JP5853639B2 - Lithium ion battery, separator for lithium ion battery, battery pack, electronic device, electric vehicle, power storage device, and power system - Google Patents

Description

The present technology relates to a lithium ion battery , a separator for the lithium ion battery , a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system.

  Due to the remarkable development of portable electronic technology in recent years, mobile phones and notebook computers are recognized as basic technologies that support an advanced information society. Research and development related to the enhancement of functions of these devices has been energetically advanced, and it has been a problem that the driving time is shortened due to the increase in power consumption due to the enhancement of functions.

  In order to secure a driving time of a certain level or higher, it is essential to increase the energy density of a secondary battery used as a driving power source. For example, a lithium ion secondary battery is expected.

  In studies aimed at increasing the capacity and safety of lithium-ion secondary batteries, it is necessary to add functionality to the polyolefin microporous membrane because sufficient performance cannot be obtained with conventional polyolefin microporous membranes alone. It is. As a method for imparting a function to the polyolefin microporous membrane, for example, a method of coating resins having different properties on the polyolefin microporous membrane has been proposed.

  For example, in Patent Document 1, a separator including a porous substrate for a separator in which plate-like inorganic oxide particles are integrated with a binder resin and a porous film containing a resin having a melting point in the range of 80 to 130 ° C. Proposed. The plate-like particles constituting the separator porous substrate have a heat-resistant temperature of 150 ° C. or higher, at least part of them has heat resistance and electrical insulation, and is electrochemically stable. The number average particle diameter of the particles is 0.1 μm or more and 15 μm or less. By using this separator as a battery separator such as a lithium ion secondary battery, lithium dendrite can be prevented by the presence of inorganic oxide particles.

  Patent Document 2 proposes a lithium ion secondary battery having a porous heat-resistant layer provided on a surface where a positive electrode plate and a negative electrode plate face each other, a polyolefin microporous film, and a nonaqueous electrolyte. In this lithium ion secondary battery, the filler of the porous heat-resistant layer has a particle size distribution of 5.0 μm or less, D10 in the particle size distribution measurement is 0.2 to 0.6 μm, and the mode diameter is 0.80. A metal oxide of ˜1.25 μm is used.

  Patent Document 3 proposes a lithium battery in which an inorganic protective film is formed on one surface of a separator interposed between an anode and a cathode. In this lithium battery, by forming an inorganic protective film on the surface of the separator, a separator / inorganic protective film structure is formed to block the movement of the cathode active material. Thereby, the self discharge of a battery and the capacity | capacitance reduction can be suppressed.

JP 2008-243825 A JP 2008-27634 A JP 2004-158453 A

In the lithium ion battery, improvement in insulation between electrodes and improvement in charge / discharge cycle characteristics are desired. Accordingly, an object of the present technology is to provide a lithium ion battery and a separator for the lithium ion battery that can improve insulation between electrodes and charge / discharge cycle characteristics, and a battery pack, electronic device, electric vehicle, power storage device, and electric power using the lithium ion battery. To provide a system.

（式中、ａ、ｂ、ｃ、ｄはそれぞれ０以上の整数である。ａ、ｂ、ｃ、ｄの和は２以上の整数であり、ａとｂとの和は１以上の整数である。ｅ、ｆ、ｇ、ｈはそれぞれ１以上の整数である。Ｒ１およびＲ２は、いずれも１価の基であり、互いに結合して環を形成してもよい。Ｒ３は、ａ、ｂ、ｃ、ｄの和を価数とする基である。）

（式中、Ｒ４は（ａ１＋ｂ１＋ｃ１）価の基である。ａ１、ｄ１、およびｎは１以上の整数であり、ｂ１およびｃ１は０以上の整数である。ただし、（ｂ１＋ｃ１）≧１である。） In order to solve the above-described problem, the present technology includes a positive electrode, a negative electrode, an insulating layer between the positive electrode and the negative electrode, and an electrolytic solution containing a solvent and an electrolyte salt. and molecular materials, inorganic oxides, silicon carbide, a first filler comprising at least one of aluminum nitride and boron nitride, and have a resin layer and a second filler consisting of lithium salt, lithium salt, carbonate Lithium, lithium fluoride, lithium sulfate, lithium nitrate, lithium tetraborate, lithium metaborate, lithium pyrophosphate, lithium tripolyphosphate, lithium orthosilicate, lithium metasilicate, dilithium oxalate, represented by the general formula (A) A lithium ion battery that is at least one selected from the group consisting of lithium salts represented by the general formula (B) .

(In the formula, a, b, c and d are each an integer of 0 or more. The sum of a, b, c and d is an integer of 2 or more, and the sum of a and b is an integer of 1 or more. E, f, g, and h are each an integer equal to or greater than 1. R1 and R2 are each a monovalent group and may be bonded to each other to form a ring, and R3 represents a, b, This is a group having the valence of the sum of c and d.)

(In the formula, R4 is a (a1 + b1 + c1) -valent group. A1, d1, and n are integers of 1 or more, and b1 and c1 are integers of 0 or more, provided that (b1 + c1) ≧ 1. )

This technique includes a first polymeric material, inorganic oxides, silicon carbide, a first filler comprising at least one of aluminum nitride and boron nitride, and a second filler consisting of lithium salt, porous structure The lithium salt comprises lithium carbonate, lithium fluoride, lithium sulfate, lithium nitrate, lithium tetraborate, lithium metaborate, lithium pyrophosphate, lithium tripolyphosphate, lithium orthosilicate, lithium metasilicate, It has an electrolyte containing a solvent and an electrolyte salt, which is at least one selected from the group consisting of dilithium acid, a lithium salt represented by the general formula (A), and a lithium salt represented by the general formula (B) It is a separator for lithium ion batteries .

  In the present technology, the battery pack, the electronic device, the electric vehicle, the power storage device, and the power system include the above-described lithium ion battery.

  In the present technology, the resin layer has a configuration including an inorganic oxide filler and a lithium salt filler. By including an inorganic oxide filler and a lithium salt filler in the resin layer, insulation between electrodes and charge / discharge cycle characteristics can be improved.

  According to the present technology, insulation between electrodes and charge / discharge cycle characteristics can be improved.

FIG. 1 is an enlarged cross-sectional view illustrating a configuration example of a separator according to the first embodiment of the present technology. FIG. 2 is a cross-sectional view showing a cross-sectional configuration of a nonaqueous electrolyte battery according to the second embodiment of the present technology. FIG. 3 is an enlarged cross-sectional view showing a part of the spirally wound electrode body 20 shown in FIG. FIG. 4A is a perspective view showing a configuration example of a nonaqueous electrolyte battery according to a third embodiment of the present technology. FIG. 4B is an exploded perspective view illustrating a configuration example of the nonaqueous electrolyte battery according to the third embodiment of the present technology. FIG. 5 is an enlarged cross-sectional view showing a part of the battery element in an enlarged manner. FIG. 6 is an enlarged cross-sectional view showing a part of the battery element in an enlarged manner. FIG. 7 is a block diagram illustrating a configuration example of the battery pack according to the embodiment of the present technology. FIG. 8 is a schematic diagram illustrating an example of application to a residential power storage system using the nonaqueous electrolyte battery of the present technology. FIG. 9 is a schematic diagram schematically illustrating an example of a configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied.

Hereinafter, embodiments of the present technology will be described with reference to the drawings as appropriate. The description will be given in the following order. Note that, in all the drawings of the embodiment, portions denoted by the same reference numerals are the same or corresponding portions, and overlapping descriptions are appropriately omitted.
1. First embodiment (example of separator)
2. Second embodiment (example of cylindrical battery)
3. Third embodiment (first example of flat battery)
4). Fourth embodiment (second example of flat battery)
5). Fifth embodiment (third example of flat battery)
6). Sixth embodiment (example of battery pack)
7). Seventh embodiment (an example of a power storage system)
8). Other embodiment (modification)

1. First Embodiment A separator according to a first embodiment of the present technology will be described. The separator according to the first embodiment of the present technology has sufficient electrolyte solution impregnation properties, and can improve separator performance and charge / discharge cycle characteristics without hindering ionic conductivity. When such a separator is provided in a battery such as a lithium ion secondary battery, better battery characteristics can be obtained.

(Configuration of separator)
FIG. 1 is an enlarged cross-sectional view illustrating a configuration example of a separator according to the first embodiment of the present technology. The separator 4 shown in FIG. 1 is an insulating material that allows lithium ions to pass through while separating a positive electrode and a negative electrode and preventing a short circuit due to contact between both electrodes. The separator 4 is comprised from the base material layer 4a and the functional resin layer 4b. In addition, in the example of FIG. 1, the functional resin layer 4b is provided on one main surface of the base material layer 4a. However, the functional resin layer 4b may be provided on both main surfaces of the base material layer 4a. . Moreover, the base material layer 4a may be provided as necessary, and the separator 4 may be formed only by the functional resin layer 4b.

(Base material layer)
The base material layer 4a is, for example, a microporous film of polyolefin resin. As the polyolefin resin, polyethylene (PE), polypropylene (PP), or a mixture of these polyolefin resins can be used. The microporous film of polyolefin resin may be a single layer film or a multi-layered film in which a plurality of microporous films of polyolefin resin are stacked. The polyolefin resin has a shutdown function that cuts off the current by clogging the opening near the melting point.

  The thickness of the base material layer 4a should just be the same grade as the separator generally used, for example, it is preferable that they are 5 micrometers or more and 20 micrometers or less. In addition, the thickness of the base material layer 4a is not limited to what was illustrated.

(Functional resin layer)
The functional resin layer 4b includes an inorganic oxide filler, a lithium salt filler, and a polymer material different from the base material layer 4a. The polymer material different from the base material layer 4a is, for example, a polymer material different from the polyolefin resin of the material of the base material layer 4a.

  The functional resin layer 4b has a porous structure. More specifically, the porous structure of the functional resin layer 4b is, for example, a porous interconnect structure in which the pores are interconnected. For example, the functional resin layer 4b has a palm porometer (CFP-1500A manufactured by Seika Sangyo Co., Ltd.) and a non-mercury porosimeter (LEP-200-A). When using the bubble point method, the half dry method, and the measurement method using the Darcy law, the most detailed diameter of the through-hole diameter of the functional resin layer 4b is the base material layer 4a. A diameter larger than the most detailed diameter of the through hole diameter is preferable. This is because the functional resin layer 4b having such a structure is superior in the impregnation property and ionic conductivity of the electrolytic solution.

  For example, if the smallest diameter of the through hole of the functional resin layer 4b is smaller than that of the base material layer 4a, the portion becomes an ion conductive bottleneck, and the ionic conductivity is higher than that of the separator composed only of the base material layer 4a. However, battery characteristics such as cycle characteristics tend to be reduced. Therefore, the function as a separator tends to be reduced. However, when the smallest diameter of the through hole of the functional resin layer is larger than that of the base material layer 4a, the function of the functional resin layer 4b can be expressed more without reducing the ionic conductivity of the base material layer 4a. Is possible. Therefore, it is preferable that the smallest diameter of the through hole of the functional resin layer 4b is larger than the smallest diameter of the through hole of the base material layer 4a.

  The functional resin layer 4b has a low contact angle with the electrolytic solution. For example, the contact angle with the electrolytic solution having a general configuration is preferably 11 degrees or less. By adding an inorganic oxide filler and a lithium salt filler to the functional resin layer 4b, the contact angle with the electrolytic solution can be reduced.

  Factors for improving the wettability of the electrolytic solution in the functional resin layer 4b are that the affinity itself between the added inorganic oxide particles, the lithium salt filler, and the electrolytic solution is high, and also due to voids existing in the functional resin layer 4b. It is mentioned that the impregnation of the electrolytic solution is promoted by capillary action.

(Fillers such as inorganic oxides)
As fillers such as inorganic oxides used in the functional resin layer 4b, aluminum oxide (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), magnesium oxide (MgO), silicon dioxide (SiO ₂₎ ) And the like, and silicon carbide (SiC), aluminum nitride (AlN), or boron nitride (BN ) are used. These may be used alone or in combination of two or more. The shapes of these fillers are not limited, and various shapes such as a spherical shape, a needle shape, an ellipsoid shape, a plate shape, and a scale shape can be used, for example.

  The inorganic oxide filler preferably has a center particle size of 0.2 μm or more and 5.0 μm or less. When the center particle size is too small, the inorganic oxide filler aggregates, and there is a possibility that it is difficult to form a good layer when forming the functional resin layer 4b. In addition, secondary particles in which the inorganic oxide filler is agglomerated locally exist and may be non-uniform. The central particle size is a particle size (D50) having an integrated value of 50% of the volume-based particle size distribution obtained by the laser diffraction method.

  On the other hand, when the center particle diameter exceeds 5.0 μm, the capillary phenomenon due to the voids formed by the mixing of the inorganic oxide filler is reduced, the wettability is reduced, or the wettability is reduced due to the non-uniformity of the voids. There is a risk of bias. Further, there is a possibility that the layer is not formed well when the functional resin layer 4b is formed. Similarly to the case where the inorganic oxide filler is aggregated, secondary particles in which the inorganic oxide filler is aggregated are locally present and may be non-uniform. That is, the formation process of the functional resin layer 4b includes a process of applying a resin solution in which a polymer material and an inorganic oxide filler are mixed. In this application process, the resin solution is spread by the inorganic oxide filler having a large particle size. There is a risk that there will be no areas.

Moreover, it is preferable that the specific surface area of an inorganic oxide filler is 2.0 m < ² > / g or more. When the specific surface area is too small, the area in contact with the electrolytic solution is small, so that the impregnation property of the electrolytic solution may be reduced. In addition, when the specific surface area is too large, the viscosity of the resin solution containing the inorganic oxide filler becomes high at the time of forming the functional resin layer 4b, and there is a concern that the gel slurry may exhibit a structural viscosity. In this case, it may be difficult to add a predetermined amount of the inorganic oxide filler. In the case of a slurry having a high viscosity, it may be difficult to form the functional resin layer 4b.

Further, when the center particle size [μm] of the inorganic oxide filler is X and the specific surface area [m ² / g] is Y, the center particle size [μm] of the inorganic oxide filler and the specific surface area [m ² / g The value of the product X × Y is preferably 1.0 or more and 18 or less. By setting the value within this range, the capacity maintenance rate can be further improved.

(Lithium salt filler)
As the lithium salt filler to be used for the functional resin layer 4b, those having poor solubility in the solvent of the electrolytic solution are used. Examples of the lithium salt of the lithium salt filler include lithium phosphate (Li ₃ PO ₄ ), lithium carbonate (Li ₂ CO ₃ ), lithium fluoride (LiF), lithium sulfate (Li ₂ SO ₄ ), and nitric acid. Lithium (LiNO ₃ ), lithium tetraborate (Li ₂ B ₄ O ₇ ), lithium metaborate (LiBO ₂ ), lithium pyrophosphate (Li ₄ P ₂ O ₇ ), lithium tripolyphosphate (Li ₅ P ₃ O ₁₀ ) , Lithium orthosilicate (Li ₄ SiO ₄ ), lithium metasilicate (Li ₂ SiO ₃ ), dilithium oxalate (Li ₂ C ₂ O ₄ ), a lithium salt represented by the following general formula (A), A lithium salt represented by the general formula (B) is used. These may be used alone or in combination of two or more. The shape of the lithium filler is not limited, and various shapes such as a spherical shape, a needle shape, an ellipsoid shape, a plate shape, and a scale shape can be used.

（式中、ａ、ｂ、ｃ、ｄはそれぞれ０以上の整数である。ａ、ｂ、ｃ、ｄの和は２以上の整数であり、ａとｂとの和は１以上の整数である。ｅ、ｆ、ｇ、ｈはそれぞれ１以上の整数である。Ｒ１およびＲ２は、いずれも１価の基であり、互いに結合して環を形成してもよい。Ｒ３は、ａ、ｂ、ｃ、ｄの和を価数とする基である。）

（式中、Ｒ４は（ａ１＋ｂ１＋ｃ１）価の基である。ａ１、ｄ１、およびｎは１以上の整数であり、ｂ１およびｃ１は０以上の整数である。ただし、（ｂ１＋ｃ１）≧１である。）

(In the formula, a, b, c and d are each an integer of 0 or more. The sum of a, b, c and d is an integer of 2 or more, and the sum of a and b is an integer of 1 or more. E, f, g, and h are each an integer equal to or greater than 1. R1 and R2 are each a monovalent group and may be bonded to each other to form a ring, and R3 represents a, b, This is a group having the valence of the sum of c and d.)

(In the formula, R4 is a (a1 + b1 + c1) -valent group. A1, d1, and n are integers of 1 or more, and b1 and c1 are integers of 0 or more, provided that (b1 + c1) ≧ 1. )

  As the lithium salt in the general formula (A), for example, R1 and R2 in the general formula (A) are each independently an alkyl group, an alkenyl group, an alkynyl group, a trialkylsilyl group, or a group obtained by halogenating them. And a lithium salt in which R3 is a hydrocarbon group. More specifically, examples of the lithium salt represented by the general formula (A) include lithium salts represented by the formula (A-1) to the formula (A-8).

  As the lithium salt represented by the general formula (B), R4 in the general formula (B) is a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, a cyclic saturated hydrocarbon group, or the like. Examples thereof include a lithium salt which is a halogenated group. More specifically, examples of the lithium salt represented by the general formula (B) include lithium salts represented by the formulas (B-1) to (B-62).

  The lithium salt filler preferably has a center particle size of 0.2 μm or more and 5.0 μm or less. When the center particle size is too small, the lithium salt filler aggregates and there is a possibility that the layer may not be formed well when the functional resin layer 4b is formed. In addition, secondary particles in which the lithium salt filler is agglomerated locally exist and may be non-uniform.

  In the functional resin layer 4b, the battery characteristics (particularly charge / discharge cycle characteristics) are improved by the inclusion of the lithium salt filler as follows. That is, a part of the lithium salt filler added to the functional resin layer 4b is dissolved in the electrolytic solution in the battery cell, and this dissolved material forms a film on the electrode surface. This contributes to the improvement of the chemical conversion property and the lithium acceptability of the surface of the negative electrode active material.

However, since the lithium salt filler applied to the present technology is poor in solubility in the solvent of the electrolytic solution, the charging voltage range in which a normal lithium ion secondary battery is used, for example, a range lower than 5 V Then, the amount dissolved in the electrolytic solution is a part of the added lithium salt filler. In other words, the lithium salt filler applied to this technology reaches the equilibrium state after being dissolved in a certain amount in the electrolytic solution in the charging voltage range where ordinary lithium ion secondary batteries are used, so that further dissolution is suppressed. It is thought that it is done. Therefore, in the present technology, the lithium salt filler as a whole dissolves and does not exhibit the effect as in the case of using a lithium salt filler that is easily and completely dissolved in the solvent of the electrolytic solution (for example, LiPF ₆ ). Things don't happen.

  On the other hand, in a situation where the charging voltage is 5 V or more, for example, the progress of dissolution of the lithium salt filler into the electrolyte solution becomes significant, and thus the entire lithium salt filler may be dissolved and disappear. For this reason, it is necessary to prevent disappearance of the functional resin layer 4b by containing an inorganic oxide filler that is stable even at a charging voltage of 5 V or more in the functional resin layer 4b. When no inorganic oxide filler is contained, the cell structure becomes unstable as the lithium salt filler dissolves in a charged state of 5 V or higher, which is not suitable. An inorganic oxide filler expresses the function which supports a cell structure at the time of charge of 5 V or more even if a small amount is added.

  In addition, the lithium salt filler component dissolved in a situation where the charging voltage is, for example, 5 V or more can suppress an excessive reaction between the electrolytic solution and the active material by forming a film on the surface of the positive electrode or the negative electrode. is there. For example, this effect can be expected to suppress the reaction between the electrolyte and the active material in an overcharged state with a charging voltage of 5 V or more, and to suppress the heat generation and thermal runaway of the battery.

(Polymer material)
As the polymer material constituting the functional resin layer 4b, a heat resistant resin, a fluorine resin, or the like can be used. Here, the heat-resistant resin means a resin having a glass transition temperature of 200 ° C. or higher in the case of an amorphous resin. In the case of a crystalline resin, it means a resin having a glass transition temperature of 200 ° C. or higher and no melting point or a melting point of 250 ° C. or higher.

  As the heat-resistant resin, a polymer material having a glass transition temperature as high as possible is preferable from the viewpoint of dimensional stability in a high-temperature atmosphere, and it does not have a melting point with melting entropy because it can reduce dimensional change and shrinkage due to flow. Resins are preferred. Specific examples of such a polymer material include polyamides such as polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, polyarylate, polyetherimide, polyamideimide, polyimide, and aramid. These may be used alone or in combination of two or more.

  When a heat-resistant resin is used as the polymer material constituting the functional resin layer 4b, the area shrinkage rate at a high temperature can be reduced. For example, at 200 ° C., the area heat shrinkage rate of the separator 4 is 60%. In the following cases, the safety of the battery can be remarkably improved.

  Examples of the fluororesin include polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, a vinylidene fluoride copolymer such as a copolymer of vinylidene fluoride, hexafluoropropylene, and chlorotrifluoroethylene, or Polytetrafluoroethylene or the like can be used. These may be used alone or in combination of two or more. When a fluorine-based resin is used as the polymer material constituting the functional resin layer 4b, the electrochemical stability, the electrolyte solution impregnation property, the electrolyte solution retention property, the flexibility, and the like can be improved.

  When such a polymer material is used, the mixing ratio between the total amount of the inorganic oxide filler and the lithium salt filler and the polymer material is preferably 10: 1 to 30: 1 (mass ratio). When the mixing amount is too small, the effect of adding the inorganic oxide filler and the lithium salt filler tends to be reduced. In addition, when the mixing amount is too large, the holding power of the inorganic oxide filler and the lithium salt filler is reduced, and for example, the inorganic oxide filler or the lithium salt filler is likely to fall off during winding. The parts where the filler and lithium salt filler have fallen tend to have poor liquid retention and battery characteristics.

  The mixing ratio of the inorganic oxide filler and the lithium salt filler is preferably in the range of 1:99 to 98: 2. When no inorganic oxide filler is contained, the cell structure becomes unstable as the lithium salt filler dissolves in a charged state of 5 V or higher, which is not suitable. An inorganic oxide filler expresses the function which supports a cell structure at the time of charge of 5 V or more even if a small amount is added. When the mixing amount of the lithium salt filler is too small, the effect of adding the lithium salt filler tends to be reduced.

  The thickness of the functional resin layer 4b is preferably, for example, 1 μm or more and 10 μm or less. In addition, the thickness of the functional resin layer 4b is not limited to what was illustrated. The center particle diameter of the inorganic oxide filler is preferably 50% or less with respect to the thickness of the functional resin layer 4b. When the center particle diameter of the inorganic oxide filler is too large with respect to the thickness of the functional resin layer 4b, it tends to be difficult to form the functional resin layer 4b. The center particle diameter of the lithium salt filler is preferably 90% or less with respect to the thickness of the functional resin layer 4b. When the center particle diameter of the inorganic oxide filler is too large with respect to the thickness of the functional resin layer 4b, it tends to be difficult to form the functional resin layer 4b.

  The separator 4 has all the through-hole diameters of the functional resin layer 4b obtained when measured by the measurement method using the bubble point method, the half dry method, and Darcy's law within the range of 0.015 μm to 20 μm. The functional resin layer 4b having a through-hole diameter of 0.02 μm or more and 10 μm or less is preferably 50% or more of the whole.

  If the through hole of the functional resin layer 4b has a hole diameter of less than 0.015 μm, the ion permeability is remarkably inhibited and battery characteristics such as deterioration of cycle characteristics tend to be reduced. If so, the apparent resin density tends to decrease and the mechanical strength of the film tends to decrease. Further, if the diameter of the through hole is 0.02 μm or more and 10 μm or less, the amount of the above phenomenon tends to easily occur if it is less than 50% of the whole.

  For example, even if the surface has a large opening, if the inside is narrow enough to deteriorate the ion path, the battery characteristics tend to be reduced. Therefore, as a porous evaluation index, it is important to know not the surface pores but the internal structure (most pore portion), and if the through-hole diameter is in the above numerical range, better battery characteristics can be obtained. Can be obtained.

  The puncture strength of the separator 4 is preferably in the range of 100 gf to 1000 gf. This is because if the puncture strength is low, a short circuit may occur, and if the puncture strength is high, the ionic conductivity tends to decrease.

  The air permeability of the separator 4 is preferably in the range of 30 sec / 100 cc or more and 1000 sec / 100 cc or less. This is because when the air permeability is low, a short circuit may occur, and when the air permeability is high, the ionic conductivity tends to decrease.

  The separator 4 is not limited to the two-layer structure of the base material layer 4a and the functional resin layer 4b described above, and may include the base material layer 4a and the functional resin layer 4b. For example, it may have a structure of three or more layers. The separator 4 may be a single layer composed of the functional resin layer 4b.

  Furthermore, as the resin constituting the functional resin layer 4b, a mixture of two or more kinds of resins may be used. Furthermore, the resin constituting the functional resin layer 4b is not limited to a heat resistant resin or a fluorine resin, and any resin can be used as long as it can improve the performance and battery characteristics of the separator. Good.

  In the separator according to the first embodiment of the present technology, the wettability of the electrolytic solution can be improved by including the functional resin layer 4b including the inorganic oxide filler and the lithium salt filler. Since the electrolyte solution retention becomes better as the specific surface area is larger, the particle diameters of the inorganic oxide filler and the lithium salt filler are preferably smaller.

  On the other hand, when at least one of the particle diameters of the inorganic oxide filler and the lithium salt filler is smaller than the pore diameter of the separator base material layer 4a, the separator compression by the expansion / contraction of the electrode accompanying charge / discharge causes the base material layer The pores tend to be filled with at least one of an inorganic oxide filler and a lithium salt filler. For this reason, the pores of the separator important for ionic conductivity tend to be clogged, and the cycle characteristics and load characteristics of the battery tend to be reduced.

  In addition, clogging is suppressed when the particle size is large, but uncoated areas tend to occur in the resin solution coating process when forming the mixed layer of inorganic oxide particles and lithium salt particles, and the coating thickness is reduced. It tends to be difficult to form.

  In the present technology, the impregnation property and the liquid retention property of the electrolytic solution may be further improved by controlling the central particle size, the specific surface area, and the value obtained by multiplying the central particle size and the specific surface area of the inorganic oxide filler. Further, by including an inorganic oxide filler in the functional resin layer, the oxidation resistance of the separator can be improved, and the heat conduction and heat sink effect of the inorganic oxide filler can be improved. Furthermore, by including a lithium salt filler in addition to the inorganic oxide filler in the functional resin layer, the lithium salt dissolves in the electrolyte in the battery cell, and a film is formed on the surfaces of the positive electrode and the negative electrode active material. Thus, charge / discharge cycle characteristics can be improved by improving the oxidation resistance of the surface of the positive electrode active material and the lithium acceptability of the surface of the negative electrode active material.

  The difference between the separator of the present technology and the technologies of Patent Documents 1 to 3 shown in the “Background Technology” column is as follows. That is, for example, Patent Document 1 exemplified in the section of “Background Art” describes that lithium dendrite is prevented by the presence of an inorganic oxide filler to improve safety, but the separator of the present technology is not described. Thus, it is not described about the point which can improve a battery characteristic or prevent the fall of a battery characteristic.

  Although Patent Document 2 describes improving heat resistance by providing a porous heat-resistant layer, it prevents battery performance from being lowered or battery characteristics from being deteriorated like the separator of the present technology. There is no mention of what can be done. Further, although there are descriptions of inorganic oxides, the embodiment is limited to magnesium oxide, and no mention is made of other inorganic oxides.

  Patent Document 3 describes that the self-discharge and capacity reduction of the battery can be suppressed by blocking the movement of the cathode active material by the separator / inorganic protective film multilayer structure in which the inorganic protective film is formed on the surface of the separator. Has been. However, this inorganic protective film is formed by a method of directly forming an inorganic protective film material such as a gas reaction method, a thermal vapor deposition method, a sputtering method, or a chemical vapor deposition method to obtain a thin film. Such a thin inorganic protective film is useful for suppressing the self-discharge of the battery, but has a high density, and on the contrary, by providing the inorganic protective film, sufficient impregnation of the electrolyte can be obtained. The problem that it becomes impossible to occur. On the other hand, in the separator of the present technology, the functional resin layer has a porous structure (preferably a porous interconnected structure in which the pores are interconnected), so that sufficient impregnation of the electrolytic solution can be obtained.

(Manufacturing method of separator)
The manufacturing method of the separator 4 of this technique is demonstrated.

(Preparation of base material layer)
First, a polyolefin microporous film or the like is prepared as the base material layer 4a. The polyolefin microporous membrane can be formed by, for example, a stretch opening method or a phase separation method. For example, in the stretch opening method, first, a molten polymer is extruded from a T die or a circular die, and further subjected to heat treatment to form a crystal structure with high regularity. Thereafter, low-temperature stretching and further high-temperature stretching are performed to separate the crystal interface to create a gap between lamellas, thereby forming a porous structure. In the phase separation method, a uniform solution prepared by mixing a polymer and a solvent at a high temperature is formed into a film by a T-die method, an inflation method, etc., and then the solvent is extracted with another volatile solvent, thereby obtaining a microporous material. A substrate can be obtained. In addition, the manufacturing method of the base material layer 4a is not limited to these, The method proposed conventionally can be used widely. Moreover, you may use the porous film etc. which can be obtained as it is marketed.

  Below, the example of preparation of a polyethylene microporous film is demonstrated as an example of the specific preparation example of the base material layer 4a. First, a polyethylene resin and liquid paraffin as a plasticizer are supplied to a twin screw extruder and melt kneaded to prepare a polyethylene solution. Next, it extrudes at a predetermined temperature from a T die attached to the tip of the extruder, and forms a gel-like sheet while winding it with a cooling roll. Then, a thin film is obtained by performing biaxial stretching with respect to this gel-like sheet.

  Next, this thin film is washed with hexane to remove residual liquid paraffin, and then dried and heat-treated to make the thin film microporous. As described above, a polyethylene microporous film as the base material layer 4a can be obtained.

(Production of functional resin layer)
Next, the functional resin layer 4b is formed on one main surface or both main surfaces of the base material layer 4a. First, a resin solution in which a polymer material, an inorganic oxide filler, and a lithium salt filler are dissolved in a polar solvent such as N-methyl-2-pyrrolidone (NMP) is applied to the base material layer 4a with a desktop coater or the like. . Thereafter, the base material layer 4a to which the resin solution is applied is immersed in a poor solvent that is compatible with the polar solvent such as water and is a poor solvent for the polymer material. At this time, solvent exchange occurs, phase separation (for example, spinodal decomposition type phase separation) occurs, and the polymer material forms a porous structure. Then, it is dried with hot air. As described above, the functional resin layer 4b having a porous structure is formed on the base material layer 4a. The porous structure of the functional resin layer 4b is, for example, a porous interconnect structure in which the pores are interconnected. For example, the inorganic oxide filler and the lithium salt filler are supported on a fine resin skeleton having a three-dimensional network structure interconnected to form a porous structure, for example. The inorganic oxide filler and the lithium salt filler can be maintained in a dispersed state without being connected to each other by being supported on the fine resin skeleton. By the above, the separator 4 in which the functional resin layer 4b is formed on one main surface or both main surfaces of the base material layer 4a can be obtained.

  In addition, in order for the structure of the functional resin layer 4b to be a porous interconnection structure, it is preferable to adjust the concentration of the resin in the resin solution applied to the base material layer 4a to an appropriate concentration.

  The resin solution is obtained by dispersing an inorganic oxide filler, a lithium salt filler, and a polymer material in N-methyl-2-pyrrolidone as a solvent. And when the density | concentration of an inorganic oxide filler, a lithium salt filler, and a polymeric material is too deep with respect to a solvent, it replaces with a poor solvent in the state after apply | coating the resin solution on the base material layer 4a. --Methyl-2-pyrrolidone voids are arranged in a spherical droplet structure. For this reason, when it puts into a water bath and phase-separates and this is dried, it will be in the state in which the space | gap was formed independently, and the layer which has a structure in which many independent pores which were not mutually connected was formed will be formed. For this reason, it does not become a porous interconnection structure.

  On the other hand, when the concentration of the inorganic oxide filler, the lithium salt filler and the polymer material is too thin with respect to the solvent, the resin has a spherical droplet structure in a state where the resin solution is applied on the base material layer 4a. End up. For this reason, when it is put into a water bath and phase-separated and dried, the resin drops off because a large number of droplet-shaped resins are not bonded to each other, so the structure of the functional resin layer 4b is porous. Does not form a connection structure.

2. Second Embodiment A nonaqueous electrolyte battery according to a second embodiment of the present technology will be described. The nonaqueous electrolyte battery according to the second embodiment of the present technology is a nonaqueous electrolyte battery using the separator 4 described above. For example, this non-aqueous electrolyte battery is a secondary battery that can be charged and discharged, and is, for example, a lithium ion secondary battery in which the capacity of the negative electrode is expressed based on insertion and extraction of lithium as an electrode reactant.

(Battery configuration)
FIG. 2 shows a cross-sectional configuration of the nonaqueous electrolyte battery according to the first embodiment of the present technology. FIG. 3 shows an enlarged part of the spirally wound electrode body 20 shown in FIG. This non-aqueous electrolyte battery is a so-called cylindrical type, in which a strip-shaped positive electrode 2 and a strip-shaped negative electrode 3 are wound through a separator 4 inside a substantially hollow cylindrical battery can 1. An electrode body 20 is provided. The separator 4 is an insulating layer that separates the positive electrode 2 and the negative electrode 3 and allows lithium ions to pass while preventing a short circuit due to contact between the two electrodes.

  The battery can 1 is made of, for example, iron (Fe) plated with nickel (Ni), and has one end closed and the other end open. Inside the battery can 1, a pair of insulating plates 5 and 6 are arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 20.

  At the open end of the battery can 1, a battery lid 7, a safety valve mechanism 8 and a thermal resistance element (PTC element) 9 provided inside the battery lid 7 are interposed via a gasket 10. It is attached by caulking and the inside of the battery can 1 is sealed.

  The battery lid 7 is made of, for example, the same material as the battery can 1. The safety valve mechanism 8 is electrically connected to the battery lid 7 via a heat sensitive resistance element 9, and the disk plate 11 is reversed when the internal pressure of the battery becomes a certain level or more due to internal short circuit or external heating. Thus, the electrical connection between the battery lid 7 and the wound electrode body 20 is cut off.

  The heat-sensitive resistor element 9 limits the current by increasing the resistance value when the temperature rises, and prevents abnormal heat generation due to a large current. The gasket 10 is made of, for example, an insulating material, and asphalt is applied to the surface.

  The wound electrode body 20 is wound around, for example, the center pin 12. A positive electrode lead 13 made of aluminum (Al) or the like is connected to the positive electrode 2 of the wound electrode body 20, and a negative electrode lead 14 made of nickel (Ni) or the like is connected to the negative electrode 3. The positive electrode lead 13 is electrically connected to the battery lid 7 by welding to the safety valve mechanism 8, and the negative electrode lead 14 is welded and electrically connected to the battery can 1.

(Positive electrode)
FIG. 3 shows an enlarged part of the spirally wound electrode body 20 shown in FIG. As shown in FIG. 3, the positive electrode 2 includes, for example, a positive electrode current collector 2 </ b> A having a pair of opposed surfaces, and a positive electrode mixture layer 2 </ b> B provided on both surfaces of the positive electrode current collector 2. In addition, you may make it have the area | region where the positive mix layer 2B was provided only in the single side | surface of 2 A of positive electrode collectors. The positive electrode current collector 2A is made of, for example, a metal foil such as an aluminum (Al) foil. The positive electrode mixture layer 2B includes, for example, a positive electrode active material, and may include a conductive agent such as graphite and a binder such as polyvinylidene fluoride as necessary.

  As the positive electrode active material, a positive electrode material capable of inserting and extracting lithium can be used. Specifically, as the positive electrode material, for example, a lithium-containing compound such as lithium oxide, lithium phosphorus oxide, lithium sulfide, or an intercalation compound containing lithium is suitable, and a mixture of two or more of these is used. Also good. In order to increase the energy density, a lithium-containing compound containing lithium (Li), a transition metal element, and oxygen (O) is preferable. Among them, as the transition metal element, cobalt (Co), nickel (Ni), manganese (Mn And at least one selected from the group consisting of iron (Fe).

  Examples of such a lithium-containing compound include a lithium composite oxide having an average composition represented by chemical formula I, more specifically chemical formula II, and a lithium composite oxide having an average composition represented by chemical formula III. be able to.

(Chemical I)
_{Li p Ni (1-qr)} Mn q M1 r O (2-s) X t
(In the formula, M1 represents at least one element selected from Group 2 to Group 15 excluding nickel (Ni) and manganese (Mn). X represents Group 16 element and Group 17 element other than oxygen (O). P, q, r, s, and t are 0 ≦ p ≦ 1.5, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.0, −0.10 ≦ s ≦. (The values are within the range of 0.20 and 0 ≦ t ≦ 0.2. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of p represents the value in a fully discharged state.)

(Chemical II)
Li _a Co _(1-b) M2 _b O _(2-c)
(Wherein M2 is vanadium (V), copper (Cu), zirconium (Zr), zinc (Zn), magnesium (Mg), aluminum (Al), gallium (Ga), yttrium (Y) and iron (Fe). Represents at least one of the group consisting of: values of a, b and c are 0.9 ≦ a ≦ 1.1, 0 ≦ b ≦ 0.3, −0.1 ≦ c ≦ 0.1 Note that the composition of lithium varies depending on the state of charge and discharge, and the value of a represents the value in a fully discharged state.)

(Chemical III)
_{Li v Ni w Co x Mn y} M3 (1-vxy) O (2-z)
(Wherein M3 is vanadium (V), copper (Cu), zirconium (Zr), zinc (Zn), magnesium (Mg), aluminum (Al), gallium (Ga), yttrium (Y) and iron (Fe). Represents at least one of the group consisting of: v, w, x, y and z have values of 0.9 ≦ v ≦ 1.1, 0 <w <1, 0 <x <1, 0 <y. <0.5, 0 ≦ 1-vxy, −0.1 ≦ z ≦ 0.1 The composition of lithium varies depending on the state of charge and discharge, and the value of v is a complete discharge. Represents the value in the state.)

  Further, examples of the lithium-containing compound include a lithium composite oxide having a spinel structure represented by Formula IV, more specifically, LidMn 2 O 4 (d≈1).

(Chemical IV)
Li _e Mn _(2-f) M4 _f O _g F _h
(In the formula, M4 is cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W). f, g, and h are values within a range of 0.9 ≦ e ≦ 1.1, 0 ≦ f ≦ 0.6, 3.7 ≦ g ≦ 4.1, and 0 ≦ h ≦ 0.1. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of e represents the value in a fully discharged state.

  Furthermore, examples of the lithium-containing compound include V, more specifically, lithium composite phosphate having an olivine type structure represented by chemical VI, and more specifically, LiiFePO4. (I≈1).

(Chemical V)
Li _j M5 _k PO ₄
(In the formula, M5 represents at least one element selected from Groups 2 to 15. j and k are in the range of 0 ≦ j ≦ 2.0 and 0.5 ≦ k ≦ 2.0. (Note that the composition of lithium varies depending on the state of charge and discharge, and the value of j represents the value in a fully discharged state.)

(Chemical VI)
Li _m M6PO ₄
(In the formula, M6 is cobalt (Co), manganese (Mn), iron (Fe), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V ), Niobium (Nb), copper (Cu), zinc (Zn), molybdenum (Mo), calcium (Ca), strontium (Sr), tungsten (W) and zirconium (Zr) M is a value in the range of 0.9 ≦ m ≦ 1.1, and the composition of lithium varies depending on the state of charge and discharge, and the value of m represents a value in a fully discharged state. )

In addition to the positive electrode materials described above, examples of positive electrode materials that can occlude and release lithium (Li) include inorganic materials such as MnO ₂ , V ₂ O ₅ , V ₆ O ₁₃ , NiS, and MoS that do not contain lithium. A compound can be mentioned.

(Negative electrode)
The negative electrode 3 has, for example, a structure in which a negative electrode mixture layer 3B is provided on both surfaces of a negative electrode current collector 3A having a pair of opposed surfaces. Although not shown, the negative electrode mixture layer 3B may be provided only on one surface of the negative electrode current collector 3A. The negative electrode current collector 3A is made of, for example, a metal foil such as a copper (Cu) foil or a nickel (Ni) foil.

  The negative electrode mixture layer 3B includes one or more negative electrode materials capable of occluding and releasing lithium as a negative electrode active material, and the positive electrode mixture layer 2B as necessary. It is comprised including the binder similar to.

  In this nonaqueous electrolyte battery, for example, the electrochemical equivalent of the negative electrode material capable of occluding and releasing lithium is larger than the electrochemical equivalent of the positive electrode 2, and the negative electrode 3 is charged with lithium during the charging. It is preferable that the metal does not precipitate.

  In addition, this nonaqueous electrolyte battery is designed such that an open circuit voltage (that is, a battery voltage) in a fully charged state is in a range of, for example, 4.2 V or more and 4.9 V or less. For example, when the open circuit voltage in the fully charged state is 4.25 V or more, the amount of lithium released per unit mass is increased even with the same positive electrode active material, compared to a 4.2 V battery. Accordingly, the amounts of the positive electrode active material and the negative electrode active material are adjusted, and a high energy density is obtained. In addition, the open circuit voltage (namely, battery voltage) in a full charge state may be less than 4.2V, for example.

  Examples of the negative electrode material capable of occluding and releasing lithium include graphite, non-graphitizable carbon, graphitizable carbon, pyrolytic carbons, cokes, glassy carbons, and fired organic polymer compounds And carbon materials such as carbon fiber and activated carbon.

  Among these, examples of coke include pitch coke, needle coke, and petroleum coke. An organic polymer compound fired body refers to a carbonized material obtained by firing a polymer material such as phenol resin or furan resin at an appropriate temperature, and part of it is non-graphitizable carbon or graphitizable carbon. Some are classified as: Examples of the polymer material include polyacetylene and polypyrrole.

  These carbon materials are preferable because the change in crystal structure that occurs during charge and discharge is very small, a high charge and discharge capacity can be obtained, and good cycle characteristics can be obtained. In particular, graphite is preferable because it has a high electrochemical equivalent and can provide a high energy density. Further, non-graphitizable carbon is preferable because excellent characteristics can be obtained. Furthermore, a battery having a low charge / discharge potential, specifically, a battery having a charge / discharge potential close to that of lithium metal is preferable because a high energy density of the battery can be easily realized.

  Examples of the negative electrode material capable of inserting and extracting lithium include materials capable of inserting and extracting lithium and containing at least one of a metal element and a metalloid element as a constituent element. This is because a high energy density can be obtained by using such a material. In particular, use with a carbon material is more preferable because a high energy density can be obtained and excellent cycle characteristics can be obtained. This negative electrode material may be a single element, alloy or compound of a metal element or a metalloid element, or may have at least a part of one or more of these phases. In the present invention, the alloy includes an alloy containing one or more metal elements and one or more metalloid elements in addition to an alloy composed of two or more metal elements. Moreover, the nonmetallic element may be included. Some of the structures include a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or two or more of them.

  Examples of metal elements or metalloid elements constituting the negative electrode material include magnesium (Mg), boron (B), aluminum (Al), gallium (Ga), indium (In), silicon (Si), and germanium (Ge). ), Tin (Sn), lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd) ) Or platinum (Pt). These may be crystalline or amorphous.

  Among these, as the negative electrode material, a material containing a 4B group metal element or a semimetal element in the short-period type periodic table as a constituent element is preferable, and at least one of silicon (Si) and tin (Sn) is particularly preferable. It is included as an element. This is because silicon (Si) and tin (Sn) have a large ability to occlude and release lithium (Li), and a high energy density can be obtained.

As an alloy of tin (Sn), for example, as a second constituent element other than tin (Sn), silicon (Si), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb), and chromium (Cr) The thing containing at least 1 sort is mentioned. As an alloy of silicon (Si), for example, as a second constituent element other than silicon (Si), tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb), and chromium (Cr). The thing containing 1 type is mentioned.

  Examples of the tin (Sn) compound or silicon (Si) compound include those containing oxygen (O) or carbon (C). In addition to tin (Sn) or silicon (Si), the above-described compounds are used. Two constituent elements may be included.

  Among them, tin (Sn), cobalt (Co) and carbon (C) are included as constituent elements, and the content of carbon (C) is in the range of 9.9 mass% to 29.7 mass%, tin (Sn) And the ratio (Co / (Sn + Co)) of cobalt (Co) with respect to the sum total of cobalt (Co) is within a range of 30% by mass or more and 70% by mass or less. This is because in such a composition range, a high energy density is obtained and an excellent cycle characteristic is obtained.

  This SnCoC-containing material may further contain other constituent elements as necessary. Examples of other constituent elements include silicon (Si), iron (Fe), nickel (Ni), chromium (Cr), indium (In), niobium (Nb), germanium (Ge), titanium (Ti), and molybdenum. (Mo), aluminum (Al), phosphorus (P), gallium (Ga), bismuth (Bi), and the like are preferable, and two or more of them may be included. This is because the capacity characteristic or cycle characteristic is further improved.

  The SnCoC-containing material has a phase containing tin (Sn), cobalt (Co), and carbon (C), and this phase has a low crystallinity or an amorphous structure. preferable. In the SnCoC-containing material, it is preferable that at least a part of carbon as a constituent element is bonded to a metal element or a metalloid element as another constituent element. The decrease in cycle characteristics is thought to be due to aggregation or crystallization of tin (Sn) or the like, but such aggregation or crystallization is suppressed when carbon is combined with other elements. It is.

  Examples of the measurement method for examining the bonding state of elements include X-ray photoelectron spectroscopy (XPS). In this XPS, in the apparatus calibrated so that the 4f orbit (Au4f) peak of gold atom is obtained at 84.0 eV, the peak of 1s orbit (C1s) of carbon appears at 284.5 eV in the case of graphite. . Moreover, if it is surface contamination carbon, it will appear at 284.8 eV. In contrast, when the charge density of the carbon element is high, for example, when carbon is bonded to a metal element or a metalloid element, the C1s peak appears in a region lower than 284.5 eV. That is, when the peak of the synthetic wave of C1s obtained for the SnCoC-containing material appears in a region lower than 284.5 eV, a metal in which at least a part of carbon (C) contained in the SnCoC-containing material is another constituent element Bonded with element or metalloid element.

  In XPS, for example, the peak of C1s is used to correct the energy axis of the spectrum. Usually, since surface-contaminated carbon exists on the surface, the C1s peak of the surface-contaminated carbon is set to 284.8 eV, which is used as an energy standard. In XPS, the waveform of the peak of C1s is obtained as a form including the peak of surface contamination carbon and the peak of carbon in the SnCoC-containing material. For example, by analyzing using commercially available software, the surface contamination The carbon peak and the carbon peak in the SnCoC-containing material are separated. In the waveform analysis, the position of the main peak existing on the lowest bound energy side is used as the energy reference (284.8 eV).

Examples of the negative electrode material capable of inserting and extracting lithium further include other metal compounds or polymer materials. Other metal compounds include lithium titanate (Li ₄ Ti ₅ O ₁₂ ), oxides such as MnO ₂ , V ₂ O ₅ and V ₆ O ₁₃ , sulfides such as NiS and MoS, and lithium such as LiN _3. Examples of the polymer material include polyacetylene, polyaniline, and polypyrrole.

  The negative electrode mixture layer 3B may be formed by any of, for example, a gas phase method, a liquid phase method, a thermal spraying method, a firing method, or coating, or a combination of two or more thereof. As the vapor phase method, for example, physical deposition method or chemical deposition method, specifically, vacuum deposition method, sputtering method, ion plating method, laser ablation method, thermal chemical vapor deposition (CVD; Chemical Vapor Deposition) Or plasma chemical vapor deposition. As the liquid phase method, a known method such as electroplating or electroless plating can be used. The firing method is, for example, a method in which a particulate negative electrode active material is mixed with a binder and dispersed in a solvent and then heat treated at a temperature higher than the melting point of the binder. A known method can also be used for the firing method, for example, an atmospheric firing method, a reactive firing method, or a hot press firing method.

(Electrolyte)
As the electrolytic solution, a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent can be used. As the non-aqueous solvent, for example, it is preferable to contain at least one of ethylene carbonate (EC) and propylene carbonate (PC). This is because the cycle characteristics can be improved. In particular, it is preferable to mix and contain ethylene carbonate (EC) and propylene carbonate (PC) because cycle characteristics can be further improved. The non-aqueous solvent also includes at least one of chain carbonates such as diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), or methyl propyl carbonate (MPC). It is preferable. This is because the cycle characteristics can be further improved.

  The non-aqueous solvent preferably further contains at least one of 2,4-difluoroanisole and vinylene carbonate (VC). This is because 2,4-difluoroanisole can improve the discharge capacity, and vinylene carbonate (VC) can further improve the cycle characteristics. In particular, it is more preferable that they are mixed and contained because both the discharge capacity and the cycle characteristics can be improved.

  Examples of the non-aqueous solvent further include butylene carbonate (BC), γ-butyrolactone, γ-valerolactone, those obtained by substituting some or all of the hydrogen groups of these compounds with fluorine groups, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, methyl acetate, methyl propionate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropironitrile, N, N- Contains one or more of dimethylformamide, N-methylpyrrolidinone, N-methyloxazolidinone, N, N-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, dimethyl sulfoxide or trimethyl phosphate You may go out.

  Depending on the electrode to be combined, the reversibility of the electrode reaction may be improved by using a material in which part or all of the hydrogen atoms of the substance contained in the non-aqueous solvent group are substituted with fluorine atoms. Therefore, these substances can be used as appropriate.

Examples of the lithium salt that is an electrolyte salt include LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiClO ₄ , LiB (C ₆ H ₅ ) ₄ , LiCH ₃ SO ₃ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) _2. , LiC (SO ₂ CF ₃ ) ₃ , LiAlCl ₄ , LiSiF ₆ , LiCl, LiBF ₂ (ox) [lithium difluorooxalate borate], LiBOB [lithium bisoxalate borate], or LiBr are suitable. Any one kind or two kinds or more can be mixed and used. Among them, LiPF ₆ is preferable because high ion conductivity can be obtained and cycle characteristics can be improved.

  The separator 4 is impregnated with an electrolytic solution. In the nonaqueous electrolyte battery according to the second embodiment of the present technology, when charged, for example, lithium ions are detached from the positive electrode 2 and inserted in the negative electrode 3 through the electrolytic solution. When discharging is performed, for example, lithium ions are detached from the negative electrode 3 and inserted into the positive electrode 2 through the electrolytic solution.

(Battery manufacturing method)
The manufacturing method of the nonaqueous electrolyte battery mentioned above is demonstrated.

(Preparation of positive electrode)
The positive electrode 2 is produced as described below. First, for example, a positive electrode active material, a conductive agent, and a binder are mixed to prepare a positive electrode mixture, and this positive electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to form a positive electrode mixture. Use slurry.

  Next, after applying this positive electrode mixture slurry to the positive electrode current collector 2A and drying the solvent, the positive electrode mixture layer 2B is formed by compression molding with a roll press or the like, and the positive electrode 2 is produced.

(Preparation of negative electrode)
The negative electrode 3 is produced as described below. First, for example, a negative electrode active material and a binder are mixed to prepare a negative electrode mixture, and the negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to obtain a negative electrode mixture slurry.

  Next, after applying this negative electrode mixture slurry to the negative electrode current collector 3A and drying the solvent, the negative electrode mixture layer 3B is formed by compression molding using a roll press or the like, and the negative electrode 3 is produced.

(Assembly of non-aqueous electrolyte battery)
Next, the positive electrode lead 13 is attached to the positive electrode current collector 2A by welding or the like, and the negative electrode lead 14 is attached to the negative electrode current collector 3A by welding or the like. Next, the positive electrode 2 and the negative electrode 3 are wound through the separator 4, and the tip of the positive electrode lead 13 is welded to the safety valve mechanism 8, and the tip of the negative electrode lead 14 is welded to the battery can 1. The rotated positive electrode 2 and negative electrode 3 are sandwiched between a pair of insulating plates 5 and 6 and stored in the battery can 1.

  Next, an electrolytic solution is injected into the battery can 1 and the separator 4 is impregnated with the electrolytic solution. Next, the battery lid 7, the safety valve mechanism 8, and the heat sensitive resistance element 9 are fixed to the opening end of the battery can 1 by caulking through the gasket 10. As described above, the nonaqueous electrolyte battery according to the second embodiment of the present technology is manufactured.

3. Third Embodiment A nonaqueous electrolyte battery according to a third embodiment of the present technology will be described. This nonaqueous electrolyte battery is, for example, a secondary battery that can be charged and discharged, and is, for example, a lithium ion secondary battery in which the capacity of the negative electrode is expressed based on insertion and extraction of lithium as an electrode reactant.

(Battery configuration)
FIG. 4A is a perspective view showing a configuration example of a nonaqueous electrolyte battery according to a third embodiment of the present technology. FIG. 4B is an exploded perspective view illustrating a configuration example of the nonaqueous electrolyte battery according to the third embodiment of the present technology. As shown in FIGS. 4A and 4B, the shape of the nonaqueous electrolyte battery is, for example, a so-called flat type. This non-aqueous electrolyte battery is a laminate-type non-aqueous electrolyte battery in which the battery element 30 is covered with an exterior material 37 such as a laminate film.

  The nonaqueous electrolyte battery includes a battery element 30 and an exterior material 37 that sheathes the battery element 30. The nonaqueous electrolyte battery has a configuration in which the battery element 30 is sealed by welding the periphery of the battery element 30 after housing the battery element 30 in the recess of the exterior member 37. The battery element 30 accommodated in the exterior member 37 is provided with a positive electrode lead 32 and a negative electrode lead 33, and adhesion to the exterior material 37 is improved on both surfaces of the positive electrode lead 32 and the negative electrode lead 33. For this purpose, a resin piece 34 and a resin piece 35 are provided. The positive electrode lead 32 is sandwiched between the facing exterior members 37 via the resin pieces 34 and pulled out, and the negative electrode lead 33 is sandwiched between the facing exterior members 37 via the resin pieces 35. And pulled out.

(Exterior material)
The exterior material 37 is, for example, a moisture-proof laminate film. The packaging material 37 has, for example, a laminated structure in which a heat sealing layer, a metal layer, and a surface protective layer are sequentially laminated. For example, the outer packaging material 37 has a three-layer structure of “thermal fusion layer / metal layer / surface protective layer”.

  The heat fusion layer is made of, for example, a polymer film. Examples of the material constituting the polymer film include polypropylene (PP), polyethylene (PE), unstretched polypropylene (CPP), linear low density polyethylene (LLDPE), and low density polyethylene (LDPE). The metal layer is made of, for example, a metal foil. Examples of the material constituting the metal foil include aluminum (Al). Moreover, it is also possible to use metals other than aluminum as a material which comprises metal foil. Examples of the material constituting the surface protective layer include nylon (Ny) and polyethylene terephthalate (PET). Note that the surface on the heat-sealing layer side is a storage surface on the side where the battery element 30 is stored.

(Battery element)
FIG. 5 shows an enlarged cross-sectional view of the battery element 30. As shown in FIG. 5, the battery element 30 has a winding structure in which a positive electrode 42 and a negative electrode 43 are stacked and wound via a separator 44 and an electrolyte layer 45. The positive electrode 42 and the negative electrode 43 are isolated by an insulating layer 46 having a separator 44 and an electrolyte layer 45, and a short circuit due to contact between both electrodes is prevented.

(Positive electrode)
The positive electrode 42 includes a strip-shaped positive electrode current collector 42A and a positive electrode mixture layer 42B formed on both surfaces of the positive electrode current collector 42A. One end of the positive electrode 42 in the longitudinal direction is provided with a positive electrode lead 32 connected by, for example, spot welding or ultrasonic welding. As a material of the positive electrode lead 32, for example, a metal such as aluminum can be used.

(Negative electrode)
The negative electrode 43 includes a strip-shaped negative electrode current collector 43A and a negative electrode mixture layer 43B formed on both surfaces of the negative electrode current collector 43A. Similarly to the positive electrode 42, the negative electrode lead 33 connected by, for example, spot welding or ultrasonic welding is also provided at one end portion of the negative electrode 43 in the longitudinal direction. As a material of the negative electrode lead 33, for example, copper (Cu), nickel (Ni), or the like can be used.

  The configurations of the positive electrode current collector 42A, the positive electrode mixture layer 42B, the negative electrode current collector 43A, and the negative electrode mixture layer 43B are respectively the positive electrode current collector 2A, the positive electrode mixture layer 2B, and the negative electrode current collector of the second embodiment. The configurations of the body 3A and the negative electrode mixture layer 3B are the same.

(Separator)
The separator 44 is the same as the separator 4 of the first embodiment. That is, the separator 44 is composed of a base material layer 4a and a functional resin layer 4b formed on one main surface or both main surfaces of the base material layer 4a. In addition, the separator 44 may be comprised only by the functional resin layer 4b.

(Electrolyte layer)
The electrolyte layer 45 includes an electrolytic solution and a polymer material that serves as a holding body that holds the electrolytic solution. The electrolyte layer 45 is, for example, a gel-like ionic conductor that is formed into a so-called gel shape by swelling a polymer material with an electrolytic solution. The electrolyte layer 45 is preferable because it can obtain high ionic conductivity and prevent battery leakage. The configuration of the electrolytic solution (that is, liquid solvent, electrolyte salt, etc.) is the same as in the second embodiment.

(Polymer material)
As the polymer material, a matrix polymer compound having a property compatible with a solvent can be used. Examples of such a polymer material include polyacrylonitrile, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, and a copolymer of vinylidene fluoride, hexafluoropropylene, and chlorotrifluoroethylene. Vinylidene fluoride copolymer, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, polysiloxane, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, Mention may be made of styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene or polycarbonate. These may be used alone or in combination of two or more. In particular, from the viewpoint of electrochemical stability, polyacrylonitrile, polyvinylidene fluoride, polyhexafluoropropylene, or polyethylene oxide is preferable.

(Battery manufacturing method)
The manufacturing method of the nonaqueous electrolyte battery mentioned above is demonstrated.

(Preparation of positive and negative electrodes)
First, each of the positive electrode 42 and the negative electrode 43 is produced in the same manner as in the second embodiment.

(Formation of electrolyte layer, etc.)
Next, each of the positive electrode 42 and the negative electrode 43 is coated with a precursor solution containing the same electrolytic solution as in the second embodiment, a polymer material, and a mixed solvent, and the mixed solvent is volatilized to form a gel. An electrolyte layer 45 is formed. In addition, the positive electrode lead 32 is attached to the end of the positive electrode current collector 42A in advance by welding, and the negative electrode lead 33 is attached to the end of the negative electrode current collector 43A by welding.

  Next, the positive electrode 42 and the negative electrode 43 on which the gel electrolyte layer 45 is formed are laminated through a separator 44 to form a laminated body, and then the laminated body is wound in the longitudinal direction thereof to form a wound battery. Element 30 is formed.

(Battery element exterior)
Next, a recess 36 is formed by deep-drawing an exterior material 37 made of a laminate film, the battery element 30 is inserted into the recess 36, and an unprocessed portion of the exterior material 37 is folded back to the upper portion of the recess 36. The outer peripheral part of is thermally welded and sealed. As described above, the nonaqueous electrolyte battery according to the third embodiment of the present technology is manufactured.

4). Fourth Embodiment A nonaqueous electrolyte battery according to a fourth embodiment of the present technology will be described. The nonaqueous electrolyte battery according to the fourth embodiment of the present technology is the same as the third embodiment except for the configuration of the separator and the electrolyte layer. Hereinafter, differences from the third embodiment will be described in detail, and descriptions of points that overlap with the third embodiment will be omitted as appropriate. That is, the fourth embodiment is the same as the third embodiment except for the points described below.

(Battery element)
FIG. 6 is an enlarged cross-sectional view of the battery element. As shown in FIG. 6, the battery element 50 has a winding structure in which a positive electrode 42 and a negative electrode 43 are stacked and wound via a separator 54 and an electrolyte layer 55. The positive electrode 42 and the negative electrode 43 are isolated by an insulating layer 56 including a separator 54 and an electrolyte layer 55, and a short circuit due to contact between both electrodes is prevented. The separator 54 may be omitted.

(Separator 54)
The separator 54 is the same as the base material layer 4a of the first embodiment. That is, the separator 54 is, for example, a microporous film of polyolefin resin. As the polyolefin resin, polyethylene (PE), polypropylene (PP), or a mixture of these polyolefin resins can be used. The microporous film of polyolefin resin may be a single-layer film, or may be a multilayer film in which a plurality of microporous films of polyolefin resin are stacked.

(Electrolyte layer 55)
The electrolyte layer 55 includes an electrolytic solution similar to that of the second embodiment, a polymer material that holds the electrolytic solution, an inorganic oxide filler, and a lithium salt filler. In the electrolyte layer 55, the electrolytic solution is held by the polymer material. The electrolyte layer 55 is, for example, a gel-like ionic conductor that is formed into a so-called gel shape by swelling a polymer material with an electrolytic solution. The electrolytic solution and the polymer material are the same as those in the third embodiment. The inorganic oxide filler and the lithium salt filler are the same as those in the first embodiment.

(Battery manufacturing method)
The manufacturing method of the nonaqueous electrolyte battery mentioned above is demonstrated.

(Preparation of positive and negative electrodes)
First, each of the positive electrode 42 and the negative electrode 43 is produced in the same manner as in the second embodiment.

(Formation of electrolyte layer, etc.)
By mixing and stirring the same electrolytic solution as in the second embodiment, a polymer material, an inorganic oxide filler, a lithium salt filler, and a viscosity adjusting solvent (for example, dimethyl carbonate), a resin is obtained. Prepare the solution.

  After the resin solution is applied to both surfaces of the positive electrode 42 and the negative electrode 43, the viscosity adjusting solvent is volatilized to form the gel electrolyte layer 45. In addition, the positive electrode lead 32 is attached to the end of the positive electrode current collector 42A in advance by welding, and the negative electrode lead 33 is attached to the end of the negative electrode current collector 43A by welding. The positive electrode 42 and the negative electrode 43 on which the gel electrolyte layer 55 is formed are laminated through the base material layer 4a to form a laminated body, and then the laminated body is wound in the longitudinal direction to obtain a wound electrode body (battery Element 50) is obtained.

  The wound battery element 50 may be formed as follows. After the resin solution is applied to both sides of the separator 54, the viscosity adjusting solvent is volatilized. Thereby, the gel electrolyte layer 55 is formed on both surfaces of the separator 54. In addition, the positive electrode lead 32 is attached to the end of the positive electrode current collector 42A in advance by welding, and the negative electrode lead 33 is attached to the end of the negative electrode current collector 43A by welding. The positive electrode 42 and the negative electrode 43 are laminated via a separator 54 having a gel electrolyte layer 55 formed on both sides to form a laminated body, and then the laminated body is wound in the longitudinal direction to obtain a wound electrode body (battery Element 50) is obtained.

(Battery element exterior)
Next, a recess 36 is formed by deep-drawing an exterior material 37 made of a laminate film, the battery element 30 is inserted into the recess 36, and an unprocessed portion of the exterior material 37 is folded back to the upper portion of the recess 36. The outer peripheral part of is thermally welded and sealed. As described above, the nonaqueous electrolyte battery according to the fourth embodiment of the present technology is manufactured.

5). Fifth Embodiment A nonaqueous electrolyte battery according to a fifth embodiment of the present technology will be described. The nonaqueous electrolyte battery according to the fifth embodiment of the present technology is different from the fourth embodiment in the method of forming the electrolyte layer 55. Hereinafter, differences from the fourth embodiment will be described in detail, and descriptions of points that overlap with the fourth embodiment will be omitted as appropriate. That is, the fifth embodiment is the same as the fourth embodiment except for the points described below.

(Battery manufacturing method)
A resin layer is formed on one main surface or both main surfaces of the separator 54. A resin solution in which a polymer material, an inorganic oxide filler, and a lithium salt filler are dissolved in a polar solvent such as N-methyl-2-pyrrolidone (NMP) is applied to the base material layer 4a with a desktop coater or the like. Thereafter, the base material layer 4a to which the resin solution is applied is immersed in a poor solvent that is compatible with the polar solvent such as water and is a poor solvent for the polymer material. At this time, solvent exchange occurs, phase separation (for example, spinodal decomposition type phase separation) occurs, and the polymer material forms a porous structure. Then, it is dried with hot air. As described above, a resin layer having a porous structure is formed on one main surface or both main surfaces of the separator 54. The porous structure of the resin layer is, for example, a porous interconnected structure in which the pores are interconnected. For example, the inorganic oxide filler and the lithium salt filler are supported on a fine resin skeleton having a three-dimensional network structure interconnected to form a porous structure, for example. The inorganic oxide filler and the lithium salt filler can be maintained in a dispersed state without being connected to each other by being supported on the fine resin skeleton.

  As the polymer material, a material having a property compatible with a solvent can be used. The polymer material is typically a fluoropolymer such as polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, or a copolymer of vinylidene fluoride, hexafluoropropylene, and chlorotrifluoroethylene. And vinylidene chloride copolymer. These may be one type or two or more types. The polymer material may contain one or more other polymer materials together with the polyvinylidene fluoride or the vinylidene fluoride copolymer.

  Next, a positive electrode and a negative electrode manufactured in the same manner as in the fourth embodiment are stacked and wound via a separator 54 having a resin layer formed on one main surface or both main surfaces, thereby having a winding structure. The battery element 50 is produced. Next, a recess 36 is formed by deep drawing the exterior material 37 made of a laminate film, the battery element 50 is inserted into the recess 36, and an unprocessed portion of the exterior material 37 is folded back to the upper portion of the recess 36. Heat welding is performed except for a part of the outer periphery (for example, one side).

  Subsequently, an electrolyte solution similar to that of the second embodiment is prepared and injected into the interior from the unwelded portion of the exterior material 37, and then the unwelded portion of the exterior material 37 is sealed by thermal fusion or the like. Finally, heat pressing is performed to heat the exterior member 37 while applying a load, and the separator 54 is brought into close contact with the positive electrode 42 and the negative electrode 43 through the resin layer. Thereby, the electrolyte solution is impregnated into the resin layer, and at least a part of the polymer material swells to form the electrolyte layer 55. Thereby, a nonaqueous electrolyte battery is completed. In the electrolyte layer 55, a part of the polymer material swells, but the pore structure may be maintained without breaking the pore structure of the resin layer.

(Electrolyte layer)
As in the fourth embodiment, the electrolyte layer 55 includes an electrolytic solution containing an electrolyte salt and a nonaqueous solvent, a polymer material, an inorganic oxide filler, and a lithium salt filler. In the electrolyte layer 55, the resin layer holds the electrolytic solution. For example, the electrolyte layer 55 includes a gel-like ion conductor in which a polymer material is swollen by an electrolytic solution. Further, for example, in the electrolyte layer 55, the electrolytic solution swells a part of the polymer material, but the porous structure of the resin layer is maintained, and the electrolytic solution is held in a state where the pores are filled. It may be.

6). Sixth embodiment (example of battery pack)
FIG. 7 is a block diagram illustrating a circuit configuration example when a nonaqueous electrolyte battery of the present technology (hereinafter appropriately referred to as a secondary battery) is applied to a battery pack. The battery pack includes a switch unit 304 including an assembled battery 301, an exterior, a charge control switch 302a, and a discharge control switch 303a, a current detection resistor 307, a temperature detection element 308, and a control unit 310.

  In addition, the battery pack includes a positive electrode terminal 321 and a negative electrode terminal 322. During charging, the positive electrode terminal 321 and the negative electrode terminal 322 are connected to the positive electrode terminal and the negative electrode terminal of the charger, respectively, and charging is performed. Further, when the electronic device is used, the positive electrode terminal 321 and the negative electrode terminal 322 are connected to the positive electrode terminal and the negative electrode terminal of the electronic device, respectively, and discharge is performed.

  The assembled battery 301 is formed by connecting a plurality of secondary batteries 301a in series and / or in parallel. The secondary battery 301a is a secondary battery of the present technology. In FIG. 7, a case where six secondary batteries 301a are connected in two parallel three series (2P3S) is shown as an example, but in addition, n parallel m series (n and m are integers) Any connection method may be used.

  The switch unit 304 includes a charge control switch 302a and a diode 302b, and a discharge control switch 303a and a diode 303b, and is controlled by the control unit 310. The diode 302b has a reverse polarity with respect to the charging current flowing from the positive terminal 321 in the direction of the assembled battery 301 and the forward polarity with respect to the discharging current flowing from the negative terminal 322 in the direction of the assembled battery 301. The diode 303b has a forward polarity with respect to the charging current and a reverse polarity with respect to the discharging current. In the example, the switch portion is provided on the + side, but may be provided on the − side.

  The charge control switch 302 a is turned off when the battery voltage becomes the overcharge detection voltage, and is controlled by the charge / discharge control unit so that the charge current does not flow in the current path of the assembled battery 301. After the charge control switch is turned off, only discharging is possible through the diode 302b. Further, it is turned off when a large current flows during charging, and is controlled by the control unit 310 so that the charging current flowing in the current path of the assembled battery 301 is cut off.

  The discharge control switch 303a is turned off when the battery voltage becomes the overdischarge detection voltage, and is controlled by the control unit 310 so that the discharge current does not flow through the current path of the assembled battery 301. After the discharge control switch 303a is turned off, only charging is possible via the diode 303b. Further, it is turned off when a large current flows during discharging, and is controlled by the control unit 310 so as to cut off the discharging current flowing in the current path of the assembled battery 301.

  The temperature detection element 308 is, for example, a thermistor, is provided in the vicinity of the assembled battery 301, measures the temperature of the 301 assembled battery 301, and supplies the measured temperature to the control unit 310. The voltage detection unit 311 measures the voltage of the assembled battery 301 and each secondary battery 301a constituting the assembled battery 301, performs A / D conversion on the measured voltage, and supplies the voltage to the control unit 310. The current measurement unit 313 measures the current using the current detection resistor 307 and supplies this measurement current to the control unit 310.

  The switch control unit 314 controls the charge control switch 302a and the discharge control switch 303a of the switch unit 304 based on the voltage and current input from the voltage detection unit 311 and the current measurement unit 313. The switch control unit 314 sends a control signal to the switch unit 304 when any voltage of the secondary battery 301a falls below the overcharge detection voltage or overdischarge detection voltage, or when a large current flows suddenly. By sending, overcharge, overdischarge, and overcurrent charge / discharge are prevented.

  Here, for example, when the secondary battery is a lithium ion secondary battery, the overcharge detection voltage is determined to be 4.20 V ± 0.05 V, for example, and the overdischarge detection voltage is determined to be 2.4 V ± 0.1 V, for example. .

  As the charge / discharge switch, for example, a semiconductor switch such as a MOSFET can be used. In this case, the parasitic diode of the MOSFET functions as the diodes 302b and 303b. When a P-channel FET is used as the charge / discharge switch, the switch control unit 314 supplies control signals DO and CO to the gates of the charge control switch 302a and the discharge control switch 303a, respectively. When the charge control switch 302a and the discharge control switch 303a are P-channel type, they are turned on by a gate potential that is lower than the source potential by a predetermined value or more. That is, in normal charging and discharging operations, the control signals CO and DO are set to the low level, and the charging control switch 302a and the discharging control switch 303a are turned on.

  For example, during overcharge or overdischarge, the control signals CO and DO are set to a high level, and the charge control switch 302a and the discharge control switch 303a are turned off.

  The memory 317 includes a RAM and a ROM, and includes, for example, an EPROM (Erasable Programmable Read Only Memory) that is a nonvolatile memory. In the memory 317, the numerical value calculated by the control unit 310, the internal resistance value of the battery in the initial state of each secondary battery 301a measured in the manufacturing process, and the like are stored in advance, and can be appropriately rewritten. . (Also, by storing the full charge capacity of the secondary battery 301a, for example, the remaining capacity can be calculated together with the control unit 310.

  The temperature detection unit 318 measures the temperature using the temperature detection element 308, performs charge / discharge control during abnormal heat generation, and performs correction in the calculation of the remaining capacity.

7). Seventh Embodiment The nonaqueous electrolyte battery and the battery pack, battery unit, and battery module using the nonaqueous electrolyte battery described above are used for mounting or supplying power to devices such as electronic devices, electric vehicles, and power storage devices, for example. be able to.

  Examples of electronic devices include notebook computers, PDAs (personal digital assistants), mobile phones, cordless phones, video movies, digital still cameras, electronic books, electronic dictionaries, music players, radios, headphones, game consoles, navigation systems, Memory card, pacemaker, hearing aid, electric tool, electric shaver, refrigerator, air conditioner, TV, stereo, water heater, microwave oven, dishwasher, washing machine, dryer, lighting equipment, toy, medical equipment, robot, road conditioner, traffic light Etc.

  In addition, examples of the electric vehicle include a railway vehicle, a golf cart, an electric cart, an electric vehicle (including a hybrid vehicle), and the like, and these are used as a driving power source or an auxiliary power source.

  Examples of the power storage device include a power storage power source for buildings such as houses or power generation facilities.

  Below, the specific example of the electrical storage system using the electrical storage apparatus to which the nonaqueous electrolyte battery of this technique mentioned above is applied among the application examples mentioned above is demonstrated.

  This power storage system has the following configuration, for example. The first power storage system is a power storage system in which a power storage device is charged by a power generation device that generates power from renewable energy. The second power storage system is a power storage system that includes a power storage device and supplies power to an electronic device connected to the power storage device. The third power storage system is an electronic device that receives power supply from the power storage device. These power storage systems are implemented as a system for efficiently supplying power in cooperation with an external power supply network.

  Further, the fourth power storage system includes an electric vehicle having a conversion device that receives power supplied from the power storage device and converts the power into a driving force of the vehicle, and a control device that performs information processing related to vehicle control based on information related to the power storage device. It is. The fifth power storage system is a power system that includes a power information transmission / reception unit that transmits / receives signals to / from other devices via a network, and performs charge / discharge control of the power storage device described above based on information received by the transmission / reception unit. . The sixth power storage system is a power system that receives power from the power storage device described above or supplies power from the power generation device or the power network to the power storage device. Hereinafter, the power storage system will be described.

(7-1) Power Storage System in a House as an Application Example An example in which a power storage device using a nonaqueous electrolyte battery of the present technology is applied to a power storage system for a house will be described with reference to FIG. For example, in a power storage system 400 for a house 401, power is stored from a centralized power system 402 such as a thermal power generation 402a, a nuclear power generation 402b, and a hydroelectric power generation 402c through a power network 409, an information network 412, a smart meter 407, a power hub 408, and the like. Supplied to the device 403. At the same time, power is supplied to the power storage device 403 from an independent power source such as the home power generation device 404. The electric power supplied to the power storage device 403 is stored. Electric power used in the house 401 is supplied using the power storage device 403. The same power storage system can be used not only for the house 401 but also for buildings.

  The house 401 is provided with a power generation device 404, a power consumption device 405, a power storage device 403, a control device 410 that controls each device, a smart meter 407, and a sensor 411 that acquires various types of information. Each device is connected by a power network 409 and an information network 412. A solar cell, a fuel cell, or the like is used as the power generation device 404, and the generated power is supplied to the power consumption device 405 and / or the power storage device 403. The power consuming device 405 is a refrigerator 405a, an air conditioner 405b, a television receiver 405c, a bath 405d, and the like. Furthermore, the electric power consumption device 405 includes an electric vehicle 406. The electric vehicle 406 is an electric vehicle 406a, a hybrid car 406b, and an electric motorcycle 406c.

  The nonaqueous electrolyte battery of the present technology is applied to the power storage device 403. The nonaqueous electrolyte battery of the present technology may be constituted by, for example, the above-described lithium ion secondary battery. The smart meter 407 has a function of measuring the usage amount of commercial power and transmitting the measured usage amount to an electric power company. The power network 409 may be any one or a combination of DC power supply, AC power supply, and non-contact power supply.

  The various sensors 411 are, for example, human sensors, illuminance sensors, object detection sensors, power consumption sensors, vibration sensors, contact sensors, temperature sensors, infrared sensors, and the like. Information acquired by various sensors 411 is transmitted to the control device 410. Based on the information from the sensor 411, the weather condition, the condition of the person, and the like can be grasped, and the power consumption device 405 can be automatically controlled to minimize the energy consumption. Furthermore, the control device 410 can transmit information regarding the house 401 to an external power company or the like via the Internet.

  The power hub 408 performs processing such as branching of power lines and DC / AC conversion. The communication method of the information network 412 connected to the control device 410 includes a method using a communication interface such as UART (Universal Asynchronous Receiver-Transceiver), wireless communication such as Bluetooth, ZigBee, and Wi-Fi. There is a method of using a sensor network according to the standard. The Bluetooth method is applied to multimedia communication and can perform one-to-many connection communication. ZigBee uses the physical layer of IEEE (Institute of Electrical and Electronics Engineers) 802.15.4. IEEE 802.15.4 is the name of a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.

  The control device 410 is connected to an external server 413. The server 413 may be managed by any one of the house 401, the power company, and the service provider. The information transmitted and received by the server 413 is, for example, information related to power consumption information, life pattern information, power charges, weather information, natural disaster information, and power transactions. These pieces of information may be transmitted / received from a power consuming device (for example, a television receiver) in the home, or may be transmitted / received from a device outside the home (for example, a mobile phone). Such information may be displayed on a device having a display function, such as a television receiver, a mobile phone, or a PDA (Personal Digital Assistants).

  A control device 410 that controls each unit includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), and the like, and is stored in the power storage device 403 in this example. The control device 410 is connected to the power storage device 403, the home power generation device 404, the power consumption device 405, various sensors 411, the server 413 and the information network 412, and adjusts, for example, the amount of commercial power used and the amount of power generation. It has a function. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.

  As described above, electric power can be stored not only in the centralized power system 402 such as the thermal power 402a, the nuclear power 402b, and the hydraulic power 402c but also in the power storage device 403 in the power generation device 404 (solar power generation, wind power generation). it can. Therefore, even if the generated power of the home power generation device 404 fluctuates, it is possible to perform control such that the amount of power sent to the outside is constant or discharged as much as necessary. For example, the power obtained by solar power generation is stored in the power storage device 403, and the nighttime power at a low charge is stored in the power storage device 403 at night, and the power stored by the power storage device 403 is discharged during a high daytime charge. You can also use it.

  In this example, the example in which the control device 410 is stored in the power storage device 403 has been described. However, the control device 410 may be stored in the smart meter 407 or may be configured independently. Furthermore, the power storage system 400 may be used for a plurality of homes in an apartment house, or may be used for a plurality of detached houses.

(7-2) Power Storage System in Vehicle as Application Example An example in which the present technology is applied to a power storage system for a vehicle will be described with reference to FIG. FIG. 9 schematically shows an example of the configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied. A series hybrid system is a car that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power once stored in a battery.

  The hybrid vehicle 500 includes an engine 501, a generator 502, a power driving force conversion device 503, driving wheels 504 a, driving wheels 504 b, wheels 505 a, wheels 505 b, a battery 508, a vehicle control device 509, various sensors 510, and a charging port 511. Is installed. The nonaqueous electrolyte battery of the present technology described above is applied to the battery 508.

  The hybrid vehicle 500 travels using the power driving force conversion device 503 as a power source. An example of the power / driving force conversion device 503 is a motor. The electric power / driving force converter 503 is operated by the electric power of the battery 508, and the rotational force of the electric power / driving force converter 503 is transmitted to the driving wheels 504a and 504b. In addition, by using DC-AC (DC-AC) or reverse conversion (AC-DC conversion) at a required place, the power driving force conversion device 503 can be applied to either an AC motor or a DC motor. The various sensors 510 control the engine speed through the vehicle control device 509 and control the opening (throttle opening) of a throttle valve (not shown). Various sensors 510 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.

  The rotational force of the engine 501 is transmitted to the generator 502, and the electric power generated by the generator 502 by the rotational force can be stored in the battery 508.

  When the hybrid vehicle 500 decelerates by a braking mechanism (not shown), the resistance force at the time of deceleration is applied as a rotational force to the electric power driving force conversion device 503, and the regenerative electric power generated by the electric power driving force conversion device 503 by this rotational force becomes the battery 508. Accumulated in.

  The battery 508 is connected to an external power source of the hybrid vehicle 500, so that the battery 508 can receive power from the external power source using the charging port 511 as an input port and store the received power.

  Although not shown, an information processing device that performs information processing related to vehicle control based on information related to the secondary battery may be provided. As such an information processing apparatus, for example, there is an information processing apparatus that displays a remaining battery level based on information on the remaining battery level.

  In addition, the above demonstrated as an example the series hybrid vehicle which drive | works with a motor using the electric power generated with the generator driven by an engine, or the electric power once stored in the battery. However, the present technology is also effective for a parallel hybrid vehicle in which the engine and motor outputs are both driving sources, and the system is switched between the three modes of driving with only the engine, driving with the motor, and engine and motor. Applicable. Furthermore, the present technology can be effectively applied to a so-called electric vehicle that travels only by a drive motor without using an engine.

  Hereinafter, specific examples of the present technology will be described in detail. However, the present technology is not limited only to these examples.

< Reference Example 1-1 ( Example 1-1 of the original specification of the application) >
The separator of Reference Example 1-1 was produced as follows.

(Preparation of base material layer)
A polyethylene microporous membrane was used as the base material layer. The polyethylene microporous membrane used was prepared as follows. First, a polyethylene resin and liquid paraffin as a plasticizer were supplied to a twin screw extruder and melt kneaded to prepare a polyethylene solution.

  Next, it extruded from the T die attached to the front-end | tip of an extruder at predetermined temperature, and formed the gel-like sheet | seat, winding up with a cooling roll. Next, the gel sheet was biaxially stretched to obtain a thin film.

  Next, this thin film is washed with hexane to extract and remove the remaining liquid paraffin, followed by drying and heat treatment to make the thin film microporous, thereby obtaining a polyethylene microporous film having a pore diameter of 17.9 nm. It was.

(Production of functional resin layer)
A functional resin layer was formed on the base material layer. First, as an inorganic oxide filler, an aluminum oxide (Al ₂ O ₃ ) filler having a center particle diameter (X) of 0.20 μm and a specific surface area (Y) of 13.0 m ^{2 /} g (X × Y = 2.60), lithium A lithium phosphate (Li ₃ PO ₄ ) filler having a center particle size (X) of 1.0 μm was prepared as a salt filler. The center particle size of each of the inorganic oxide filler and the lithium salt filler is a particle size (D50) having an integrated value of 50% of the volume-based particle size distribution measured by a laser diffraction method.

Next, an aluminum oxide (Al ₂ O ₃ ) filler, polyvinylidene fluoride (PVdF) as a binder, and a lithium phosphate (Li ₃ PO ₄ ) filler are mixed with Al ₂ O ₃ : PVdF: Li ₃ PO ₄ (mass ratio). ) = 52: 8: 40. Thereafter, these were dissolved in N-methyl-pyrrolidone as a solvent to obtain a resin solution.

The prepared resin solution was coated on a polyethylene microporous membrane with a desktop coater, put in a water bath, phase-separated, and then dried with hot air. This includes a base material layer made of a polyethylene microporous film, an aluminum oxide (Al ₂ O ₃ ) filler, a polyvinylidene fluoride (PVdF), and a lithium phosphate (Li ₃ PO ₄ ) filler, and has a porous interconnect structure. A multilayer separator provided with a functional resin layer was obtained.

<Example 1-2>
In preparing the resin solution, a lithium carbonate (Li ₂ CO ₃ ) filler was used as the lithium salt filler instead of the lithium phosphate (Li ₃ PO ₄ ) filler. An aluminum oxide (Al ₂ O ₃ ) filler, polyvinylidene fluoride (PVdF), and a lithium carbonate (Li ₂ CO ₃ ) filler are mixed with Al ₂ O ₃ : PVdF: Li ₂ CO ₃ (mass ratio) = 82: 8: 10. Mixed with. Except for the above, a multilayer separator was produced in the same manner as in Reference Example 1-1.

<Example 1-3>
As the lithium salt filler, a lithium fluoride (LiF) filler was used in place of the lithium phosphate (Li ₃ PO ₄ ) filler. Aluminum oxide (Al ₂ O ₃ ) filler, polyvinylidene fluoride (PVdF), and lithium fluoride (LiF) filler were mixed at Al ₂ O ₃ : PVdF: LiF (mass ratio) = 62: 8: 30. Except for the above, a multilayer separator was produced in the same manner as in Reference Example 1-1.

< Reference Example 1-4 ( Example 1-4 of the original specification of the application) >
As a lithium salt filler, a lithium fluoride (LiF) filler was used together with a lithium phosphate (Li ₃ PO ₄ ) filler. An aluminum oxide (Al ₂ O ₃ ) filler, polyvinylidene fluoride (PVdF), a lithium phosphate (Li ₃ PO ₄ ) filler, and a lithium fluoride (LiF) filler are mixed with Al ₂ O ₃ : PVdF: Li ₃ PO ₄ : LiF (mass ratio) was mixed at 32: 8: 30: 30. Except for the above, a multilayer separator was produced in the same manner as in Reference Example 1-1.

<Example 1-5>
In preparing the resin solution, a lithium carbonate (Li ₂ CO ₃ ) filler was used as the lithium salt filler instead of the lithium phosphate (Li ₃ PO ₄ ) filler. An aluminum oxide (Al ₂ O ₃ ) filler, polyvinylidene fluoride (PVdF), and a lithium carbonate (Li ₂ CO ₃ ) filler are mixed with Al ₂ O ₃ : PVdF: Li ₂ CO ₃ (mass ratio) = 91: 8: 1. Mixed with. Except for the above, a multilayer separator was produced in the same manner as in Reference Example 1-1.

<Example 1-6>
In preparing the resin solution, a lithium sulfate (Li ₂ SO ₄ ) filler was used as the lithium salt filler instead of the lithium phosphate (Li ₃ PO ₄ ) filler. An aluminum oxide (Al ₂ O ₃ ) filler, polyvinylidene fluoride (PVdF), and a lithium sulfate (Li ₂ SO ₄ ) filler are mixed with Al ₂ O ₃ : PVdF: Li ₂ SO ₄ (mass ratio) = 12: 8: 80. Mixed with. Except for the above, a multilayer separator was produced in the same manner as in Reference Example 1-1.

<Example 1-7>
In preparing the resin solution, a lithium nitrate (LiNO ₃ ) filler was used as the lithium salt filler instead of the lithium phosphate (Li ₃ PO ₄ ) filler. Aluminum oxide (Al ₂ O ₃ ) filler, polyvinylidene fluoride (PVdF), and lithium nitrate (LiNO ₃ ) filler were mixed at Al ₂ O ₃ : PVdF: LiNO ₃ (mass ratio) = 72: 8: 20. Except for the above, a multilayer separator was produced in the same manner as in Reference Example 1-1.

<Example 1-8>
In the preparation of the resin solution, instead of lithium phosphate (Li ₃ PO ₄ ) filler, lithium salt filler of formula (A-2) (dilithium filler of 1,3-propanedisulfonic acid) is used as the lithium salt filler. Using. An aluminum oxide (Al ₂ O ₃ ) filler, polyvinylidene fluoride (PVdF) and a lithium salt filler of the formula (A-2) are mixed with an Al ₂ O ₃ : PVdF: lithium salt filler of the formula (A-2) (mass ratio). ) = 42: 8: 50. Except for the above, a multilayer separator was produced in the same manner as in Reference Example 1-1.

<Example 1-9>
In preparing the resin solution, a lithium salt filler of formula (B-4) (lithium 3-hydroxypropanesulfonate) was used instead of the lithium phosphate (Li ₃ PO ₄ ) filler as the lithium salt filler. . An aluminum oxide (Al ₂ O ₃ ) filler, polyvinylidene fluoride (PVdF), and a lithium salt filler of the formula (B-4), an Al ₂ O ₃ : PVdF: lithium salt filler of the formula (B-4) (mass ratio) ) = 32: 8: 60. Except for the above, a multilayer separator was produced in the same manner as in Reference Example 1-1.

<Comparative Example 1-1>
In preparing the resin solution, as the lithium salt filler, lithium phosphate (Li ₃ PO ₄ ) filler is not used, but aluminum oxide (Al ₂ O ₃ ) filler and polyvinylidene fluoride (PVdF) are mixed with Al ₂ O _3. : PVdF (mass ratio) = 92: 8. Except for the above, a multilayer separator was produced in the same manner as in Reference Example 1-1.

<Comparative Example 1-2>
A single layer separator having only a base material layer (the same polyethylene microporous membrane as in Reference Example 1-1) was used without providing a functional resin layer.

<Comparative Example 1-3>
In preparing the resin solution, aluminum oxide (Al ₂ O ₃ ) is not mixed, and lithium carbonate (Li ₂ CO ₃ ) filler is used instead of lithium phosphate (Li ₃ PO ₄ ) filler as a lithium salt filler. Using. Polyvinylidene fluoride (PVdF) and lithium carbonate (Li ₂ CO ₃ ) filler were mixed at PVdF: Li ₂ CO ₃ (mass ratio) = 8: 92. Except for the above, a multilayer separator was produced in the same manner as in Reference Example 1-1.

<Comparative Example 1-4>
In preparing the resin solution, a lithium hexafluorophosphate (LiPF ₆ ) filler was used instead of the lithium phosphate (Li ₃ PO ₄ ) filler. Aluminum oxide (Al ₂ O ₃ ), polyvinylidene fluoride (PVdF), and lithium hexafluorophosphate (LiPF ₆ ) filler were mixed at Al ₂ O ₃ : PVdF: LiPF ₆ (mass ratio) = 30: 8: 62. . Except for the above, a multilayer separator was produced in the same manner as in Reference Example 1-1.

(Evaluation of non-aqueous electrolyte battery)
Using each separator of Reference Example 1-1 , Reference Example 1-4, Example 1-2 to Example 1-3, Example 1-5 to Example 1-9 and Comparative Example 1 to Comparative Example 4, A 2016 size coin type battery was prepared as follows, and the capacity retention rate at 100 cycles in a 45 ° C. environment was measured.

(Preparation of positive electrode)
Lithium cobaltate (LiCoO ₂ ) as a positive electrode, carbon black as a conductive agent, and polyvinylidene fluoride as a binder were mixed in a LiCoO ₂ : carbon black: polyvinylidene fluoride = 85: 5: 10 (mass ratio). Then, it was sufficiently dispersed in N-methyl-2-pyrrolidone to obtain a positive electrode mixture slurry.

  Next, the positive electrode mixture slurry was applied to a positive electrode current collector (Al foil), dried, and N-methyl-2-pyrrolidone was volatilized, followed by compression molding at a constant pressure to produce a strip-shaped positive electrode. .

(Preparation of negative electrode)
Graphite as a negative electrode active material and polyvinylidene fluoride as a binder are mixed in a ratio of graphite: polyvinylidene fluoride = 90: 10 (mass ratio) and sufficiently dispersed in N-methyl-2-pyrrolidone to be a negative electrode mixture A slurry was obtained.

  Next, the negative electrode mixture slurry was applied to a negative electrode current collector (Cu foil), dried, and N-methyl-2-pyrrolidone was volatilized, followed by compression molding at a constant pressure to produce a strip-shaped negative electrode. .

(Preparation of non-aqueous electrolyte)
As the non-aqueous solvent, a mixture of ethylene carbonate (EC): dimethyl carbonate (DMC) at a ratio of EC: DMC (volume ratio) = 4: 6 was used. Further, lithium hexafluorophosphate (LiPF ₆ ) was used as an electrolyte salt, and 1.0 mol / L was dissolved in a non-aqueous solvent to obtain a non-aqueous electrolyte.

(Assembly of non-aqueous electrolyte battery)
The belt-like positive electrode and negative electrode produced as described above were punched into a disc shape, and the positive electrode, the negative electrode, and the produced separator were laminated in the order of the positive electrode, the separator, and the negative electrode, and stored in the positive electrode can. Next, after pouring the above-mentioned non-aqueous electrolyte into the battery can, the positive electrode can and the negative electrode can were caulked through a gasket having a surface coated with asphalt. As a result, a 2016 size coin type battery was obtained.

(Evaluation)
(Measurement of capacity maintenance rate)
After the prepared coin-type battery was charged so that the open circuit voltage in a fully charged state was 4.35 V, the discharge capacity when discharging to 3.0 V at a constant current of 0.2 C (first time Capacity). Thereafter, charging and discharging were performed up to the 100th cycle under the same conditions, and the discharge capacity at the 100th cycle was measured. Then, the capacity retention rate was calculated by the following formula.
Capacity maintenance ratio [%] = (discharge capacity at the 100th cycle / initial capacity) × 100

(Insulation test at 5V overcharge)
The manufactured coin-type battery was maintained at a charge state for 3 days with an external voltage of 5.00 V, and the insulation property was evaluated by measuring the leakage current value. The case where no increase in leakage current value was observed up to the test flow rate was “OK”, and the case where the leakage current value increased was “NG”.

In addition, after carrying out 1 cycle of charging / discharging on the coin-type battery produced using the separator of the reference example 1-1 on the same conditions as "a measurement of a capacity | capacitance maintenance rate", the inorganic oxide filler in a separator, a lithium salt filler, As a result, the mixing ratio of the inorganic oxide filler and the lithium salt filler was almost the same as the mixing ratio at the time of preparing the resin solution. That is, it was confirmed that the mixing ratio of the inorganic oxide filler and the lithium salt filler in the separator tends not to change greatly from the mixing ratio at the time of preparing the resin solution even after driving the battery.

  Table 1 shows the measurement results of “Measurement of capacity maintenance ratio” and “Insulation test at 5 V overcharge”.

As shown in Table 1, in Reference Example 1-1 , Reference Example 1-4, Example 1-2 to Example 1-3, and Example 1-5 to Example 1-9, By including an alumina filler of an inorganic oxide filler and a lithium salt filler, the insulating properties can be improved, and the functional resin layer includes Comparative Example 1-1 that does not include a lithium salt filler, and a functional resin layer. It was possible to improve the discharge capacity retention rate compared to Comparative Example 1-2. Although the mechanism of the effect of improving the discharge capacity retention rate has not been clarified strictly, for example, the following may be considered. That is, the lithium salt in the functional resin layer in contact with the positive electrode on the high voltage side in the charged state elutes in the electrolytic solution, precipitates on the positive electrode and negative electrode surfaces, and forms a film on the active material surface, thereby forming the active material It is thought that the deterioration of the is suppressed. Moreover, in Comparative Example 1-2, since the functional resin layer was not provided, the leakage current preventing effect was not exhibited and the insulation was poor. Moreover, in Comparative Example 1-3, since the functional resin layer was not provided with the inorganic oxide filler, insulation was bad. That is, in Comparative Example 1-3, since the decomposition of Li ₂ CO ₃ was promoted at a charging voltage of 5.00 V and dissolved in the electrolytic solution, the function of the functional resin layer disappeared, and the leakage current prevention effect was not exhibited. . In Comparative Example 1-4, LiPF ₆ was soluble in the non-aqueous solvent contained in the lithium ion secondary battery, and thus completely dissolved simultaneously with the injection of the electrolytic solution. Therefore, the function which prevents the deterioration of the original battery characteristic of a functional resin layer was not exhibited.

< Reference Example 2-1 ( Example 2-1 of Initial Specification of Application) >
The nonaqueous electrolyte secondary battery of Reference Example 2-1 was produced as follows.

(Preparation of non-aqueous electrolyte material)
A non-aqueous electrolyte material was produced as follows. First, 90 parts by mass of the nonaqueous electrolyte and 10 parts by mass of a polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF: HFP = 93.1: 6.9 (mass ratio)) as a matrix polymer were mixed. The material was prepared. Then, this mixed material, silicon carbide (SiC) powder having a center particle diameter of 0.3μm as off filler, a lithium phosphate (Li ₃ PO ₄₎ powder having a center particle diameter of 0.3μm as a lithium salt filler, Silicon carbide (SiC) powder: lithium salt powder: matrix polymer = 45: 5: 50 (mass ratio) is added, and dimethyl carbonate (DMC) is further added as a viscosity adjusting solvent, and the viscosity is 50 mPa・ Adjusted to s. At this time, the weight average molecular weight of the polyvinylidene fluoride-hexafluoropropylene copolymer as the matrix polymer was 60 × 10 ⁴ . The non-aqueous electrolyte is a non-aqueous solvent in which ethylene carbonate (EC) and propylene carbonate (PC) are mixed at a ratio of ethylene carbonate (EC): propylene carbonate (PC) = 6: 4 (mass ratio). Then, lithium hexafluorophosphate (LiPF ₆ ) as an electrolyte salt dissolved in a concentration of 1.0 mol / kg was used. Since dimethyl carbonate (DMC) is volatilized eventually, it does not remain in the battery.

(Preparation of non-aqueous electrolyte secondary battery)
The non-aqueous electrolyte material described above was applied to both the positive electrode and the negative electrode, and the solvent was volatilized to form a gel electrolyte layer. In this case, the combined amount of the full filler and a lithium salt filler in the gel electrolyte was 0.6mg per unit area of the positive or negative electrode / cm ^2. The positive electrode and the negative electrode were laminated and wound through a separator made of a microporous polyethylene film having a thickness of 12 μm, and sealed in an exterior material made of an aluminum laminate film to obtain a non-aqueous electrolyte secondary battery.

<Example 2-2>
As the lithium salt filler, lithium carbonate (Li ₂ CO ₃ ) powder was used instead of lithium phosphate (Li ₃ PO ₄ ) powder. The mixing ratio of silicon carbide (SiC) powder, polyvinylidene fluoride (PVdF) and lithium carbonate (Li ₂ CO ₃ ) powder was set to SiC: PVdF: Li ₂ CO ₃ (mass ratio) = 40: 50: 10. Except for the above, a nonaqueous electrolyte secondary battery was obtained in the same manner as Reference Example 2-1.

<Example 2-3>
As the lithium salt filler, lithium fluoride (LiF) powder was used instead of lithium phosphate (Li ₃ PO ₄ ) powder. The mixing ratio of silicon carbide (SiC) powder, polyvinylidene fluoride (PVdF), and lithium fluoride (LiF) powder was SiC: PVdF: LiF (mass ratio) = 20: 50: 30. Except for the above, a nonaqueous electrolyte secondary battery was obtained in the same manner as Reference Example 2-1.

<Example 2-4>
As the lithium salt filler, lithium fluoride (LiF) powder was used together with lithium phosphate (Li ₃ PO ₄ ) powder. The mixing ratio of silicon carbide (SiC) powder, polyvinylidene fluoride (PVdF), lithium phosphate (Li ₃ PO ₄ ) powder, and lithium fluoride (LiF) powder is calculated as follows: SiC: PVdF: Li ₃ PO ₄ : LiF (mass) Ratio) = 50: 40: 5: 5. Except for the above, a nonaqueous electrolyte secondary battery was obtained in the same manner as Reference Example 2-1.

<Example 2-5>
Aluminum nitride (AlN) powder was used instead of silicon carbide (SiC) powder. The mixing ratio of aluminum nitride (AlN) powder, polyvinylidene fluoride (PVdF) powder, and lithium phosphate (Li ₃ PO ₄ ) powder is AlN: PVdF: Li ₃ PO ₄ (mass ratio) = 45: 30: 25 did. Except for the above, a nonaqueous electrolyte secondary battery was obtained in the same manner as Reference Example 2-1.

<Example 2-6>
Boron nitride (BN) powder was used instead of silicon carbide (SiC) powder. The mixing ratio of boron nitride (BN) powder, polyvinylidene fluoride (PVdF), and lithium phosphate (Li ₃ PO ₄ ) powder was BN: PVdF: Li ₃ PO ₄ (mass ratio) = 60: 20: 20. . Except for the above, a nonaqueous electrolyte secondary battery was obtained in the same manner as Reference Example 2-1.

<Comparative Example 2-1>
Lithium phosphate (Li ₃ PO ₄ ) powder was not used, and the mixing ratio of silicon carbide (SiC) powder and polyvinylidene fluoride (PVdF) was SiC: PVdF (mass ratio) = 50: 50. Except for the above, a nonaqueous electrolyte secondary battery was obtained in the same manner as Reference Example 2-1.

<Comparative Example 2-2>
A gel electrolyte layer was not formed. That is, an electrode body in which separators made of a positive electrode, a negative electrode, and a microporous polyethylene film were laminated and wound was housed in an exterior material, and then a non-aqueous electrolyte was injected. Except for the above, a non-aqueous electrolyte secondary battery was produced in the same manner as in Reference Example 2-1.

<Comparative Example 2-3>
Without using silicon carbide (SiC) powder, the mixing ratio of polyvinylidene fluoride (PVdF) and lithium carbonate (Li ₂ CO ₃ ) was PVdF: Li ₂ CO ₃ (mass ratio) = 50: 50. Except for the above, a nonaqueous electrolyte secondary battery was obtained in the same manner as Reference Example 2-1.

(Evaluation)
About each nonaqueous electrolyte secondary battery of produced Reference Example 2-1 , Example 2-2 to Example 2-6, and Comparative Example 2-1 to Comparative Example 2-3, “45 ° C.” “Discharge capacity maintenance rate after 100 cycles in environment” and “insulation test at 5V overcharge” were performed.

  Table 2 shows the measurement results of the discharge capacity retention ratio and the results of the insulation test at the time of 5 V overcharge.

As shown in Table 2, Reference Examples 2-1, Example 2-2 to Example 2-6, the functional resin layer, off filler (silicon carbide (SiC) powder, boron nitride (BN) powder or By including aluminum nitride (AlN) powder) and a lithium salt filler, the insulation can be improved, and the functional resin layer includes a comparative example 2-1 that does not include a lithium salt filler, and a functional resin layer. It was possible to improve the discharge capacity retention rate compared to Comparative Example 2-2. Moreover, in Comparative Example 2-2, since the functional resin layer was not provided, the leakage current preventing effect was not exhibited and the insulation was poor. Moreover, in Comparative Example 2-3, the functional resin layer did not include a filler ( silicon carbide (SiC) powder, boron nitride (BN) powder, or aluminum nitride (AlN) powder), and thus insulation was poor.

8). Other Embodiments The present technology is not limited to the above-described embodiments of the present technology, and various modifications and applications can be made without departing from the gist of the present technology. In the above-described embodiment, the lithium ion secondary battery has been described as an example. However, the present invention can be applied to, for example, a nickel metal hydride battery, a nickel cadmium battery, a lithium-manganese dioxide battery, and a lithium-iron sulfide battery. In addition, for example, in the third embodiment, a battery configuration using a liquid electrolyte instead of the gel electrolyte layer 45 may be used as the electrolyte.

  In the above-described embodiments and examples, a so-called lithium ion secondary battery in which the capacity of the negative electrode is represented by a capacity component due to insertion and extraction of lithium has been described. The charge capacity of a so-called lithium metal secondary battery in which the capacity of the negative electrode is represented by a capacity component due to precipitation and dissolution of lithium, or the negative electrode material capable of occluding and releasing lithium is greater than the charge capacity of the positive electrode The same applies to a lithium ion secondary battery in which the capacity of the negative electrode includes a capacity component due to insertion and extraction of lithium and a capacity component due to precipitation and dissolution of lithium, and is represented by the sum thereof. Can be applied to. In the present technology, as described above, the lithium ion secondary battery includes a battery in which lithium is deposited at the time of charging and dissolved at the time of discharging.

  Furthermore, in the above-described embodiment, the non-aqueous electrolyte secondary battery having a winding structure has been described. However, for example, in the present invention, the positive electrode and the negative electrode are folded in a zigzag manner, or a plurality of positive electrodes and negative electrodes are stacked. The present invention can be similarly applied to a stacked battery having a structure. Further, the shape of the battery is not limited, and the present invention can also be applied to a rectangular battery. Furthermore, it is not limited to a secondary battery, but can be applied to a primary battery.

（式中、ａ、ｂ、ｃ、ｄはそれぞれ０以上の整数である。ａ、ｂ、ｃ、ｄの和は２以上の整数であり、ａとｂとの和は１以上の整数である。ｅ、ｆ、ｇ、ｈはそれぞれ１以上の整数である。Ｒ１およびＲ２は、いずれも１価の基であり、互いに結合して環を形成してもよい。Ｒ３は、ａ、ｂ、ｃ、ｄの和を価数とする基である。）

（式中、Ｒ４は（ａ１＋ｂ１＋ｃ１）価の基である。ａ１、ｄ１、およびｎは１以上の整数であり、ｂ１およびｃ１は０以上の整数である。ただし、（ｂ１＋ｃ１）≧１である。）
［７］
上記無機酸化物フィラーと、上記リチウム塩フィラーとの質量比（無機酸化物フィラー：リチウム塩フィラー）は、１：９９〜９８：２の範囲内である［１］〜［６］の何れかに記載のリチウムイオン電池。
［８］
上記第１の高分子材料は、耐熱性樹脂およびフッ素系樹脂の少なくとも１種を含む［１］〜［７］の何れかに記載のリチウムイオン電池。
［９］
上記フッ素系樹脂は、ポリフッ化ビニリデン、フッ化ビニリデン共重合体およびポリテトラフルオロエチレンからなる群から選ばれた少なくとも１種を含み、
上記耐熱性樹脂は、ポリフェニレンスルフィド、ポリスルホン、ポリエーテルスルホン、ポリエーテルエーテルケトン、ポリアリレート、ポリエーテルイミド、ポリアミドイミド、ポリイミドおよびポリアミドからなる群から選ばれた少なくとも１種を含む［８］に記載のリチウムイオン電池。
［１０］
溶媒および電解質塩を含む電解液をさらに備えた［１］〜［９］の何れかに記載のリチウムイオン電池。
［１１］
上記樹脂層は、上記電解液により上記第１の高分子材料が膨潤されたゲル状のイオン伝導体を含む［１０］に記載のリチウムイオン電池。
［１２］
上記絶縁層は、上記電解液により膨潤された第３の高分子材料を含むゲル状の電解質層をさらに有する［１０］に記載のリチウムイオン電池。
［１３］
第１の高分子材料と無機酸化物フィラーとリチウム塩フィラーとを含み、多孔構造を有する樹脂層を備えたセパレータ。
［１４］
少なくとも一主面に上記樹脂層が設けられた多孔構造を有する基材層をさらに有し、
上記基材層は、上記第１の高分子材料と異なる第２の高分子材料を含み、
上記第２の高分子材料は、ポリオレフィン樹脂を含む［１３］に記載のセパレータ。
［１５］
［１］〜［１２］の何れかに記載のリチウムイオン電池と、
上記リチウムイオン電池について制御する制御部と、
上記リチウムイオン電池を内包する外装を有する電池パック。
［１６］
［１］〜［１２］の何れかに記載のリチウムイオン電池を有し、
上記リチウムイオン電池から電力の供給を受ける電子機器。
［１７］
［１］〜［１２］の何れかに記載のリチウムイオン電池を有し、
上記リチウムイオン電池から電力の供給を受けて車両の駆動力に変換する変換装置と、
上記リチウムイオン電池に関する情報に基づいて車両制御に関する情報処理を行う制御装置と
を有する電動車両。
［１８］
［１］〜［１２］の何れかに記載のリチウムイオン電池を有し、
上記リチウムイオン電池に接続される電子機器に電力を供給する蓄電装置。
［１９］
他の機器とネットワークを介して信号を送受信する電力情報制御装置を備え、
上記電力情報制御装置が受信した情報に基づき、上記リチウムイオン電池の充放電制御を行う［１８］に記載の蓄電装置。
［２０］
［１］〜［１２］の何れかに記載のリチウムイオン電池から電力の供給を受け、または、発電装置若しくは電力網から上記リチウムイオン電池に電力が供給される電力システム。 The present technology can also have the following configurations.
[1]
A positive electrode;
A negative electrode,
An insulating layer between the positive electrode and the negative electrode,
The insulating layer is a lithium ion battery having a resin layer including a first polymer material, an inorganic oxide filler, and a lithium salt filler.
[2]
The insulating layer further includes a base material layer having a porous structure in which the resin layer is provided on at least one main surface,
The base material layer includes a second polymer material different from the first polymer material,
The lithium ion battery according to [1], wherein the second polymer material includes a polyolefin resin.
[3]
The lithium ion battery according to any one of [1] to [2], wherein the resin layer has a porous structure.
[4]
The porous structure according to [3], wherein the porous structure is a porous interconnected structure in which the pores are interconnected.
[5]
[1] to [4], wherein the inorganic oxide filler is at least one selected from the group consisting of aluminum oxide, zirconium oxide, titanium oxide, magnesium oxide, silicon dioxide, silicon carbide, aluminum nitride, and boron nitride. The lithium ion battery in any one.
[6]
The lithium salt filler is lithium phosphate, lithium carbonate, lithium fluoride, lithium sulfate, lithium nitrate, lithium tetraborate, lithium metaborate, lithium pyrophosphate, lithium tripolyphosphate, lithium orthosilicate, lithium metasilicate, oxalic acid Any one of [1] to [5], which is at least one selected from the group consisting of dilithium, a lithium salt represented by the general formula (A), and a lithium salt represented by the general formula (B) Lithium-ion battery.

(In the formula, a, b, c and d are each an integer of 0 or more. The sum of a, b, c and d is an integer of 2 or more, and the sum of a and b is an integer of 1 or more. E, f, g, and h are each an integer equal to or greater than 1. R1 and R2 are each a monovalent group and may be bonded to each other to form a ring, and R3 represents a, b, This is a group having the valence of the sum of c and d.)

(In the formula, R4 is a (a1 + b1 + c1) -valent group. A1, d1, and n are integers of 1 or more, and b1 and c1 are integers of 0 or more, provided that (b1 + c1) ≧ 1. )
[7]
The mass ratio of the inorganic oxide filler to the lithium salt filler (inorganic oxide filler: lithium salt filler) is any one of [1] to [6] in the range of 1:99 to 98: 2. The lithium ion battery as described.
[8]
The lithium ion battery according to any one of [1] to [7], wherein the first polymer material includes at least one of a heat resistant resin and a fluorine resin.
[9]
The fluororesin includes at least one selected from the group consisting of polyvinylidene fluoride, a vinylidene fluoride copolymer and polytetrafluoroethylene,
The heat-resistant resin includes at least one selected from the group consisting of polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyarylate, polyetherimide, polyamideimide, polyimide and polyamide [8]. Lithium-ion battery.
[10]
The lithium ion battery according to any one of [1] to [9], further comprising an electrolytic solution containing a solvent and an electrolyte salt.
[11]
The lithium ion battery according to [10], wherein the resin layer includes a gel ion conductor in which the first polymer material is swollen by the electrolytic solution.
[12]
The lithium ion battery according to [10], wherein the insulating layer further includes a gel electrolyte layer containing a third polymer material swollen by the electrolytic solution.
[13]
The separator provided with the resin layer which contains a 1st polymeric material, an inorganic oxide filler, and a lithium salt filler, and has a porous structure.
[14]
It further has a base material layer having a porous structure in which the resin layer is provided on at least one main surface,
The base material layer includes a second polymer material different from the first polymer material,
The separator according to [13], wherein the second polymer material includes a polyolefin resin.
[15]
The lithium ion battery according to any one of [1] to [12],
A control unit for controlling the lithium ion battery;
A battery pack having an exterior housing the lithium ion battery.
[16]
It has a lithium ion battery in any one of [1]-[12],
An electronic device that is supplied with power from the lithium ion battery.
[17]
It has a lithium ion battery in any one of [1]-[12],
A conversion device that receives supply of electric power from the lithium ion battery and converts it into driving force of the vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the lithium ion battery.
[18]
It has a lithium ion battery in any one of [1]-[12],
A power storage device that supplies electric power to an electronic device connected to the lithium ion battery.
[19]
A power information control device that transmits and receives signals to and from other devices via a network,
The power storage device according to [18], wherein charge / discharge control of the lithium ion battery is performed based on information received by the power information control device.
[20]
[1] A power system that receives power from the lithium ion battery according to any one of [12], or that supplies power to the lithium ion battery from a power generation device or a power network.

  DESCRIPTION OF SYMBOLS 1 ... Battery can, 2 ... Positive electrode, 2A ... Positive electrode collector, 2 ... Positive electrode collector, 2B ... Positive electrode mixture layer, 3 ... Negative electrode, 3A ... Negative electrode current collector, 3B ... Negative electrode mixture layer, 4 ... Separator, 4a ... Base material layer, 4b ... Functional resin layer, 5, 6 ... Insulating plate, 7 ... Battery lid, 8 ... Safety valve mechanism, 9 ... Heat sensitive resistance element, 10 ... Gasket, 11 ... Disc plate, 12 ... Center pin, 13 ... Positive electrode lead, 14 ... Negative electrode lead, 20 ... wound electrode body, 30 ... battery element, 32 ... positive electrode lead, 33 ... negative electrode lead, 34, 35 ... resin piece, 36 ... recess, 37 ..Exterior material, 42... Positive electrode, 42A... Positive electrode current collector, 42B... Positive electrode mixture layer, 43... Negative electrode, 43A. Mixture layer, 44 ... separator, 45 ... electrolyte layer, 46 ... insulating layer, 50 ... battery element, 54 ... separator, 55 ... electrolyte layer, 56 ... insulating layer , 301 ... assembled battery, 301a ... secondary battery, 302a ... charge control switch, 303a ... discharge control switch, 303b ... discharge control switch, 303b ... diode, 304 ... Switch unit, 307 ... Current detection resistor, 308 ... Temperature detection element, 310 ... Control unit, 311 ... Voltage detection unit, 313 ... Current measurement unit, 314 ... Switch control unit, 317 ... Memory, 318 ... Temperature detector, 321 ... Positive terminal, 322 ... Negative terminal, 400 ... Power storage system, 401 ... House, 402a ... Thermal power generation, 402b ..Nuclear power 402c: Hydroelectric power generation, 402: Centralized power system, 403 ... Power storage device, 404 ... Power generation device, 405 ... Power consumption device, 405a ... Refrigerator, 405b ... Air conditioning Device, 405c ... Television receiver, 405d ... Bath, 406 ... Electric vehicle, 406a ... Electric car, 406b ... Hybrid car, 406c ... Electric bike, 407 ... Smart Meter, 408 ... Power hub, 409 ... Power network, 410 ... Control device, 411 ... Sensor, 412 ... Information network, 413 ... Server, 500 ... Hybrid vehicle, 501 ... -Engine, 502 ... Generator, 503 ... Power driving force conversion device, 504a ... Driving wheel, 504b ... Driving wheel, 504a, 504b ... Driving wheel, 5 05a, 505b ... wheel, 508 ... battery, 509 ... vehicle control device, 510 ... various sensors, 511 ... charging port

Claims (18)

A positive electrode;
A negative electrode,
An insulating layer between the positive electrode and the negative electrode ;
An electrolyte solution containing a solvent and an electrolyte salt ; and
The insulating layer includes a first polymeric material, inorganic oxides, silicon carbide, resin layer containing a first filler comprising at least one of aluminum nitride and boron nitride, and a second filler consisting of lithium salt I have a,
The lithium salt is lithium carbonate, lithium fluoride, lithium sulfate, lithium nitrate, lithium tetraborate, lithium metaborate, lithium pyrophosphate, lithium tripolyphosphate, lithium orthosilicate, lithium metasilicate, dilithium oxalate, general formula A lithium ion battery that is at least one selected from the group consisting of a lithium salt represented by (A) and a lithium salt represented by formula (B) .

(In the formula, a, b, c and d are each an integer of 0 or more. The sum of a, b, c and d is an integer of 2 or more, and the sum of a and b is an integer of 1 or more. E, f, g, and h are each an integer equal to or greater than 1. R1 and R2 are each a monovalent group and may be bonded to each other to form a ring, and R3 represents a, b, This is a group having the valence of the sum of c and d.)

(In the formula, R4 is a (a1 + b1 + c1) -valent group. A1, d1, and n are integers of 1 or more, and b1 and c1 are integers of 0 or more, provided that (b1 + c1) ≧ 1. ) The insulating layer further includes a base material layer having a porous structure in which the resin layer is provided on at least one main surface,
The base material layer includes a second polymer material different from the first polymer material,
The lithium ion battery according to claim 1, wherein the second polymer material includes a polyolefin resin. The lithium ion battery according to any one of claims 1 to 2 , wherein the resin layer has a porous structure.   The lithium ion battery according to claim 3, wherein the porous structure is a porous interconnected structure in which pores are interconnected. The inorganic oxide, aluminum oxide, zirconium oxide, titanium oxide, lithium-ion battery according to any one of claims 1-4 is at least one selected from the group consisting of magnesium oxide and silicon dioxide. The first filler, the weight ratio of the second filler (first filler: second filler) is 1: 99 to 98: in the second range is claims 1-5 any one of The lithium ion battery according to item . The first polymeric material, saw including at least one heat-resistant resin and a fluorine-based resin,
The heat-resistant resin, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, polyarylate, polyetherimide, polyamideimide, claim 1-6 comprising at least one selected from the group consisting of polyimide and polyamide The lithium ion battery according to any one of the above. The fluorine-based resin, polyvinylidene fluoride, lithium ion battery according to at least one selected from the group consisting of vinylidene fluoride copolymer and polytetrafluoroethylene including claim 7. The lithium ion battery according to any one of claims 1 to 8, wherein the resin layer includes a gel ion conductor in which the first polymer material is swollen by the electrolytic solution. The lithium ion battery according to any one of claims 1 to 8, wherein the insulating layer further includes a gel electrolyte layer containing a third polymer material swollen by the electrolyte solution. A first polymeric material, inorganic oxides, silicon carbide, comprising: a first filler comprising at least one of aluminum nitride and boron nitride, and a second filler consisting of lithium salt, a resin layer having a porous structure equipped with a,
The lithium salt is lithium carbonate, lithium fluoride, lithium sulfate, lithium nitrate, lithium tetraborate, lithium metaborate, lithium pyrophosphate, lithium tripolyphosphate, lithium orthosilicate, lithium metasilicate, dilithium oxalate, general formula A separator for a lithium ion battery having an electrolytic solution containing a solvent and an electrolyte salt, which is at least one selected from the group consisting of a lithium salt represented by (A) and a lithium salt represented by formula (B) .

(In the formula, a, b, c and d are each an integer of 0 or more. The sum of a, b, c and d is an integer of 2 or more, and the sum of a and b is an integer of 1 or more. E, f, g, and h are each an integer equal to or greater than 1. R1 and R2 are each a monovalent group and may be bonded to each other to form a ring, and R3 represents a, b, This is a group having the valence of the sum of c and d.)

(In the formula, R4 is a (a1 + b1 + c1) -valent group. A1, d1, and n are integers of 1 or more, and b1 and c1 are integers of 0 or more, provided that (b1 + c1) ≧ 1. ) It further has a base material layer having a porous structure in which the resin layer is provided on at least one main surface,
The base material layer includes a second polymer material different from the first polymer material,
The second polymeric material separator according to claim 1 1 comprising a polyolefin resin. The lithium ion battery according to any one of claims 1 to 10 ,
A control unit for controlling the lithium ion battery;
A battery pack having an exterior housing the lithium ion battery. It has a lithium ion battery according to any one of claims 1 to 10 ,
An electronic device that is supplied with power from the lithium ion battery. It has a lithium ion battery according to any one of claims 1 to 10 ,
A conversion device that receives supply of electric power from the lithium ion battery and converts it into driving force of the vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the lithium ion battery. It has a lithium ion battery according to any one of claims 1 to 10 ,
A power storage device that supplies electric power to an electronic device connected to the lithium ion battery. A power information control device that transmits and receives signals to and from other devices via a network,
The power storage device according to claim 16 , wherein charge / discharge control of the lithium ion battery is performed based on information received by the power information control device. The electric power system which receives supply of electric power from the lithium ion battery as described in any one of Claims 1-10, or supplies electric power to the said lithium ion battery from an electric power generating apparatus or an electric power network.

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