal polymerization, UV polymerization, radiation polymerization, or electron beam polymerization, of a polymerizable polymer for forming a polymer electrolyte (for example, PEO or PPO) using a proper polymerization initiator.
In addition, as a separator, a separator in which a heat resistant insulating layer is laminated on a porous substrate (a separator with a heat resistant insulating layer) may be used. The heat resistant insulating layer is a ceramic layer containing inorganic particles and a binder. As the separator with a heat resistant insulating layer, those exhibiting high heat resistance, namely, having a melting point or a heat softening point of 150° C. or higher and preferably 200° C. or higher, are used. By having a heat resistant insulating layer, internal stress of the separator which increases when the temperature increases is alleviated so that the effect of suppressing thermal shrinkage can be obtained. As a result, an occurrence of a short circuit between electrodes of the battery can be prevented so that a battery configuration in which the deterioration in performance due to an increase in temperature hardly occurs is obtained. In addition, by having a heat resistant insulating layer, the mechanical strength of the separator with a heat resistant insulating layer is improved so that the membrane of the separator is hardly broken. Further, because of the effect of suppressing thermal shrinkage and a high mechanical strength, the separator is hardly curled during the producing process of the battery.
The inorganic particles in the heat resistant insulating layer contribute to the mechanical strength or the effect of suppressing thermal shrinkage of the heat resistant insulating layer. The material used as the inorganic particles is not particularly limited. Examples thereof include oxides (SiO2, Al2O3, ZrO2, and TiO2), hydroxides, and nitrides of silicon, aluminum, zirconium, and titanium, and a composite thereof. These inorganic particles may be those which are derived from mineral resources such as boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, and mica, or those which are artificially synthesized. Further, these inorganic particles may be used singly or two or more kinds thereof may be used concurrently. Among them, it is preferable to use silica (SiO2) or alumina (Al2O3) and it is more preferable to use alumina (Al2O3) from the viewpoint of cost.
The weight per unit area of the inorganic particles is not particularly limited, but is preferably 5 to 15 g/m2. It is preferable that the weight per unit area is within this range since sufficient ion conductivity is obtained and the heat resistant strength is maintained.
The binder in the heat resistant insulating layer has a role to bond the inorganic particles to one another or the inorganic particles to a resin porous substrate layer. The heat resistant insulating layer is stably formed by this binder and also peeling between the porous substrate layer and the heat resistant insulating layer is prevented.
The binder used in the heat resistant insulating layer is not particularly limited, and for example, compounds such as carboxymethyl cellulose (CMC), polyacrylonitrile, cellulose, an ethylene-vinyl acetate copolymer, polyvinylidene chloride, styrene-butadiene rubber (SBR), isoprene rubber, butadiene rubber, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), and methyl acrylate can be used as the binder. Among these, carboxymethyl cellulose (CMC), methyl acrylate, or polyvinylidene fluoride (PVDF) is preferably used. These compounds may be used singly or two or more kinds thereof may be used concurrently.
The content of the binder 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. When the content of the binder is 2% by weight or more, the peeling strength between the heat resistant insulating layer and the porous substrate layer can be enhanced and vibration resistance of the separator can be improved. On the other hand, when the content of the binder is 20% by weight or less, a gap between the inorganic particles is properly kept so that sufficient lithium ion conductivity can be secured.
The thermal shrinkage rate of the separator with a heat resistant insulating layer is preferably 10% or less in both MD and TD after being held for 1 hour under the condition of 150° C. and 2 gf/cm2. Shrinkage of the separator can be effectively prevented even when the internal temperature of the battery reaches 150° C. due to an increased amount of heat generated from the positive electrode as such a highly heat resistant material is used. As a result, an occurrence of a short circuit between electrodes of the battery can be prevented so that a battery configuration in which the deterioration in performance due to an increase in temperature hardly occurs is obtained.
[Positive Electrode Current Collecting Plate and Negative Electrode Current Collecting Plate]
The material of the current collecting plate (25, 27) is not particularly limited, and a known highly conductive material which has been used as a current collecting plate for a lithium ion secondary battery in the related art can be used. Preferred examples of the material constituting the current collecting plate include metal materials such as aluminum, copper, titanium, nickel, stainless steel (SUS), and an alloy thereof. From the viewpoint of light weightiness, resistance to corrosion, and high conductivity, aluminum and copper are more preferable, and aluminum is particularly preferable. Incidentally, the same material or different materials may be used in the positive electrode current collecting plate 27 and the negative electrode current collecting plate 25.
[Positive Electrode Lead and Negative Electrode Lead]
Further, although it is not illustrated, the current collector 11 and the current collecting plate (25, 27) may be electrically connected to each other via a positive electrode lead or a negative electrode lead. A known material that is used in a lithium ion secondary battery of the related art can be used as the material constituting the positive electrode lead and the negative electrode lead in the same manner. Incidentally, a portion taken out from the outer casing is preferably coated with a heat resistant and insulating thermally shrunken tube or the like so that it is not in contact with the neighboring device or wire to cause electric leakage which affects the product (for example, an automobile component, in particular, an electronic device or the like).
[Battery Outer Casing Material (Battery Outer Casing Body)]
As the battery outer casing material (battery outer casing body) 29, an envelope-shaped casing which can cover the power generating element and uses a laminate film containing aluminum can be used in addition to a known metal can casing. As the laminate film, a laminate film having a three-layer structure formed by laminating PP, aluminum, and nylon in this order can be used, but it is not limited thereto. A laminate film is preferable from the viewpoint of an increase in output and excellent cooling performance and of being suitably utilizable in a battery for a large-sized device for EV or HEV, and an aluminum laminate film is more preferable from the viewpoint of weight saving.
[Ratio of Rated Capacity to Pore Volume of Positive Electrode Active Material Layer]
In the first embodiment, the ratio of the rated capacity to the pore volume of the positive electrode active material layer is 1.40 Ah/cc or more. The ratio of the capacity to the pore volume of the positive electrode active material layer is an index indicating high capacity densification of the positive electrode active material layer. Herein, in “g/cc” representing the active material density of the positive electrode active material layer, it is necessary to consider the density of the positive electrode active material itself. For example, in a material having a small density of the active material, even when the same degree of the active material is filled in the same capacity, as compared to a material having a large density of the active material, since the density of the positive electrode active material layer becomes smaller, it is not possible to determine whether the density is small or the weight of the positive electrode active material is small. For this reason, in the present specification, a capacity per pore volume is defined and this capacity per pore volume is used as an index for the height of the capacity density. Further, by using the capacity per pore volume as the index, the capacity per pore volume corresponds to an index for the density indicating how densely the positive electrode active material is filled.
Further, when, by increasing the capacity of the battery, the Li ions in the active material layer increases but the pore volume in the active material layer is decreased, diffusibility of Li ions is degraded. Therefore, the ratio of the capacity to the pore volume of the positive electrode corresponds to an index for diffusibility of Li ions, even under an environment of low diffusibility of Li ions in which the ratio of the capacity to the pore volume of the positive electrode is 1.40 Ah/cc or more, by setting the variation in porosity in the positive electrode active material layer to 6.0% or less, cycle characteristics are significantly improved.
The upper limit of the ratio of the rated capacity to the pore volume of the positive electrode active material layer is not particularly limited, but in consideration of diffusibility of Li ions, the ratio of the capacity to the pore volume of the positive electrode is preferably 3.2 Ah/cc or less and more preferably 3.0 Ah/cc or less. Further, from the viewpoint of increasing the density, the ratio of the capacity to the pore volume of the positive electrode active material layer is preferably 1.2 Ah/cc or more, and from the viewpoint of more easily exerting the effect of the present invention, the ratio of the capacity to the pore volume of the positive electrode active material layer is more preferably 1.5 Ah/cc or more.
The pore volume of the positive electrode active material layer is measured as follows. The positive electrode active material layer is extracted from the non-aqueous electrolyte secondary battery and then cut into a sample of 10 cm×10 cm. The volume of pores (micropores) existing in the sample is measured by micropore distribution measurement according to a mercury intrusion method using a mercury intrusion porosimeter. In a case where a capillary tube is set upright in a liquid, a liquid wetting a wall ascends in the capillary; on the other hand, a liquid not wetting a wall descends. It is needless to say that, in this capillary phenomenon, pressure acts in meniscus due to surface tension so that a material not wetted by a general substance, such as mercury, does not enter the inside of the capillary until pressure is applied. Since a mercury porosimeter uses the above-described matter, mercury is press-inserted to micropores, and then the diameter of micropores is obtained from a necessary pressure and the pore volume of the sample is obtained from the press-inserted amount. The pore volume of the positive electrode active material layer is calculated from the pore volume of the sample in consideration of the area of the positive electrode active material layer and the number of laminated layers.
The rated capacity is measured by the following procedures 1 and 2 at a temperature of 25° C. in a predetermined voltage range.
Procedure 1: After the voltage reaches the upper limit voltage at a constant current charge of 0.2 C, charge for 2.5 hours at a constant voltage charge, and then rest for 10 seconds.
Procedure 2: After the voltage reaches the lower limit voltage at a constant current discharge of 0.2 C, stop for 10 seconds.
Rated capacity: Discharge capacity in constant current discharge in the procedure 2 is regarded as the rated capacity.
[Ratio of Battery Area to Rated Capacity and Rated Capacity]
A general electric vehicle has a battery storage space of about 170 L. A cell and an auxiliary machine such as a device for controlling charge and discharge are stored in this space, and thus the storage space efficiency of a common cell is about 50%. The cell loading efficiency into this space is a factor to determine the cruising distance of an electric vehicle. The loading efficiency is impaired as the size of a single cell decreases, and thus it is not possible to secure the cruising distance.
Therefore, in the present invention, the battery structure of which the power generating element is covered with an outer casing body preferably has a large size. Further, as described above, in the large-sized battery, the effect of the present invention is exerted. Specifically, in this embodiment, largeness of the battery is defined from a relation between the battery area and the battery capacity. Specifically, the non-aqueous electrolyte secondary battery according to this embodiment has a ratio value of the battery area to the rated capacity of 4.0 cm2/Ah or more. In the present invention, since the rated capacity is large, that is, 30 Ah or more, the battery area is inevitably 120 cm2 or more, and thus the battery has a large size. In view of a high capacity, a higher ratio of the battery area to the rated capacity is preferable, but in the relation with the in-vehicle volume, the ratio of the battery area to the rated capacity is usually 18 cm2/Ah or less. The ratio value of the battery area to the rated capacity is preferably 5.0 to 15 cm2/Ah.
Herein, the battery area indicates an area of the positive electrode (in the plane direction). In a case where there are a plurality of positive electrodes and areas thereof are different, the maximum positive electrode area is regarded as the battery area.
In this embodiment, the rated capacity is 30 Ah or more. In the case of a large-area high-capacity battery in which the ratio value of the battery area to the rated capacity is 4.0 cm2/Ah or more and the rated capacity is 30 Ah or more, it is further difficult to maintain a high capacity due to a repetition of the charge and discharge cycle, and thus a problem of improvement in cycle characteristics is further significantly exhibited. On the other hand, in the case of a battery, which does not have a large area and a large capacity as described above, such as a consumer battery of the related art, such a problem does not significantly occur (see Comparative Examples 4 and 6 described later). A larger rated capacity is preferable, and the upper limit thereof is not particularly limited. The rated capacity is preferably 30 to 150 Ah and more preferably 40 to 100 Ah. Incidentally, as the rated capacity, a value measured by a method described in the following Examples is employed.
Further, regarding the physical size of the electrode, the length of the short side of the battery is preferably 100 mm or more. Such a large-sized battery can be used for a vehicle. Herein, the length of the short side of the battery indicates a side having the shortest length. The upper limit of the length of the short side is not particularly limited, but is usually 400 mm or less. Incidentally, the size of the electrode is defined as the size of the positive electrode. Further, the positive electrode and the negative electrode may have the same size or different sizes, but it is preferable that both the electrodes have the above-described size.
Further, the aspect ratio of a rectangular electrode is preferably 1 to 3 and more preferably 1 to 2. Incidentally, the aspect ratio of the electrode is defined as the length/width ratio of a positive electrode active material layer with a rectangular shape. When the aspect ratio is in this range, an advantage of having both the performance required for a vehicle and mounting space can be achieved.
[Assembled Battery]
An assembled battery is constituted by connecting a plurality of batteries. In detail, the assembled battery is constituted by connecting at least two or more batteries in series, in parallel, or in series and parallel. It is possible to freely control the capacity and voltage by connecting the batteries in series and in parallel.
It is also possible to form a detachable small-sized assembled battery by connecting plural batteries in series or in parallel. Moreover, by further connecting a plurality of detachable small-sized assembled batteries in series or parallel, it is possible to form an assembled battery having a high capacity and a high output which is suitable as a power source or an auxiliary power source for driving a vehicle requiring a high volume energy density and a high volume output density. The number of the connected batteries for producing an assembled battery or the number of the laminated small-sized assembled batteries for producing an assembled battery having a high capacity may be determined depending on the capacity or output of the battery that is mounted to a vehicle (electric vehicle).
A cell unit obtained by laminating a plurality of batteries in this way may be housed in upper and lower cases (for example, metal cases) to form an assembled battery. At this time, generally, the metal cases are fastened by a fastening member so that the assembled battery is accommodated in the cases. Therefore, the battery is pressurized in the laminating direction inside the cases. By such pressurization, in-plane pressure distribution easily occurs in a large-sized battery, and accordingly, a load is applied to the electrode active material at the time of charging and discharging so that battery lifetime easily deteriorates. On the other hand, according to the configuration of this embodiment, it is considered that, since the variation in porosity in the positive electrode active material is small, electro-current constriction caused by pressure distribution can be alleviated.
[Vehicle]
The non-aqueous electrolyte secondary battery of this embodiment can maintain a discharge capacity even when being used for a long period of time and thus exhibits favorable cycle characteristics. For use in a vehicle such as an electric vehicle, a hybrid electric vehicle, a fuel cell electric vehicle, or a hybrid fuel cell electric vehicle, a long lifespan is required as well as a high capacity and a large size compared to use in an electric and mobile electronic device. Therefore, the non-aqueous electrolyte secondary battery can be suitably utilized as a power source for a vehicle, for example, as a power source or as an auxiliary power source for driving a vehicle.
Specifically, the battery or the assembled battery formed by combining a plurality of batteries can be mounted on a vehicle. In this embodiment, a battery exhibiting excellent long term reliability, output characteristics, and a long lifespan can be formed, and thus, by mounting such a battery, a plug-in hybrid electric vehicle having a long EV driving distance and an electric vehicle having a long driving distance per one charge can be constituted. This is because a vehicle having a long lifespan and high reliability can be provided as the battery or an assembled battery formed by combining a plurality of batteries is used in, for example, a vehicle such as a hybrid car, a fuel cell electric car, or an electric car (including a two-wheel vehicle (motor bike) or a three-wheel vehicle in addition to all four-wheel vehicles (a passenger vehicle, a truck, a commercial vehicle such as a bus, a compact car, or the like)). However, the use is not limited to a vehicle, but the battery or the assembled battery can be applied to various kinds of power sources of other vehicles, for example, a moving object such as an electric train, and it can be also utilized as a built-in power source of an uninterruptable power source unit.
[Production Method]
Next, an example of a method for producing a non-aqueous electrolyte secondary battery of the present invention will be described, but the present invention is not limited only to such an example.
A preferred method for producing a non-aqueous electrolyte secondary battery of the present invention includes a process of mixing a positive electrode active material, a binder, a solvent, and the like and subjecting the resultant mixture to stiff-kneading (hereinafter, also simply referred to as a stiff-kneading process), a process of further adding a solvent to the mixture and mixing the resultant product to obtain a slurry composition, and a drying process of applying the slurry composition on a positive electrode current collector and drying the resultant product to obtain a positive electrode. Further, it is preferable to perform press processing after the drying process, and at this time, press processing is more preferably a hot pressing process.
In the stiff-kneading process, the positive electrode active material, the binder, and other blended components (for example, a conductive aid) are put in an appropriate solvent and mixed and dispersed by a disperser to prepare a paste. The stiff-kneading indicates that kneading is performed in a state where a solid content is higher than a final slurry for forming an active material layer. When kneading is performed in a state where the solid content is high in this way, a composition in which each material is uniformly dispersed can be obtained. By such uniform dispersing, respective components are in a state of being in close contact with each other, and thus the density of the active material layer can be increased.
A solvent used in the stiff-kneading process is not particularly limited, but for example, ketones such as acetone, aromatic hydrocarbon solvents such as toluene and xylene, polar solvents such as N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), and acetonitrile, and the like can be used. These may be used singly or as a mixture of two or more kinds thereof.
A kneader used for mixing in the stiff-kneading process is not particularly limited, and examples thereof include a planetary mixer, a twin-screw kneader, and a triple-screw kneader. Further, the addition order to the kneader is not particularly limited, but powder of the active material or the like is put in the kneader, and then a solvent is added thereto: the powder of the active material or the like and the solvent may be put substantially at the same time.
The solid content concentration in the stiff-kneading process is preferably 75 to 90% by weight in the mixture since a high shear force can be applied.
The variation in porosity of the positive electrode active material layer is not particularly limited, but can be controlled by controlling a coating condition of the positive electrode active material layer. Specifically, by increasing dispersibility of the active material or the like in the slurry, the variation in porosity becomes smaller. For example, when the stiff-kneading time is lengthened, the variation in porosity in the positive electrode active material layer can be made small. A shorter stiff-kneading time is preferable in consideration of production efficiency. However, in this embodiment, it is necessary to decrease the variation to 6.0% or less, and a longer stiff-kneading time is preferable for the purpose of increasing dispersibility of the active material or the like. Specifically, the stiff-kneading time is preferably 100 minutes or longer, more preferably longer than 100 minutes, and still more preferably 110 minutes or longer. The upper limit of the stiff-kneading time is not particularly limited, but inconsideration of production efficiency and effect saturation, is preferably 200 minutes or shorter. In addition, the temperature at the time of performing stiff-kneading is preferably 15 to 40° C. in view of coating property.
Then, a solvent is added to obtain a slurry composition. As the solvent, the solvent used in the stiff-kneading process can be used. The solid content concentration of the slurry composition is not particularly limited, but in consideration of ease of coating, is preferably 45 to 65% by weight.
A method of applying the slurry composition for a positive electrode active material layer on the positive electrode current collector is not particularly limited, but a method capable of forming a thick coating layer, such as die coating (such as slide die coating), comma direct coating, or comma reverse coating, is suitable. However, depending on a coating weight, the slurry composition may be applied by gravure coating, gravure reverse coating, or the like.
The weight per unit area (coating amount on one surface) when the slurry composition is applied on the positive electrode current collector is not particularly limited, but from the viewpoint of increasing the capacity and decreasing the weight, the weight per unit area is preferably 10.0 to 30.0 mg/cm2 and more preferably 13.0 to 25.0 mg/cm2.
As a heat source in the drying process, hot air, infrared rays, far infrared rays, microwave, high-frequency wave, or a combination thereof can be used. In the drying process, drying may be performed by heat released by heating a metal roller or a metal sheet which supports or presses the current collector. Further, by irradiation with an electron beam or radiation after drying, the binder is subjected to cross-linking reaction so that an active material layer can also be obtained. Applying and drying may be repeated in plural times.
It is preferable that the electrode drying temperature is typically high to some extent in order to shorten the drying time in consideration of production efficiency. However, in this embodiment, it is necessary to decrease the variation to 6.0% or less, and it is important to control the electrode drying temperature to be low. When the electrode drying temperature is low, convection flow in the slurry hardly occurs, and it can be suppressed that convection flow partially occurs so that pores become non-uniform. The electrode drying temperature is preferably 120° C. or lower, preferably 118° C. or lower, more preferably 115° C. or lower, and particularly preferably 110° C. or lower. In addition, the drying time is appropriately set to a time at which the drying is completed at the above-described temperature, but is, for example, 2 seconds to 1 hour.
Further, by subjecting the obtained positive electrode active material layer to press processing, the density of the active material layer, adhesiveness with respect to the current collector, and homogeneity can be improved.
The press processing is performed, for example, using a metal roll, an elastic roll, a heating roll (heat roll), a sheet press machine, or the like. The press temperature in this embodiment may be room temperature as long as it is lower than a temperature at which the coating film of the active material layer is dried or the press processing may be performed under heating condition, but the press processing is preferably performed under heating condition. By performing pressing (hot pressing) under heating condition, the variation in porosity can be decreased. The reason for this is considered that softening of the binder is accelerated, and the pore distribution is likely to become uniform. The temperature at the time of hot pressing (the temperature of a processing machine (for example, a roll)) is preferably 100 to 150° C., more preferably 110 to 140° C., and particularly preferably 115 to 130° C. Incidentally, in the case of a higher press temperature, the variation in porosity tends to be decreased.
The positive electrode can be produced by such a process. From the above description, in controlling of the variation in porosity in the positive electrode to 6.0% or less, it is particularly preferable that the stiff-kneading time and the press temperature are set in the above ranges.
Producing of the negative electrode active material layer and assembling of the battery can be performed by a known method of the related art.
The effect of the present invention will be described by means of the following Examples and Comparative Examples. In examples, the words “part(s)” or “%” may be used, and “part(s)” or “%” in Examples represents “part(s) by weight” or “% by weight” unless otherwise specified. In addition, respective operations are performed at room temperature (25° C.) unless otherwise specified.
1. Production of Electrolyte Solution
A mixed solvent of ethylene carbonate (EC), ethylmethyl carbonate (EMC), and diethyl carbonate (DEC) (30:30:40 (volume ratio)) was used as a solvent. In addition, 1.0 M LiPF6 was used as a lithium salt. Further, 2.0% by weight of vinylene carbonate with respect to the total 100% by weight of the solvent and the lithium salt was added to produce an electrolyte solution. Incidentally, “1.0 M LiPF6” means 1.0 M concentration of the lithium salt (LiPF6) in a mixture of the mixed solvent and the lithium salt.
2. Production of Positive Electrode
A solid content consisting of 90% by weight of LiNi1/3Mn1/3Co1/3O2 (average particle diameter: 15 μm) as a positive electrode active material, 5% by weight of acetylene black as a conductive aid, and 5% by weight of PVdF as a binder was prepared. To this solid content, an appropriate amount of N-methyl-2-pyrrolidone (NMP) as a slurry viscosity adjusting solvent was added to adjust a solid content concentration to 80% by weight, and then stiff-kneading was performed by a planetary mixer for 130 minutes. Further, an appropriate amount of N-methyl-2-pyrrolidone (NMP) as a slurry viscosity adjusting solvent was added to produce a positive electrode slurry composition (solid content: 55% by weight). Next, the positive electrode slurry composition was applied to both surfaces of an aluminum foil (thickness: 20 μm) as a current collector by a die coater. The electrode drying temperature immediately after applying was set to 115° C. Thereafter, hot pressing was performed by a heat roll press at 120° C. (roll temperature) to produce a positive electrode having a density of the positive electrode active material layer of 2.9 g/cm3, a coating amount of the positive electrode active material layer on one surface of 15.0 mg/cm2, and a thickness of the positive electrode active material layer of 50 μm.
3. Production of Negative Electrode
A solid content consisting of 94% by weight of natural graphite (average particle diameter: 20 μm) as a negative electrode active material, 2% by weight of acetylene black as a conductive aid, 3% by weight of styrene-butadiene rubber (SBR) as a binder, and 1% by weight of carboxymethyl cellulose (CMC) was prepared. To this solid content, an appropriate amount of ion-exchanged water as a slurry viscosity adjusting solvent was added to produce a negative electrode active material slurry composition. Next, the negative electrode active material slurry composition was applied to both surfaces of a copper foil (10 μm) as a current collector and subjected to drying and pressing, to produce a negative electrode having a density of the negative electrode active material layer of 1.4 g/cm3 and a coating amount on one surface of 7.3 mg/cm2.
4. Completion Process of Single Battery
The positive electrode produced above was cut to a rectangular shape of 200 mm×204 mm, and the negative electrode was cut to a rectangular shape of 205×209 mm (24 pieces of the positive electrode and 25 pieces of the negative electrode). These positive electrode and negative electrode were alternately laminated with a separator of 210×214 mm (polypropylene microporous membrane, thickness: 25 μm, porosity: 55%) interposed therebetween, thereby producing a power generating element.
The obtained power generating element was welded with a tab and sealed together with an electrolyte solution in an outer casing formed of an aluminum laminate film to complete a battery. Thereafter, the battery was inserted with a urethane rubber sheet (thickness: 3 mm) having a larger area than the area of the electrode, further the battery was sandwiched by Al plates (thickness: 5 mm), and the battery was appropriately pressed from both sides in the lamination direction. Then, the battery obtained in this way was subjected to initial charging over 5 hours (upper limit voltage: 4.2V). Thereafter, aging for 5 days was performed at 45° C., and degassing and discharging were performed, thereby completing a battery of this Example. The rated capacity (cell capacity) of the battery produced in this way was 40 Ah, and the ratio value of the positive electrode area to the rated capacity was 10.2 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured, and as a result, the ratio thereof was 1.42 Ah/cc.
Incidentally, the rated capacity of the battery was obtained by the following method.
«Measurement of Rated Capacity»
The rated capacity is measured by the following procedures 1 and 2 at a temperature of 25° C. in a voltage range of 3.0 V to 4.15 V.
Procedure 1: After the voltage reaches 4.15 V at a constant current charge of 0.2 C, charge for 2.5 hours at a constant voltage charge, and then rest for 10 seconds.
Procedure 2: After the voltage reaches 3.0 V at a constant current discharge of 0.2 C, stop for 10 seconds.
Rated capacity: Discharge capacity in discharge from constant current discharge to constant voltage discharge in the procedure 2 was regarded as the rated capacity.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 1, except that in the production of the positive electrode, the stiff-kneading time was set to 140 minutes, the electrode drying temperature was set to 109° C., the press temperature was set to 125° C., the density of the positive electrode active material layer was set to 3.2 g/cm3, the coating amount of the positive electrode active material layer on one surface was set to 18.0 mg/cm2, the coating amount of the negative electrode active material layer on one surface was set to 8.8 mg/cm2, and the size of the electrode was set as described in Table 2.
The rated capacity (cell capacity) of the battery was 50 Ah and the ratio value of the positive electrode area to the rated capacity was 8.4 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 2.08 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 1, except that in the production of the positive electrode, the stiff-kneading time was set to 150 minutes, the electrode drying temperature was set to 108° C., the press temperature was set to 130° C., the density of the positive electrode active material layer was set to 3.3 g/cm3, the coating amount of the positive electrode active material layer on one surface was set to 21.5 mg/cm2, the coating amount of the negative electrode active material layer on one surface was set to 10.5 mg/cm2, and the size of the electrode was set as described in Table 2.
The rated capacity (cell capacity) of the battery was 60 Ah and the ratio value of the positive electrode area to the rated capacity was 7.0 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 2.50 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 1, except that in the production of the positive electrode, the stiff-kneading time was set to 120 minutes, the electrode drying temperature was set to 120° C., and the press temperature was set to 120° C.
The rated capacity (cell capacity) of the battery was 40 Ah and the ratio value of the positive electrode area to the rated capacity was 10.2 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 1.42 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 2, except that in the production of the positive electrode, the stiff-kneading time was set to 130 minutes, the electrode drying temperature was set to 115° C., and the press temperature was set to 120° C.
The rated capacity (cell capacity) of the battery was 50 Ah and the ratio value of the positive electrode area to the rated capacity was 8.4 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 2.08 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 3, except that in the production of the positive electrode, the stiff-kneading time was set to 140 minutes, the electrode drying temperature was set to 110° C., and the press temperature was set to 125° C.
The rated capacity (cell capacity) of the battery was 60 Ah and the ratio value of the positive electrode area to the rated capacity was 7.0 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 2.50 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 1, except that in the production of the positive electrode, the stiff-kneading time was set to 110 minutes, the electrode drying temperature was set to 120° C., and the press temperature was set to 115° C.
The rated capacity (cell capacity) of the battery was 40 Ah and the ratio value of the positive electrode area to the rated capacity was 10.2 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 1.42 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 2, except that in the production of the positive electrode, the stiff-kneading time was set to 120 minutes, the electrode drying temperature was set to 118° C., and the press temperature was set to 115° C.
The rated capacity (cell capacity) of the battery was 50 Ah and the ratio value of the positive electrode area to the rated capacity was 8.4 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 2.08 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 3, except that in the production of the positive electrode, the stiff-kneading time was set to 130 minutes, the electrode drying temperature was set to 115° C., and the press temperature was set to 120° C.
The rated capacity (cell capacity) of the battery was 60 Ah and the ratio value of the positive electrode area to the rated capacity was 7.0 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 2.50 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 1, except that in the production of the positive electrode, the stiff-kneading time was set to 100 minutes, the electrode drying temperature was set to 120° C., and the press temperature was set to 115° C.
The rated capacity (cell capacity) of the battery was 40 Ah and the ratio value of the positive electrode area to the rated capacity was 10.2 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 1.42 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 2, except that in the production of the positive electrode, the stiff-kneading time was set to 100 minutes, the electrode drying temperature was set to 118° C., and the press temperature was set to 115° C.
The rated capacity (cell capacity) of the battery was 50 Ah and the ratio value of the positive electrode area to the rated capacity was 8.4 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 2.08 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 3, except that in the production of the positive electrode, the stiff-kneading time was set to 110 minutes, the electrode drying temperature was set to 118° C., and the press temperature was set to 115° C.
The rated capacity (cell capacity) of the battery was 60 Ah and the ratio value of the positive electrode area to the rated capacity was 7.0 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 2.50 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 1, except that in the production of the positive electrode, the stiff-kneading time was set to 80 minutes, the electrode drying temperature was set to 120° C., and heating was not performed at the time of pressing.
The rated capacity (cell capacity) of the battery was 40 Ah and the ratio value of the positive electrode area to the rated capacity was 10.2 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 1.42 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 2, except that in the production of the positive electrode, the stiff-kneading time was set to 90 minutes, the electrode drying temperature was set to 120° C., and heating was not performed at the time of pressing.
The rated capacity (cell capacity) of the battery was 50 Ah and the ratio value of the positive electrode area to the rated capacity was 8.4 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 2.08 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 3, except that in the production of the positive electrode, the stiff-kneading time was set to 100 minutes, the electrode drying temperature was set to 120° C., and heating was not performed at the time of pressing.
The rated capacity (cell capacity) of the battery was 60 Ah and the ratio value of the positive electrode area to the rated capacity was 7.0 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 2.50 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Comparative Example 2, except that the density of the positive electrode active material layer was set to 3.2 g/cm3, the coating amount of the positive electrode active material layer on one surface was set to 10.2 mg/cm2, the coating amount of the negative electrode active material layer on one surface was set to 5.3 mg/cm2, and the size of the electrode was set as described in Table 2.
The rated capacity (cell capacity) of the battery was 25 Ah and the ratio value of the positive electrode area to the rated capacity was 14.3 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 2.08 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 1, except that in the production of the positive electrode, the stiff-kneading time was set to 70 minutes, the electrode drying temperature was set to 120° C., heating was not performed at the time of pressing, the density of the positive electrode active material layer was set to 2.7 g/cm3, the coating amount of the positive electrode active material layer on one surface was set to 11.8 mg/cm2, the coating amount of the negative electrode active material layer on one surface was set to 5.6 mg/cm2, and the size of the electrode was set as described in Table 2.
The rated capacity (cell capacity) of the battery was 35 Ah and the ratio value of the positive electrode area to the rated capacity was 12.9 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 1.12 Ah/cc.
A non-aqueous electrolyte secondary battery was obtained in the same manner as in Comparative Example 2, except that the density of the positive electrode active material layer was set to 3.2 g/cm3, the coating amount of the positive electrode active material layer on one surface was set to 26 mg/cm2, the coating amount of the negative electrode active material layer on one surface was set to 12.7 mg/cm2, and the size of the electrode was set as described in Table 2.
The rated capacity (cell capacity) of the battery was 15 Ah and the ratio value of the positive electrode area to the rated capacity was 3.3 cm2/Ah. Further, the ratio of the rated capacity to the pore volume of the positive electrode active material layer of the obtained battery was measured and, as a result, the ratio was 2.08 Ah/cc.
(Cycle Characteristics)
The battery produced in each of Examples and Comparative Examples was charged to a cutoff voltage of 4.15 V with a current density of 2 mA/cm2 for the positive electrode to have an initial charge capacity. Then, the capacity at the time of discharging to a cutoff voltage of 3.0 V after resting for 1 hour was used as an initial discharge capacity. This charge and discharge cycle was repeated 500 times. A ratio of the discharge capacity in the 500th cycle to the initial discharge capacity was regarded as a capacity retention rate (%) and evaluated as cycle durability.
The production conditions and the results of cycle characteristics of each of Examples and Comparative Examples are presented in the following Table 1.
Further, the size of the electrode, the number of laminated layers, the weight per unit area of the positive electrode, the density of the positive electrode, the weight per unit area of the negative electrode, and the density of the negative electrode of each of Examples and Comparative Examples are presented in the following Table 2.
From the above results, it is found that the non-aqueous electrolyte secondary batteries of Examples are excellent in cycle characteristics. Further, from comparison between Example 9 and Example 12, it is found that, in a case where the ratio of the capacity to the pore volume of the positive electrode active material layer is 2.20 Ah/cc or more, by setting the variation in porosity in the positive electrode active material layer to 5.0% or less, cycle characteristics are further significantly improved. Further, it is found that cycle characteristics of the non-aqueous electrolyte secondary batteries of Examples 1 to 6 in which the variation in porosity in the positive electrode active material layer is 4.0% or less are particularly excellent.
On the other hand, in Comparative Example 4 having a small rated capacity, Comparative Example 5 having a small rated capacity with respect to the pore volume of the positive electrode active material layer, and Comparative Example 6 having a small cell area, it is found that, even when the variation exceeds 6.0%, the capacity retention rate is high, and by setting the variation to 6.0% or less in a battery having a high capacity, a high capacity density, and a large area, cycle characteristics are significantly improved.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2016/067136 | 6/8/2016 | WO | 00 |
