Patent Application
20180323439
The present invention relates to a lithium ion secondary battery and a method for producing a lithium ion secondary battery.
In view of a problem of global warming and depletion of fuel, an electric vehicle (EV) has been developed by each auto manufacturer. As a power source of the EV, use of a lithium ion secondary battery with high energy density is required. In general, a lithium ion secondary battery has a positive electrode, a negative electrode, and a separator as a main constitutional element. The separator consists of a porous resin such as polyethylene or polypropylene, and its function is to have pass-through of lithium ions only while insulating the positive electrode and negative electrode. Furthermore, regarding the negative electrode, an active material containing silicon (Si) has been expected in recent years in order to achieve the high energy densification. However, with pure Si only, volume changes associated with charging and discharging are large. As such, determinations are made to suppress the volume changes associated with charging and discharging by using SiOx in which Si is trapped within SiO2, Si alloy in which Si is trapped within a metal material such as Ti or Fe, or the like.
As a technique for suppressing a decrease in battery characteristics that is associated with expansion⋅shrinkage of a negative electrode, a complex for a power storage device characterized in that it consists of silicon oxide (A) expressed in SiOx (1.77≤x≤1.90) and a conductive material (B) formed of a carbonaceous material as a raw material capable of adsorbing and desorbing lithium ions is disclosed in PTL 1. It is described that, according to this constitution, a deterioration of cycle characteristics which is caused by disruption of conductive network as a result of expansion⋅shrinkage of an electrode and disruption⋅degradation of a negative electrode material can be suppressed.
Furthermore, disclosed in PTL 2 is a negative electrode for a lithium ion secondary battery which has, on the surface of a current collector, a metal containing layer with thickness of 20 to 70 μm that contains a carbon material and silicon and/or tin as a metal capable of alloying with lithium of 1 to 100 parts by mass relative to 100 parts by mass of the carbon material, and a carbon material layer on top of the metal containing layer, characterized in that the carbon material in the metal containing layer includes natural graphite and a carbonaceous material, and the metal containing layer is obtained by mixing the metal, natural graphite, and a precursor of the carbonaceous material followed by a heating treatment. According to the above constitution, a metal containing layer containing a carbon material and a metal capable of alloying is provided on the surface of a current collector and a carbon material layer is provided on the metal containing layer. As such, even when the metal is pulverized due to expansion⋅shrinkage associated with charging and discharging, separation of the metal from the metal containing layer does not occur. Furthermore, since the metal containing layer contains a carbon material which has low expansion rate compared to the metal and good adhesiveness to a current collector, the conductivity can be maintained without deteriorating the adhesiveness of the metal containing layer to a current collector even when charging and discharging are repeated. It is described that, as a result, a lithium ion secondary battery manufactured by using a negative electrode for a lithium ion secondary battery that is described in PTL 2 has high discharge capacity, high initial charging and discharging efficiency, and excellent cycle characteristics.
Meanwhile, high safety⋅reliability is required for a lithium ion secondary battery. As a technique for enhancing the reliability of a lithium ion secondary battery, a battery separator consisting of insulating microparticles, which are stable at least against an organic electrolyte solution, and an organic binder and having 60° gloss of 5 or more is disclosed in PTL 3. It is described that, according to the constitution, if a separator is formed such that the filling property of the insulating microparticles in separator is further enhanced and the 60° gloss is 5 or more, a more compact and uniform structure can be obtained so that a separator with high reliability can be constituted.
Furthermore, disclosed in PTL 4 is a separator for nonaqueous electrolyte secondary battery having a resin base and a porous heat resistant layer disposed on the base, in which the porous heat resistant layer includes at least an inorganic filler and a hollow body, the hollow body has a shell part made of an acrylic resin and a hollow part formed inside the hollow body, and the shell part is provided with an opening which extends through the shell part and spatially connects the hollow part to the outside thereof. It is described that, according to the above constitution, as the hollow body is included within the porous heat resistant layer, the separator can be provided with excellent flexibility, elasticity, or a property of maintaining the shape, and as such, collapse of the separator is prevented. For example, as it is unlikely to be affected by the stress (pressure) which may be applied to a separator according to the battery restraining force or repetitive charging and discharging, it becomes possible to maintain stably the shape of a separator (typically, thickness). Accordingly, the distance between a positive electrode and a negative electrode of a nonaqueous electrolyte secondary battery can be suitably maintained so that a capacity decrease caused by a tiny internal short circuit or self discharge can be prevented. Furthermore, a suitable reaction of a gas generator can be obtained during overcharging. It is also described that, since the hollow body is electrochemically stable in a nonaqueous electrolyte and can gather the nonaqueous electrolyte in a hollow part, an excellent liquid-retaining property can be stably maintained and exhibited over a long period of time.
PTL 1: JP 5058494 B2
PTL 2: JP 2006-59704 A
PTL 3: JP 2008-210782 A
PTL 4: JP 2015-106511 A
In recent years, there is an ever-increasing demand for a lithium ion secondary battery with high energy density, high cycle characteristics, and high safety. As described in the above, when an active material containing Si is used for having high energy densification of a lithium ion secondary battery, high stress during expansion⋅shrinkage remains as a problem. In general, the biggest problem associated with the expansion⋅shrinkage of a battery is lowered safety. Namely, it is considered that short circuit of a positive electrode and a negative electrode is caused by stress occurring during expansion⋅shrinkage of a negative electrode. As such, in the case of using an active material containing Si, a solution for preventing the short circuit caused by high stress during expansion⋅shrinkage is essentially required. However, there is a possibility that the above described PTLs 1 to 4 may not be sufficient for achieving the high level that is recently required in terms of the prevention of short circuit.
As such, in consideration of the circumstances that are described above, the present invention is to provide a lithium ion secondary battery that prevents short circuit in which energy density, cycle characteristics, and safety are all balanced at high levels; and a method for producing a lithium ion secondary battery which allows production of such lithium ion secondary battery.
A lithium ion secondary battery according to the present invention includes: a positive electrode; a negative electrode; and a separator provided between the positive electrode and the negative electrode, wherein the negative electrode contains a negative electrode active material containing silicon, hardness of the negative electrode active material is 10 GPa or more and 20 GPa or less, and the separator has a constitution in which a resin layer and a porous layer are laminated, the thickness of the porous layer is 2 μm or more and 10 μm or less when the thickness of the resin layer is 25 μm or more and 30 μm or less, and the thickness of the porous layer is 5 μm or more and 20 μm or less when the thickness of the resin layer is 15 μm or more but less than 25 μm.
According to the present invention, a lithium ion secondary battery that prevents short circuit in which energy density, cycle characteristics, and safety are all balanced at high levels; and a method for producing a lithium ion secondary battery which allows production of such lithium ion secondary battery can be provided.
Hereinbelow, embodiments of the present invention are explained in view of the drawings.
In general, the major disadvantage associated with the expansion and shrinkage of a battery is a safety problem, and it is considered that short circuit of a positive electrode and a negative electrode occurs due to mispositioning that is associated with expansion of a negative electrode. However, the inventors of the present invention found that there are more causes for having short circuit other than that. Specifically, it was found that a battery in which a negative electrode having a negative electrode active material containing Si with hardness at certain level or higher is used allows high energy densification and achievement of long service life, but in case of a resin separator which is generally used, the separator is under pressure so that short circuit may easily occur.
Accordingly, the inventors of the present invention conducted intensive studies on a constitution of a lithium ion secondary battery to prevent the short circuit. As a result, it was found that, by having a constitution of the separator 3 which allows relief of the stress occurring during expansion⋅shrinkage of a negative electrode by lamination of a resin layer and a porous layer, and, after figuring out the relationship between the hardness of a negative electrode active material and film thickness of a resin layer and a porous layer, by setting each of them within a predetermined range, the aforementioned short circuit can be prevented. The present invention is based on this finding.
Hereinbelow, the constitution of the separator 3 of a lithium ion secondary battery according to the present invention is explained in detail.
As illustrated in
The resin layer 31 is not particularly limited, but a heat resistant resin such as polyethylene, polypropylene, polyamide, polyamideimide, polyimide, polysulfone, polyether sulfone, polyphenyl sulfone, or polyacrylonitrile is suitable.
The porous layer 32 is preferably a porous material having flexibility and thermal conductivity to which an electrolyte solution can infiltrate. Preferred examples thereof include silicon dioxide (SiO2), aluminum oxide (Al2O3), montmorillonite, mica, zinc oxide (ZnO), titanium oxide (TiO2), barium titanate (BaTiO3), and zirconium oxide (ZrO2). Among them, SiO2 and Al2O3 are particularly preferable in view of cost.
Porosity of the porous layer 32 is preferably 50% or more and 90% or less, and more preferably 80% or more and 90% or less. Because the porous layer 32 according to the present invention is to relieve mainly the stress, it has higher porosity than the porosity of a case in which heat resistance is required (for example, PTL 4).
Hereinbelow, explanations are given for the constitution other than the separator 3 of a lithium ion secondary battery according to the present invention. On a single surface or both surfaces of a positive electrode current collector (for example, aluminum foil), a positive electrode mixture slurry containing positive electrode active material is coated and dried, press molding is carried out using a roll press or the like, and cutting to a predetermined size is carried out to produce the positive electrode 1 constituting a lithium ion secondary battery. Similarly, on a single surface or both surfaces of a negative electrode current collector (for example, copper foil), a negative electrode mixture slurry containing negative electrode active material is coated and dried, press molding is carried out using a roll press or the like, and cutting to a predetermined size is carried out to produce the negative electrode 2 constituting a lithium ion secondary battery.
The positive electrode active material used for the positive electrode 1 is not particularly limited as long as it is a lithium compound capable of adsorbing and releasing lithium ions. Examples thereof include composite oxide of lithium and transition metal such as lithium manganese oxide, lithium cobalt oxide, or lithium nickel oxide. One of them may be used either singly, or it is possible to use a mixture of two or more kinds of them. If necessary, by mixing the positive electrode active material with a binder (polyimide, polyamide, polyvinylidene fluoride (PVDF), styrene butadiene rubber (SBR), or a mixture thereof), a thickening agent, a conductive material, a solvent, or the like, a positive electrode mixture slurry is prepared.
The negative electrode active material used for the negative electrode 2 essentially has a negative electrode active material containing Si, and it may be also a mixture containing, other than the negative electrode active material containing Si, one or more kinds selected from artificial graphite, natural graphite, non-graphatizable carbons, metal oxide, metal nitride, and activated carbon. By changing their mixing ratio, the discharge capacity can be modified. Their mixing ratio (mixing mass ratio) is preferably as follows; negative electrode active material containing Si:graphite=20:80 to 70:30. When the mixing ratio of the negative electrode active material containing Si is less than that value, high energy density cannot be achieved. On the other hand, when the mixing ratio is higher than that value, expansion of a negative electrode is excessively high so that high cycle characteristics cannot be obtained.
As for the negative electrode active material containing Si, SiO can be used. Furthermore, an alloy (Si alloy) containing Si and a different kind of a metal element including one or more of aluminum (Al), nickel (Ni), copper (Cu), iron (Fe), titanium (Ti), and manganese (Mn) can be used. SiO is preferably SiO (0.5≤x≤1.5). Furthermore, preferred specific examples of the Si alloy include Si70Ti15Fe15, Si70Cu30 and Si70Ti30. Furthermore, Si alloy is in a state in which fine particles of metal silicon (Si) are dispersed in each particle of other metal elements, or in a state in which other metal elements are dispersed in each Si particle. As for the other metal element, a thing is preferable. As a method for producing the Si alloy, mechanical synthesis based on mechanical alloy method is possible, or production can be made by heating and cooling a mixture of Si particles and other metal elements. Composition of the Si alloy is, in terms of the atomic ratio between Si and other metal elements, preferably 50:50 to 90:10, and more preferably 60:40 to 80:20.
It is possible that both SiO and Si alloy are coated with carbon. Hardness of the negative electrode active material is set at 10 GPa or more and 20 GPa or less as described in the above. Hardness of the negative electrode active material can be measured by using a nanoindentation method or the like. By mixing the negative electrode active material with a binder, a thickening agent, a conductive material, a solvent, or the like, if necessary, a negative electrode mixture slurry is produced.
As for the electrolyte solution, an organic electrolyte solution prepared by dissolving one or more kinds of lithium salts selected from LiPF6, LiBF4, LiClO4, LiN(C2F5SO2)2, and the like into one or more kinds of nonaqueous solvent selected from ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, γ-butyrolactone, γ-valerolactone, methyl acetate, ethyl acetate, methyl propionate, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethan, 1-ethoxy-2-methoxyethene, 3-methyltetrahydrofuran, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, and the like, or a known electrolyte used in battery including a solid electrolyte having conductivity of a lithium ion, a gel phase electrolyte, and a molten salt can be used.
As for the battery can 4 and the battery cover 9, aluminum or stainless steel is preferably used.
The discharge capacity of the negative electrode of a lithium ion secondary battery according to the present invention (negative electrode capacity) is preferably 600 Ah/kg or more and 1000 Ah/kg or less. That is because, when it is less than 600 Ah/kg, the expansion amount is small, and thus it is unlikely to have an occurrence of short circuit, and, when it is more than 1000 Ah/kg, the battery cycle service life is significantly impaired so that it is difficult to be used for a battery. Furthermore, when it is less than 600 Ah/kg, contribution to high energy densification is small.
The lithium ion secondary battery according to the present invention is suitable for suppressing short circuit of a wound type battery illustrated in
The lithium ion secondary battery illustrated in
(1) Production of Lithium Ion Secondary Battery
As a positive electrode active material, LiNi0.8Co0.1Mn0.1 was used for all. As a negative electrode active material containing Si, Si70Ti15Fe15, Si70Cu30 or Si70Ti30 was used in Examples 1 to 15. In Comparative Examples 1 to 9, Si70Ti15Fe15 or SiO was used. In Reference Examples 1 and 2, Si70Ti15Fe15 or Si (pure Si) was used. A mixture in which the negative electrode active material containing Si and graphite are mixed at predetermined mixing ratio was used as a negative electrode active material. Furthermore, for any negative electrode active material containing Si, the material coated with carbon to have thickness of 10 nm or so was used. Constitution of the negative electrode active materials of Examples 1 to 15, Comparative Examples 1 to 9, and Reference Examples 1 and 2 is shown in the following Table 1.
As for the separator, polyethylene was used as a resin layer and SiO2 was used as a porous layer. Film thickness of the resin layer and porous layer is also described in the following Table 1.
As an electrolyte solution, an electrolyte of 1 M LiPF6 was used, and the electrolyte dissolved in solvent (EC:EMC=1:3, % by volume) was used.
A negative electrode mixture slurry was prepared and applied on top of a current collecting foil followed by pressing to produce a negative electrode. The negative electrode slurry was prepared by using, other than the aforementioned negative electrode active material and a binder, acetylene black as a conductive material with weight ratio of 92:5:3 in the order, and mixing with NMP as a solvent such that the viscosity is 5000 to 8000 mPa and also the solid content ratio is 70% or more and 90% or less. Furthermore, the viscosity value of the slurry in the present invention indicates the viscosity 600 seconds after stirring the slurry at 0.5 rpm. Furthermore, a planetary mixer was used for the slurry production.
By using the obtained negative electrode slurry, application on copper foil was carried out with a table top comma coater. The application was made such that, like the positive electrode which will be described later, a negative electrode non-coated part not applied with the negative electrode active material mixture is formed on part of the copper foil.
As for the current collecting foil, each of the three kinds of stainless foil, copper foil containing a different kind of an element (one or more kinds of zirconium, silver, and tin) in copper with purity of 99.9% or more, and copper foil with purity of 99.99% or more, was used.
As for the application amount, the negative electrode application amount was adjusted for each such that the volume ratio between the positive electrode and negative electrode is 1.0 when the positive electrode application amount of 240 g/m2 is used. First drying was carried out by passing it through a drying furnace with drying temperature of 100° C. In addition, the electrode was subjected to vacuum drying for 1 hour at 300° C. (second drying), and the density was adjusted by using a roll press. With regard to the density, pressing was carried out so as to have the electrode porosity of 20 to 40% or so, the negative electrode containing Si and SiO was prepared to have density of 1.4 g/cm3, and the negative electrode containing Si alloy was prepared to have density of 2.3 g/cm3 or so.
The positive electrode having a lead which has been produced accordingly is illustrated in
As a positive electrode current collecting foil, aluminum foil was used. On both surfaces of the aluminum foil, a positive electrode mixture layer was formed. As a positive electrode active material mixture, a positive electrode active material of LiNi0.8Co0.1Mn0.1 was used, and by having a conductive material consisted of a carbon material and PVDF as a binder (binding material) with their weight ratio at 90:5:5, a positive electrode slurry was prepared. The application amount was set at 240 g/m2. For application of the positive electrode active material mixture onto aluminum foil, the viscosity of the positive electrode slurry was adjusted with N-methyl-2-pyrrolidone as a dispersion solvent. At that time, as described in the above, the application was made such that the positive electrode non-coated 14 that is not applied with the positive electrode active material mixture is formed on part of the aluminum foil. Namely, the aluminum foil is exposed on the positive electrode non-coated part 14. The positive electrode was prepared to have density of 3.5 g/cm3 by using a roll press after drying the positive electrode mixture layer.
The prepared positive electrode and negative electrode were wound while they are mediated by a separator, and then inserted to a battery can. The negative electrode current collecting lead stripe 6 was collectively welded by ultrasonication to the nickel negative electrode current collecting lead part 8, and the current collecting lead part was welded to the bottom of the can. Meanwhile, the positive electrode current collecting lead stripe 5 was welded by ultrasonication to the aluminum current collecting lead part 7, and then the aluminum lead part was subjected to resistance welding to the cover 9. After injecting an electrolyte solution, the cover was sealed by coking of the can 4 to obtain a battery. Furthermore, between the top part of the can and the cover, a gasket 12 was inserted. Accordingly, a battery of 1 Ah grade was produced.
(2) Measurement of Hardness of Negative Electrode Active Material
The hardness was measured based on a nanoindentation method. As an apparatus, Nano Indenter XP/DCM manufactured by Keysight Technologies was used. The indentation depth was 200 nm and the average value of 10 active material particles containing Si was calculated. The measurement results are shown in the following Table 2.
(3) Evaluation of Battery Characteristics
(i) Measurement of Negative Electrode Capacity
A 10 mAh grade model cell was produced by using single electrode Li metal. 0.1 CA static current charging was carried out with lower limit voltage of 0.01 V when compared to the counter electrode Li followed by static voltage charging for 2 hours. Then, after resting for 15 minutes, 0.1 CA static current discharging was carried out till to have upper limit voltage of 1.5 V. From discharged current value (A)×time for discharging (h) Weight of active material (kg) at that time, the discharge capacity (Ah/kg) was calculated. In the present invention, a lithium ion secondary battery which has negative electrode discharge capacity of 600 Ah/kg or more and 1000 Ah/kg or less was produced. The measurement results are described in the following Table 2.
(ii) Measurement of Energy Density, Cycle Characteristics (Capacity Retention Rate), and Safety (Short Circuit Rate)
After carrying out static current charging with voltage of 4.2 V and current of ⅓ CA by using the produced cell, static voltage charging was carried out for 2 hours. As for the discharging, static current discharging with voltage of 2.0 V and current of ⅓ CA was carried out. 3 Cycles of this process were carried out. Then, after static current charging with voltage of 3.7 V and current of ⅓ CA followed by static voltage charging for 2 hours, the cell was allowed to stand for 1 week. After the standing, a cell with 3.4 V or less was defined as short circuit, and number of short circuits among 10 cells was calculated as occurrence rate of short circuit.
After that, to calculate the energy density, static current charging with voltage of 4.2 V and current of ⅓ CA was carried out followed by static voltage charging for 2 hours. As for the discharging, static current discharging with voltage of 2.0 V and current of ⅓ CA was carried out. From the discharge capacity (Ah) and mean voltage (V), the energy (Wh) was calculated. According to division of the energy by the cell weight, the energy density (Wh/kg) was calculated. Furthermore, when 100 cycles of the above charging and discharging conditions are carried out, according to the division of the capacity at the hundredth cycle by the capacity at the first cycle, the cycle capacity retention rate was calculated. The measurement results are described in the following Table 2.
As shown in Tables 1 and 2, it is found that the lithium ion secondary battery according to the present invention (Examples 1 to 115) achieves a high level in all of the energy density, cycle characteristics, and safety.
More specifically, in Examples 1 to 11, an active material in which Si70Ti15Fe15 was used as a negative electrode active material containing Si and mixed with graphite at ratio of 50% by mass is used, and film thickness of a resin layer and film thickness of a porous layer of the separator are varied. It was found that the short circuit rate is 0% for all 10 cells, illustrating the cells have high safety and also high energy density and high cycle characteristics.
In Examples 12 and 13, the negative electrode active material containing Si of Example 3 was changed and Si70Cu30 and Si70Ti30 are used instead of Si70Ti15Fe15 of Example 3. It was also found that Examples 12 and 13 also have high safety and also high energy density and high cycle characteristics.
In Examples 14 and 15, the graphite mixing ratio of Example 3 was changed. The negative electrode capacity was found to be modified by changing the mixing ratio.
On the other hand, it was found that all of Comparative Examples 1 to 9 in which the constitution of a lithium ion secondary battery is outside the range of the present invention cannot sufficiently satisfy any of the energy density, cycle characteristics, and safety.
More specifically, it was found that, as the separator of Comparative Examples 1 to 7 has film thickness of a resin layer and film thickness of a porous layer that are different from those defined by the present invention and due to an easy occurrence of short circuit, it is impossible to achieve the high safety. As a result of disassembling and examining the battery, scorching referred to as a black spot was observed from a separator between the current collecting lead part of the positive electrode and the negative electrode mixture layer. It is easily considered to be a result of mispositioning of an electrode member that is caused by high expansion amount of a negative electrode and the stress during expansion⋅shrinkage of a negative electrode. Furthermore, as a result of measuring the expansion amount for each of the Si alloy as an active material containing Si used in Examples (mixture with 50% by mass of graphite), SiO used in Comparative Examples (mixture with 50% by mass of graphite), Si (mixture with 50% by mass of graphite, and graphite, the result was found to be 1.2 times for Si alloy, 1.2 times also for SiO, and 3 times or so for Si compared to graphite. The expansion amount indicates a difference of the thickness of the negative electrode mixture layer between 100% SOC (State Of Charge) (counter electrode Li potential of 0.01 V) and 0% SOC (counter electrode Li potential of 1.5 V).
In Comparative Example 6, the resin layer and porous layer of the separator are outside those defined by the present invention, and the amount of the negative electrode active material containing Si is also small. Because the amount of the negative electrode active material containing Si is small, it is unlikely to have short circuit, but high energy densification cannot be achieved.
In Comparative Example 8, only the graphite is present as a negative electrode active material, and because the negative electrode active material containing Si is not included, the high energy densification cannot be expected.
In Comparative Example 9, the negative electrode active material containing Si is SiO, and the electrode density is as low as 1.4 g/cm3 compared to the electrode density of 2.3 g/cm3 of Si alloy. However, because the irreversible capacity is as high as 16% compared to the irreversible capacity of 8% of Si alloy, the high energy densification cannot be expected. Furthermore, since SiO tends to have soft particles, it was found that short circuit is not likely to occur even with the same expansion rate.
In Reference Example 1, the film thickness of a resin layer and the film thickness of a porous layer of the separator satisfy the requirements of the present invention. However, as there is a large amount of the negative electrode active material containing Si, the cycle characteristics are significantly deteriorated so that the practical application is not possible.
In Reference Example 2, the film thickness of a resin layer and the film thickness of a porous layer of the separator satisfy the requirements of the present invention. However, as the negative electrode active material containing Si is Si, it was found that the discharge capacity and energy density of the negative electrode are low, cycle characteristics are poor, and it cannot be used as a battery. As a result of disassembling and examining the battery, separation of the negative electrode mixture layer was illustrated. This can be considered to be a phenomenon that is caused by a high expansion amount.
Furthermore, although the resin layer was a single layer of polyethylene in the above Examples, it was confirmed that the same effect as those Examples is obtained even from a case in which a resin layer with three-layer structure as illustrated in
As explained in the above, it was illustrated that a lithium ion secondary battery that prevents short circuit of a battery and in which energy density, cycle characteristics, and safety are all balanced at high levels, and a method for producing the lithium ion secondary battery can be provided by the present invention.
Furthermore, the present invention is not limited to the aforementioned Examples, and various modification examples are included herein. For example, the aforementioned Examples have been explained in detail to help easy understanding of the present invention, and the present invention is not necessarily limited to those having all the constitutions that are described above. Furthermore, part of a constitution of any Example may be replaced with a constitution of another Example, and also a constitution of an Example may be added to a constitution of another Example. Furthermore, part of the constitution of each Example may be added, deleted, or replaced with another constitution.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2015-209866 | Oct 2015 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2016/081651 | 10/26/2016 | WO | 00 |
