JP2016119213A - Battery, battery pack, electronic apparatus, electric vehicle, power storage device, and power system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a battery, battery pack, electronic apparatus, electric vehicle, power storage device, and power system that are capable of improving overcharge resistance.SOLUTION: Between an anode active material layer and a separator, an anode side depression impregnation area that includes arranged electrolytes and solid particles and includes a depression between adjacent anode active material particles positioned on the outermost surface of the anode active material layer is formed. Between a cathode active material layer and a separator, a cathode side depression impregnation area that includes arranged electrolytes and solid particles and includes a depression between adjacent cathode active material particles positioned on the outermost surface of the cathode active material layer is formed. A concentration of solid particles in at least one of the cathode and anode side depression impregnation areas is equal to or higher than 30 vol.%. The electrolytes include a predetermined metal salt.SELECTED DRAWING: Figure 3

Description

  The present technology relates to a battery, a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system.

  In recent years, electronic devices typified by mobile phones or portable information terminal devices have become widespread, and further downsizing, weight reduction, and long life have been strongly demanded. Accordingly, as a power source, development of a battery, in particular, a secondary battery that is small and lightweight and capable of obtaining a high energy density is in progress.

  In recent years, this secondary battery is not limited to the above-described electronic devices, but can be applied to various uses represented by power storage systems such as electric tools such as electric drills, electric vehicles such as electric vehicles, and household electric power servers. Has also been considered. As these power sources, development of secondary batteries with high output and high capacity is in progress.

  In a secondary battery, an additive is added to an electrolytic solution in order to improve performance (see Patent Document 1).

JP 2013-134659 A

  Batteries are required to improve overcharge resistance.

  Therefore, an object of the present technology is to provide a battery, a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system that can improve overcharge resistance.

（式中、Ｘ３１は長周期型周期表における１族元素または２族元素、またはＡｌである。Ｍ３１は遷移金属、または長周期型周期表における１３族元素、１４族元素または１５族元素である。Ｒ７１はハロゲン基である。Ｙ３１は−Ｃ（＝Ｏ）−Ｒ７２−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＣＲ７３₂−、または−Ｃ（＝Ｏ）−Ｃ（＝Ｏ）−である。ただし、Ｒ７２はアルキレン基、ハロゲン化アルキレン基、アリーレン基またはハロゲン化アリーレン基である。Ｒ７３はアルキル基、ハロゲン化アルキル基、アリール基またはハロゲン化アリール基である。なお、ａ３は１〜４の整数であり、ｂ３は０、２または４の整数であり、ｃ３、ｄ３、ｍ３およびｎ３は１〜３の整数である。）

（式中、Ｘ４１は長周期型周期表における１族元素または２族元素である。Ｍ４１は遷移金属、または長周期型周期表における１３族元素、１４族元素または１５族元素である。Ｙ４１は−Ｃ（＝Ｏ）−（ＣＲ８１₂）_b4−Ｃ（＝Ｏ）−、−Ｒ８３₂Ｃ−（ＣＲ８２₂）_c4−Ｃ（＝Ｏ）−、−Ｒ８３₂Ｃ−（ＣＲ８２₂）_c4−ＣＲ８３₂−、−Ｒ８３₂Ｃ−（ＣＲ８２₂）_c4−Ｓ（＝Ｏ）₂−、−Ｓ（＝Ｏ）₂−（ＣＲ８２₂）_d4−Ｓ（＝Ｏ）₂−、または−Ｃ（＝Ｏ）−（ＣＲ８２₂）_d4−Ｓ（＝Ｏ）₂−である。ただし、Ｒ８１およびＲ８３は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基であり、それぞれのうちの少なくとも１つはハロゲン基またはハロゲン化アルキル基である。Ｒ８２は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基である。なお、ａ４、ｅ４およびｎ４は１または２の整数であり、ｂ４およびｄ４は１〜４の整数であり、ｃ４は０〜４の整数であり、ｆ４およびｍ４は１〜３の整数である。）

（式中、Ｘ５１は長周期型周期表における１族元素または２族元素である。Ｍ５１は遷移金属、または長周期型周期表における１３族元素、１４族元素または１５族元素である。Ｒｆはフッ素化アルキル基またはフッ素化アリール基であり、いずれの炭素数も１〜１０である。Ｙ５１は−Ｃ（＝Ｏ）−（ＣＲ９１₂）_d5−Ｃ（＝Ｏ）−、−Ｒ９２₂Ｃ−（ＣＲ９１₂）_d5−Ｃ（＝Ｏ）−、−Ｒ９２₂Ｃ−（ＣＲ９１₂）_d5−ＣＲ９２₂−、−Ｒ９２₂Ｃ−（ＣＲ９１₂）_d5−Ｓ（＝Ｏ）₂−、−Ｓ（＝Ｏ）₂−（ＣＲ９１₂）_e5−Ｓ（＝Ｏ）₂−、または−Ｃ（＝Ｏ）−（ＣＲ９１₂）_e5−Ｓ（＝Ｏ）₂−である。ただし、Ｒ９１は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基である。Ｒ９２は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基であり、そのうちの少なくとも１つはハロゲン基またはハロゲン化アルキル基である。なお、ａ５、ｆ５およびｎ５は１または２の整数であり、ｂ５、ｃ５およびｅ５は１〜４の整数であり、ｄ５は０〜４の整数であり、ｇ５およびｍ５は１〜３の整数である。）

（式中、Ｒ９２は、２価のハロゲン化炭化水素基である。）

（式中、Ｍ⁺は１価のカチオンであり、ＹはＳＯ₂またはＣＯであり、Ｚはそれぞれ独立してハロゲン基または有機基である。）

ＬｉＣ（Ｃ_pＦ_2p+1ＳＯ₂）（Ｃ_qＦ_2q+1ＳＯ₂）（Ｃ_rＦ_2r+1ＳＯ₂）・・・（６）
（式中、ｐ、ｑおよびｒは１以上の整数である。）

In order to solve the above-described problem, the present technology provides a positive electrode having a positive electrode active material layer including positive electrode active material particles, a negative electrode having a negative electrode active material layer including negative electrode active material particles, a positive electrode active material layer, and a negative electrode active material. A separator between the material layers, an electrolyte containing an electrolytic solution, and solid particles; a depression-impregnated region on the negative electrode side and a deep region on the negative electrode side; and a depression-impregnated region on the positive electrode side and a deep region on the positive electrode side. It has at least one dent-impregnated region and a deep region, and the dent-impregnated region on the negative electrode side includes a dent between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer in which the electrolyte and solid particles are arranged. The deep region on the negative electrode side is a region inside the negative electrode active material layer on the deeper side than the depression impregnation region on the negative electrode side where the electrolyte or the electrolyte and solid particles are arranged, and the depression impregnation region on the positive electrode side is , Electric Is a region including a depression between adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer, in which the electrolyte or electrolyte and solid particles are arranged in the deep region on the positive electrode side , A region inside the positive electrode active material layer on the deeper side than the depression-impregnated region on the positive electrode side, the concentration of solid particles in at least one of the depression-impregnated regions is 30% by volume or more, and the electrolytic solution is expressed by the following formula (1 ) To at least one metal salt represented by formula (7).

(In the formula, X31 is a group 1 element or group 2 element in the long-period periodic table, or Al. M31 is a transition metal, or a group 13 element, group 14 element, or group 15 element in the long-period periodic table. R71 is a halogen group Y31 is —C (═O) —R72—C (═O) —, —C (═O) —CR73 ₂ —, or —C (═O) —C (═O) Where R72 is an alkylene group, a halogenated alkylene group, an arylene group or a halogenated arylene group, R73 is an alkyl group, a halogenated alkyl group, an aryl group or a halogenated aryl group, wherein a3 is (It is an integer of 1 to 4, b3 is an integer of 0, 2 or 4, and c3, d3, m3 and n3 are integers of 1 to 3.)

(In the formula, X41 is a group 1 element or group 2 element in the long-period periodic table. M41 is a transition metal, or a group 13, element, or group 15 element in the long-period periodic table. Y41 is -C (= O) - (CR81 2) b4 -C (= O) -, - R83 2 C- (CR82 2) c4 -C (= O) -, - R83 2 C- (CR82 2) c4 -CR83 ₂ −, —R83 ₂ C— (CR82 ₂ ) _c4 —S (═O) ₂ —, —S (═O) ₂ — (CR82 ₂ ) _d4 —S (═O) ₂ —, or —C (═O ) — (CR82 ₂ ) _d4 —S (═O) ₂ —, wherein R81 and R83 are a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group, and at least one of each is a halogen group Or a halogenated alkyl group, wherein R82 represents a hydrogen group, an alkyl group, A4, e4 and n4 are integers of 1 or 2, b4 and d4 are integers of 1 to 4, c4 is an integer of 0 to 4, f4 and m4 is an integer of 1 to 3.)

(In the formula, X51 is a group 1 element or a group 2 element in the long-period periodic table. M51 is a transition metal, or a group 13, element, or group 15 element in the long-period periodic table. Rf is A fluorinated alkyl group or a fluorinated aryl group, each having 1 to 10 carbon atoms, Y51 is —C (═O) — (CR91 ₂ ) _d5 —C (═O) —, —R92 ₂ C— _{(CR91 2) d5 -C (=} O) -, - R92 2 C- (CR91 2) d5 -CR92 2 -, - R92 2 C- (CR91 2) d5 -S (= O) 2 -, - S ( ═O) ₂ — (CR91 ₂ ) _e5 —S (═O) ₂ —, or —C (═O) — (CR91 ₂ ) _e5 —S (═O) ₂ —, wherein R91 is a hydrogen group, An alkyl group, a halogen group or a halogenated alkyl group, and R92 represents a hydrogen group, an alkyl group, A gen group or a halogenated alkyl group, at least one of which is a halogen group or a halogenated alkyl group, wherein a5, f5 and n5 are integers of 1 or 2, and b5, c5 and e5 are from 1 to 2, 4 is an integer, d5 is an integer of 0 to 4, and g5 and m5 are integers of 1 to 3.)

(In the formula, R92 is a divalent halogenated hydrocarbon group.)

(Wherein M ⁺ is a monovalent cation, Y is SO ₂ or CO, and Z is independently a halogen group or an organic group.)

LiC (C _p F _{2p + 1} SO ₂ ) (C _q F _{2q + 1} SO ₂ ) (C _r F _{2r + 1} SO ₂ ) (6)
(In the formula, p, q and r are integers of 1 or more.)

  The battery pack, the electronic device, the electric vehicle, the power storage device, and the power system of the present technology include the above-described battery.

  According to the present technology, there is an effect that the overcharge resistance can be improved.

FIG. 1 is an exploded perspective view showing a configuration of a laminated film type nonaqueous electrolyte battery according to an embodiment of the present technology. FIG. 2 is a cross-sectional view illustrating a cross-sectional configuration along the line II of the spirally wound electrode body illustrated in FIG. 3A and 3B are schematic cross-sectional views showing the internal configuration of the nonaqueous electrolyte battery. 4A to 4C are exploded perspective views showing the configuration of a laminated film type non-aqueous electrolyte battery using a laminated electrode body. FIG. 5 is a cross-sectional view showing a configuration of a cylindrical nonaqueous electrolyte battery according to an embodiment of the present technology. FIG. 6 is an enlarged cross-sectional view showing a part of a wound electrode body housed in a cylindrical nonaqueous electrolyte battery. FIG. 7 is a perspective view showing a configuration of a prismatic nonaqueous electrolyte battery according to an embodiment of the present technology. FIG. 8 is a perspective view showing a configuration of an application example of a secondary battery (battery pack: single cell). FIG. 9 is a block diagram showing the configuration of the battery pack shown in FIG. FIG. 10 is a block diagram illustrating a circuit configuration example of the battery pack according to the embodiment of the present technology. FIG. 11 is a schematic diagram showing an example applied to a residential power storage system using the nonaqueous electrolyte battery of the present technology. FIG. 12 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.

(Outline of this technology)
First, in order to facilitate understanding of the present technology, an outline of the present technology will be described. Secondary batteries, such as high voltage charging and rapid charging for high capacity, have been used harshly in recent years. Safety is ensured so as not to exceed the limit by a protection circuit or the like, but the margin of the battery itself is reduced, and particularly, improvement of the limit against overcharge is required.

  During overcharge, lithium dendritic precipitates grow on the negative electrode toward the positive electrode. In the worst case, this breaks through the separator and causes a short circuit accident. Since the separator has a function of stopping the progress of dendritic precipitates, it has been attempted to increase the strength, reduce the pores, decrease the porosity, or increase the thickness. However, these things decrease the output of a battery and reduce a capacity | capacitance.

  Precipitates formed in the vicinity of the separator are destroyed by the separator before the growth proceeds and stop growing, but the precipitates formed in the recesses between the active material particles located on the outermost surface of the electrode are protected by the surrounding active material. It can be a thick trunk of a precipitate that breaks through the separator.

  As a result of intensive studies by the present inventors, a dendritic precipitate of lithium grows on the counter electrode side by using an electrolyte salt containing at least one of the metal salts represented by the formulas (1) to (7). It was found that the growth direction can be changed in the plane direction of the electrode.

  However, when these metal salts are used as the main component of the electrolyte salt, there is a problem that a side reaction occurs in the mixture layer and the internal resistance increases. In the present technology, when at least one of the metal salts represented by the formulas (1) to (7) is dissolved in the electrolytic solution (preferably from the viewpoint of further suppressing the side reaction), It was found that solid particles selectively attract these metal salts. Then, the solid particles were selectively placed in the depressions between the adjacent active material particles on the negative electrode side, thereby succeeding in effectively keeping the precipitates in the depressions.

  When solid particles are arranged in the depressions between adjacent active material particles on the outermost surface of the positive electrode, most of the lithium ions that have come out of the positive electrode pass through this portion, and therefore, are expressed by the equations (1) to (7). To provide a large amount of at least one anion of the metal salt. Therefore, even if the solid particles are arranged only in the positive electrode side depression, or the solid particles are arranged in both the negative electrode side depression and the positive electrode side depression, the metal represented by the formulas (1) to (7). The lithium precipitate can be flattened by at least one salt, and side reactions can be suppressed. The side reaction can be minimized by preferably adding a small amount. In the present technology having the above-described operation, it is possible to raise a limit voltage that leads to a short circuit during overcharge.

Hereinafter, embodiments of the present technology will be described with reference to the drawings. The description will be given in the following order.
1. First embodiment (example of laminated film type battery)
2. Second embodiment (example of cylindrical battery)
3. Third embodiment (an example of a square battery)
4). Fourth embodiment (example of battery pack)
5). Fifth embodiment (example of battery pack)
6). Sixth embodiment (an example of a power storage system)
7). Other embodiment (modification)
The embodiments described below are suitable specific examples of the present technology, and the contents of the present technology are not limited to these embodiments. Moreover, the effect described in this specification is an illustration to the last, is not limited, and does not deny that the effect different from the illustrated effect exists.

1. First Embodiment In the first embodiment of the present technology, an example of a laminate film type battery will be described. This battery is, for example, a non-aqueous electrolyte battery, a secondary battery that can be charged and discharged, and a lithium ion secondary battery.

(1-1) Configuration of Example of Nonaqueous Electrolyte Battery FIG. 1 shows the configuration of the nonaqueous electrolyte battery according to the first embodiment. This non-aqueous electrolyte battery is a so-called laminate film type, in which a wound electrode body 50 to which a positive electrode lead 51 and a negative electrode lead 52 are attached is housed inside a film-shaped exterior member 60.

  The positive electrode lead 51 and the negative electrode lead 52 are led out from the inside of the exterior member 60 to the outside, for example, in the same direction. The positive electrode lead 51 and the negative electrode lead 52 are made of, for example, a metal material such as aluminum, copper, nickel, or stainless steel, and each have a thin plate shape or a mesh shape.

  The exterior member 60 is made of, for example, a laminate film in which resin layers are formed on both surfaces of a metal layer. In the laminate film, an outer resin layer is formed on the surface of the metal layer that is exposed to the outside of the battery, and an inner resin layer is formed on the inner surface of the battery facing the power generation element such as the wound electrode body 50.

  The metal layer plays the most important role in protecting the contents by preventing the ingress of moisture, oxygen and light, and aluminum (Al) is most often used because of its lightness, extensibility, price and ease of processing. The outer resin layer has a beautiful appearance, toughness, flexibility, and the like, and a resin material such as nylon or polyethylene terephthalate (PET) is used. Since the inner resin layer is a portion that melts and fuses with heat or ultrasonic waves, a polyolefin resin is appropriate, and unstretched polypropylene (CPP) is often used. An adhesive layer may be provided between the metal layer, the outer resin layer, and the inner resin layer as necessary.

  The exterior member 60 is provided with a recess that accommodates the wound electrode body 50 formed by, for example, deep drawing from the inner resin layer side toward the outer resin layer, and the inner resin layer serves as the wound electrode body 50. It is arrange | positioned so that it may oppose. The inner resin layers facing each other of the exterior member 60 are in close contact with each other by fusion or the like at the outer edge of the recess. Between the exterior member 60 and the positive electrode lead 51 and the negative electrode lead 52, there is an adhesive film 61 for improving the adhesion between the inner resin layer of the exterior member 60 and the positive electrode lead 51 and the negative electrode lead 52 made of a metal material. Has been placed. The adhesion film 61 is made of a resin material having high adhesion to a metal material, and is made of, for example, polyethylene, polypropylene, or a polyolefin resin such as modified polyethylene or modified polypropylene obtained by modifying these materials.

  The exterior member 60 may be made of a laminate film having another structure, a polymer film such as polypropylene, or a metal film, instead of the aluminum laminate film whose metal layer is made of aluminum (Al).

  FIG. 2 shows a cross-sectional structure taken along line II of the spirally wound electrode body 50 shown in FIG. As shown in FIG. 1, the wound electrode body 50 is obtained by laminating a belt-like positive electrode 53 and a belt-like negative electrode 54 via a belt-like separator 55 and an electrolyte layer 56, and the outermost peripheral portion is It is protected by a protective tape 57 as necessary.

(Positive electrode)
The positive electrode 53 has a structure in which a positive electrode active material layer 53B is provided on one or both surfaces of the positive electrode current collector 53A.

  In the positive electrode 53, a positive electrode active material layer 53B containing a positive electrode active material is formed on both surfaces of the positive electrode current collector 53A. Although not shown, the positive electrode active material layer 53B may be provided only on one surface of the positive electrode current collector 53A. As the positive electrode current collector 53A, for example, a metal foil such as an aluminum (Al) foil, a nickel (Ni) foil, or a stainless steel (SUS) foil can be used.

  The positive electrode active material layer 53B includes, for example, a positive electrode active material, a conductive agent, and a binder. As the positive electrode active material, any one or more of positive electrode materials capable of inserting and extracting lithium can be used, and other materials such as a binder and a conductive agent can be used as necessary. May be included.

  As a positive electrode material capable of inserting and extracting lithium, for example, a lithium-containing compound is preferable. This is because a high energy density can be obtained. Examples of the lithium-containing compound include a composite oxide containing lithium and a transition metal element, and a phosphate compound containing lithium and a transition metal element. Especially, what contains at least 1 sort (s) of the group which consists of cobalt (Co), nickel (Ni), manganese (Mn), and iron (Fe) as a transition metal element is preferable. This is because a higher voltage can be obtained.

As the positive electrode material, for example, a lithium-containing compound represented by Li _x M1O ₂ or Li _y M2PO ₄ can be used. In the formula, M1 and M2 represent one or more transition metal elements. The values of x and y vary depending on the charge / discharge state of the battery, and are generally 0.05 ≦ x ≦ 1.10 and 0.05 ≦ y ≦ 1.10. Examples of the composite oxide containing lithium and a transition metal element include lithium cobalt composite oxide (Li _x CoO ₂ ), lithium nickel composite oxide (Li _x NiO ₂ ), and lithium nickel cobalt composite oxide (Li _x Ni). _1-z Co _z O ₂ (0 <z <1)), lithium nickel cobalt manganese composite oxide (Li _x Ni _(1-vw) Co _v Mn _w O ₂ (0 <v + w <1, v> 0, w > 0)), or lithium manganese composite oxide (LiMn ₂ O ₄ ) or lithium manganese nickel composite oxide (LiMn _2−t N _t O ₄ (0 <t <2)) having a spinel structure. . Among these, a complex oxide containing cobalt is preferable. This is because a high capacity can be obtained and excellent cycle characteristics can be obtained. Examples of the phosphate compound containing lithium and a transition metal element include a lithium iron phosphate compound (LiFePO ₄ ) or a lithium iron manganese phosphate compound (LiFe _1-u Mn _u PO ₄ (0 <u <1). ) And the like.

Specific examples of such a lithium composite oxide include lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), and lithium manganate (LiMn ₂ O ₄ ). A solid solution in which a part of the transition metal element is substituted with another element can also be used. Examples thereof include nickel cobalt composite lithium oxide (LiNi _0.5 Co _0.5 O ₂ , LiNi _0.8 Co _0.2 O _2, etc.). These lithium composite oxides can generate a high voltage and have an excellent energy density.

  Furthermore, from the viewpoint that higher electrode filling properties and cycle characteristics can be obtained, composite particles in which the surfaces of particles made of any of the above lithium-containing compounds are coated with fine particles made of any of the other lithium-containing compounds can be used. Good.

In addition, examples of positive electrode materials capable of inserting and extracting lithium include oxides such as vanadium oxide (V ₂ O ₅ ), titanium dioxide (TiO ₂ ), manganese dioxide (MnO ₂ ), and iron disulfide. (FeS ₂ ), disulfides such as titanium disulfide (TiS ₂ ) and molybdenum disulfide (MoS ₂ ), and chalcogenides containing no lithium such as niobium diselenide (NbSe ₂ ) (particularly layered compounds and spinel compounds) ), Lithium-containing compounds containing lithium, and conductive polymers such as sulfur, polyaniline, polythiophene, polyacetylene, or polypyrrole. Of course, the positive electrode material capable of inserting and extracting lithium may be other than the above. Further, two or more kinds of the series of positive electrode materials described above may be mixed in any combination.

  As the conductive agent, for example, a carbon material such as carbon black or graphite is used. Examples of the binder include resin materials such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), styrene butadiene rubber (SBR), and carboxymethyl cellulose (CMC), and these resin materials. At least one selected from a copolymer or the like mainly composed of is used.

  The positive electrode 53 has a positive electrode lead 51 connected to one end of the positive electrode current collector 53A by spot welding or ultrasonic welding. The positive electrode lead 51 is preferably a metal foil or a mesh-like one, but there is no problem even if it is not a metal as long as it is electrochemically and chemically stable and can conduct electricity. Examples of the material of the positive electrode lead 51 include aluminum (Al) and nickel (Ni).

(Negative electrode)
The negative electrode 54 has a structure in which a negative electrode active material layer 54B is provided on one surface or both surfaces of a negative electrode current collector 54A, and the negative electrode active material layer 54B and the positive electrode active material layer 53B are arranged to face each other. Yes.

  Although not shown, the negative electrode active material layer 54B may be provided only on one surface of the negative electrode current collector 54A. The negative electrode current collector 54A is made of, for example, a metal foil such as a copper foil.

  The negative electrode active material layer 54B includes one or more negative electrode materials capable of occluding and releasing lithium as the negative electrode active material, and the positive electrode active material layer 53B as necessary. Other materials such as a binder and a conductive agent similar to those described above may be included.

  In this non-aqueous electrolyte battery, the electrochemical equivalent of the negative electrode material capable of occluding and releasing lithium is larger than the electrochemical equivalent of the positive electrode 53. Lithium metal is not deposited.

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, 2.80 V or more and 6.00 V or less. In particular, when a material that becomes a lithium alloy or a material that occludes lithium is used as a negative electrode active material at a voltage close to 0 V with respect to Li / Li ⁺ , the open circuit voltage in a fully charged state is, for example, 4.20 V or more and It is designed to be within the range of 00V or less. In this case, the open circuit voltage in the fully charged state is preferably 4.25V or more and 6.00V or less. When the open circuit voltage in the fully charged state is 4.25 V or higher, the amount of lithium released per unit mass is increased even with the same positive electrode active material as compared to the 4.20 V battery. Accordingly, the amounts of the positive electrode active material and the negative electrode active material are adjusted. Thereby, a high energy density can be obtained.

  Examples of the negative electrode material capable of inserting and extracting lithium include non-graphitizable carbon, graphitizable carbon, graphite, pyrolytic carbons, cokes, glassy carbons, and fired organic polymer compounds And carbon materials such as carbon fiber and activated carbon. Of these, examples of coke include pitch coke, needle coke, and petroleum coke. An organic polymer compound fired body is a carbonized material obtained by firing a polymer material such as a phenol resin or a furan resin at an appropriate temperature, and part of it is non-graphitizable carbon or graphitizable carbon. Some are classified as: 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 cycle characteristics can be obtained. Furthermore, those having a low charge / discharge potential, specifically, those having a charge / discharge potential close to that of lithium metal are preferable because a high energy density of the battery can be easily realized.

  As another anode material capable of inserting and extracting lithium and capable of increasing the capacity, lithium can be inserted and extracted, and at least one of a metal element and a metalloid element can be used. Also included is a material containing as a constituent element. This is because a high energy density can be obtained by using such a material. In particular, the use with a carbon material is more preferable because a high energy density can be obtained and excellent cycle characteristics can be obtained. The negative electrode material may be a single element, alloy or compound of a metal element or metalloid element, or may have at least a part of one or more of these phases. In the present technology, the alloy includes an alloy including 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 the metal element or metalloid element constituting the negative electrode material include a metal element or metalloid element capable of forming an alloy with lithium. Specifically, magnesium (Mg), boron (B), aluminum (Al), titanium (Ti), gallium (Ga), indium (In), silicon (Si), 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) Can be mentioned. These may be crystalline or amorphous.

  The negative electrode material preferably includes a 4B group metal element or metalloid element in the short periodic table as a constituent element, and more preferably includes at least one of silicon (Si) and tin (Sn) as a constituent element. And particularly preferably those containing at least silicon. This is because silicon (Si) and tin (Sn) have a large ability to occlude and release lithium, and a high energy density can be obtained. Examples of the negative electrode material having at least one of silicon and tin include at least a part of a simple substance, an alloy or a compound of silicon, a simple substance, an alloy or a compound of tin, or one or more phases thereof. The material which has in is mentioned.

  As an alloy of silicon, for example, as a second constituent element other than silicon, tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc ( One containing at least one of the group consisting of Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr) Can be mentioned. Examples of tin alloys include silicon (Si), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), and manganese (Mn) as second constituent elements other than tin (Sn). , Zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr). Including.

  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 these, as the negative electrode material, cobalt (Co), tin (Sn), and carbon (C) are included as constituent elements, and the carbon content is 9.9 mass% or more and 29.7 mass% or less. And the SnCoC containing material whose ratio of cobalt (Co) with respect to the sum total of tin (Sn) and cobalt (Co) is 30 mass% or more and 70 mass% or less is preferable. This is because a high energy density can be obtained in such a composition range, and excellent cycle characteristics can be 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) or bismuth (Bi) are preferable and may contain two or more. This is because the capacity or cycle characteristics can be further improved.

  This 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. It is preferable. In this SnCoC-containing material, it is preferable that at least a part of carbon (C) as a constituent element is bonded to a metal element or a metalloid element as another constituent element. The decrease in cycle characteristics is considered to be due to aggregation or crystallization of tin (Sn) or the like. However, the combination of carbon (C) with other elements suppresses such aggregation or crystallization. Because it can.

  As a measuring method for examining the bonding state of elements, for example, X-ray photoelectron spectroscopy (XPS) can be cited. In XPS, the peak of the carbon 1s orbital (C1s) appears at 284.5 eV in an energy calibrated apparatus so that the peak of the gold atom 4f orbital (Au4f) is obtained at 84.0 eV if it is graphite. . Moreover, if it is surface contamination carbon, it will appear at 284.8 eV. On the other hand, when the charge density of the carbon element increases, 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, at least a part of the carbon contained in the SnCoC-containing material is a metal element or a half of other constituent elements. Combined with metal elements.

  In XPS measurement, for example, the C1s peak 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 the XPS measurement, the waveform of the C1s peak is obtained as a shape including the surface contamination carbon peak and the carbon peak in the SnCoC-containing material. Therefore, by analyzing using, for example, 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 occluding and releasing lithium include metal oxides and polymer compounds capable of occluding and releasing lithium. Examples of the metal oxide include lithium titanium oxide containing titanium and lithium such as lithium titanate (Li ₄ Ti ₅ O ₁₂ ), iron oxide, ruthenium oxide, or molybdenum oxide. Examples of the polymer compound include polyacetylene, polyaniline, polypyrrole, and the like.

(Separator)
The separator 55 is a porous film made of an insulating film having a high ion permeability and a predetermined mechanical strength. A non-aqueous electrolyte is held in the pores of the separator 55.

  The separator 55 is a porous film made of resin, for example. A porous film made of a resin is one in which a material such as a resin is thinly stretched and has a porous structure. For example, a porous film made of a resin is obtained by molding a material such as a resin by a stretch hole method, a phase separation method, or the like. 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, stretching at a low temperature and then at a high temperature are performed to separate the crystal interface to form 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 or the like, and then the solvent is extracted with another volatile solvent, thereby forming a resin. A porous membrane can be obtained. In addition, the manufacturing method of the porous membrane which consists of resin is not limited to these, The method proposed conventionally can be used widely. For example, a polyolefin resin such as polypropylene or polyethylene, an acrylic resin, a styrene resin, a polyester resin, or a nylon resin is preferably used as the resin material constituting the separator 55. In particular, polyethylene such as low density polyethylene, high density polyethylene and linear polyethylene, or their low molecular weight wax content, or polyolefin resin such as polypropylene is suitable because it has an appropriate melting temperature and is easily available. Moreover, it is good also as a porous film formed by melt-kneading the structure which laminated | stacked these 2 or more types of porous films, or 2 or more types of resin materials. A material including a porous film made of a polyolefin resin is excellent in separability between the positive electrode 53 and the negative electrode 54 and can further reduce a decrease in internal short circuit.

  Separator 55 may be an unemployed cloth. Non-woven fabrics are structures that are made by bonding or entanglement between fibers, or by bonding and entanglement, without mechanically or chemically woven or knitting fibers, or a combination of these. Most materials that can be processed into fibers can be used as the raw material of the nonwoven fabric, and by adjusting the shape such as fiber length and thickness, it is possible to provide functions according to the purpose and application. The method for producing a nonwoven fabric typically has two stages: a process of forming a fiber accumulation layer called a fleece, and a bonding process of bonding fleece fibers. At each stage, there are various production methods, which are selected according to the raw material, purpose, and use of the nonwoven fabric. For example, as a process for forming the fleece, a dry method, a wet method, a spun bond method, a melt blow method, or the like can be used. As a bonding step for bonding the fibers of the fleece, a thermal bond method, a chemical bond method, a needle punch method, a spunlace method (a hydroentanglement method), a stitch bond method, a steam jet method, or the like can be used.

  Examples of the nonwoven fabric include a polyethylene terephthalate permeable membrane (polyethylene terephthalate nonwoven fabric) using polyethylene terephthalate (PET) fibers. Note that the air permeable film refers to a film having air permeability. In addition, examples of the nonwoven fabric include aramid fibers, glass fibers, cellulose fibers, polyolefin fibers, nylon fibers, and the like. The nonwoven fabric may use two or more kinds of fibers.

  The thickness of the separator 55 can be arbitrarily set as long as it is equal to or greater than a thickness that can maintain a required strength. The separator 55 insulates between the positive electrode 53 and the negative electrode 54 to prevent a short circuit and the like, and has ion permeability for suitably performing a battery reaction via the separator 55, and the battery reaction in the battery. It is preferable to set the thickness so that the volumetric efficiency of the active material layer contributing to the above can be as high as possible. Specifically, the thickness of the separator 55 is preferably, for example, 4 μm or more and 20 μm or less.

(Electrolyte layer)
The electrolyte layer 56 includes a matrix polymer compound, a nonaqueous electrolytic solution, and solid particles. The electrolyte layer 56 is, for example, a layer in which a nonaqueous electrolyte is held by a matrix polymer compound, and is, for example, a layer made of a so-called gel electrolyte. The solid particles may be included in the negative electrode active material layer 53B and / or in the positive electrode active material layer 54. Further, although details will be described in a later-described modification, a nonaqueous electrolytic solution that is a liquid electrolyte may be used instead of the electrolyte layer 56. In this case, the nonaqueous electrolyte battery includes a wound body having a configuration in which the electrolyte layer 56 is omitted from the wound electrode body 50 in place of the wound electrode body 50. The wound body is impregnated with a nonaqueous electrolytic solution that is a liquid electrolyte filled in the exterior member 60.

(Matrix polymer compound)
As the matrix polymer compound (resin) for holding the electrolytic solution, those having a property compatible with the solvent can be used. Examples of such matrix polymer compounds include fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene, fluorine-containing rubbers such as vinylidene fluoride-tetrafluoroethylene copolymer and ethylene-tetrafluoroethylene copolymer, and styrene. -Butadiene copolymer and hydride thereof, acrylonitrile-butadiene copolymer and hydride thereof, acrylonitrile-butadiene-styrene copolymer and hydride thereof, methacrylic acid ester-acrylic acid ester copolymer, styrene-acrylic acid ester Copolymer, acrylonitrile-acrylic acid ester copolymer, rubber such as ethylene propylene rubber, polyvinyl alcohol, polyvinyl acetate, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carbo Cellulose derivatives such as dimethyl cellulose, polyphenylene ether, polysulfone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide (especially aramid), polyamideimide, polyacrylonitrile, polyvinyl alcohol, polyether, acrylic resin or polyester Examples thereof include a resin having at least one of a melting point and a glass transition temperature of 180 ° C. or higher, and polyethylene glycol.

(Nonaqueous electrolyte)
The nonaqueous electrolytic solution includes an electrolyte salt and a nonaqueous solvent that dissolves the electrolyte salt.

(Electrolyte salt)
The electrolyte salt contains at least one metal salt represented by the formulas (1) to (7).

（式中、Ｘ３１は長周期型周期表における１族元素または２族元素、またはＡｌである。Ｍ３１は遷移金属、または長周期型周期表における１３族元素、１４族元素または１５族元素である。Ｒ７１はハロゲン基である。Ｙ３１は−Ｃ（＝Ｏ）−Ｒ７２−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＣＲ７３₂−、または−Ｃ（＝Ｏ）−Ｃ（＝Ｏ）−である。ただし、Ｒ７２はアルキレン基、ハロゲン化アルキレン基、アリーレン基またはハロゲン化アリーレン基である。Ｒ７３はアルキル基、ハロゲン化アルキル基、アリール基またはハロゲン化アリール基である。なお、ａ３は１〜４の整数であり、ｂ３は０、２または４の整数であり、ｃ３、ｄ３、ｍ３およびｎ３は１〜３の整数である。）

(In the formula, X31 is a group 1 element or group 2 element in the long-period periodic table, or Al. M31 is a transition metal, or a group 13 element, group 14 element, or group 15 element in the long-period periodic table. R71 is a halogen group Y31 is —C (═O) —R72—C (═O) —, —C (═O) —CR73 ₂ —, or —C (═O) —C (═O) Where R72 is an alkylene group, a halogenated alkylene group, an arylene group or a halogenated arylene group, R73 is an alkyl group, a halogenated alkyl group, an aryl group or a halogenated aryl group, wherein a3 is (It is an integer of 1 to 4, b3 is an integer of 0, 2 or 4, and c3, d3, m3 and n3 are integers of 1 to 3.)

（式中、Ｘ４１は長周期型周期表における１族元素または２族元素である。Ｍ４１は遷移金属、または長周期型周期表における１３族元素、１４族元素または１５族元素である。Ｙ４１は−Ｃ（＝Ｏ）−（ＣＲ８１₂）_b4−Ｃ（＝Ｏ）−、−Ｒ８３₂Ｃ−（ＣＲ８２₂）_c4−Ｃ（＝Ｏ）−、−Ｒ８３₂Ｃ−（ＣＲ８２₂）_c4−ＣＲ８３₂−、−Ｒ８３₂Ｃ−（ＣＲ８２₂）_c4−Ｓ（＝Ｏ）₂−、−Ｓ（＝Ｏ）₂−（ＣＲ８２₂）_d4−Ｓ（＝Ｏ）₂−、または−Ｃ（＝Ｏ）−（ＣＲ８２₂）_d4−Ｓ（＝Ｏ）₂−である。ただし、Ｒ８１およびＲ８３は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基であり、それぞれのうちの少なくとも１つはハロゲン基またはハロゲン化アルキル基である。Ｒ８２は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基である。なお、ａ４、ｅ４およびｎ４は１または２の整数であり、ｂ４およびｄ４は１〜４の整数であり、ｃ４は０〜４の整数であり、ｆ４およびｍ４は１〜３の整数である。）

(In the formula, X41 is a group 1 element or group 2 element in the long-period periodic table. M41 is a transition metal, or a group 13, element, or group 15 element in the long-period periodic table. Y41 is -C (= O) - (CR81 2) b4 -C (= O) -, - R83 2 C- (CR82 2) c4 -C (= O) -, - R83 2 C- (CR82 2) c4 -CR83 ₂ −, —R83 ₂ C— (CR82 ₂ ) _c4 —S (═O) ₂ —, —S (═O) ₂ — (CR82 ₂ ) _d4 —S (═O) ₂ —, or —C (═O ) — (CR82 ₂ ) _d4 —S (═O) ₂ —, wherein R81 and R83 are a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group, and at least one of each is a halogen group Or a halogenated alkyl group, wherein R82 represents a hydrogen group, an alkyl group, A4, e4 and n4 are integers of 1 or 2, b4 and d4 are integers of 1 to 4, c4 is an integer of 0 to 4, f4 and m4 is an integer of 1 to 3.)

（式中、Ｘ５１は長周期型周期表における１族元素または２族元素である。Ｍ５１は遷移金属、または長周期型周期表における１３族元素、１４族元素または１５族元素である。Ｒｆはフッ素化アルキル基またはフッ素化アリール基であり、いずれの炭素数も１〜１０である。Ｙ５１は−Ｃ（＝Ｏ）−（ＣＲ９１₂）_d5−Ｃ（＝Ｏ）−、−Ｒ９２₂Ｃ−（ＣＲ９１₂）_d5−Ｃ（＝Ｏ）−、−Ｒ９２₂Ｃ−（ＣＲ９１₂）_d5−ＣＲ９２₂−、−Ｒ９２₂Ｃ−（ＣＲ９１₂）_d5−Ｓ（＝Ｏ）₂−、−Ｓ（＝Ｏ）₂−（ＣＲ９１₂）_e5−Ｓ（＝Ｏ）₂−、または−Ｃ（＝Ｏ）−（ＣＲ９１₂）_e5−Ｓ（＝Ｏ）₂−である。ただし、Ｒ９１は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基である。Ｒ９２は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基であり、そのうちの少なくとも１つはハロゲン基またはハロゲン化アルキル基である。なお、ａ５、ｆ５およびｎ５は１または２の整数であり、ｂ５、ｃ５およびｅ５は１〜４の整数であり、ｄ５は０〜４の整数であり、ｇ５およびｍ５は１〜３の整数である。）

(In the formula, X51 is a group 1 element or a group 2 element in the long-period periodic table. M51 is a transition metal, or a group 13, element, or group 15 element in the long-period periodic table. Rf is A fluorinated alkyl group or a fluorinated aryl group, each having 1 to 10 carbon atoms, Y51 is —C (═O) — (CR91 ₂ ) _d5 —C (═O) —, —R92 ₂ C— _{(CR91 2) d5 -C (=} O) -, - R92 2 C- (CR91 2) d5 -CR92 2 -, - R92 2 C- (CR91 2) d5 -S (= O) 2 -, - S ( ═O) ₂ — (CR91 ₂ ) _e5 —S (═O) ₂ —, or —C (═O) — (CR91 ₂ ) _e5 —S (═O) ₂ —, wherein R91 is a hydrogen group, An alkyl group, a halogen group or a halogenated alkyl group, and R92 represents a hydrogen group, an alkyl group, A gen group or a halogenated alkyl group, at least one of which is a halogen group or a halogenated alkyl group, wherein a5, f5 and n5 are integers of 1 or 2, and b5, c5 and e5 are from 1 to 2, 4 is an integer, d5 is an integer of 0 to 4, and g5 and m5 are integers of 1 to 3.)

  Examples of the metal salt represented by the formula (1) include lithium salts represented by the formulas (1-1) to (1-6). Examples of the metal salt represented by the formula (2) include lithium salts represented by the formulas (2-1) to (2-8). The metal salt represented by the formula (3) is a lithium salt represented by the formula (3-1).

（式中、Ｒ９２は、２価のハロゲン化炭化水素基である。）

(In the formula, R92 is a divalent halogenated hydrocarbon group.)

  Examples of the metal salt represented by the formula (4) include lithium salts represented by the formulas (4-1) to (4-4).

（式中、Ｍ⁺は１価のカチオンであり、ＹはＳＯ₂またはＣＯであり、Ｚはそれぞれ独立してハロゲン基または有機基である。）

(Wherein M ⁺ is a monovalent cation, Y is SO ₂ or CO, and Z is independently a halogen group or an organic group.)

Examples of the organic group include a monovalent hydrocarbon group, a monovalent halogenated hydrocarbon group, a monovalent oxygen-containing hydrocarbon group, and a monovalent halogenated oxygen-containing hydrocarbon group. The halogen group is a fluorine group, a chlorine group, a bromine group or an iodine group. Examples of the cation constituting M ⁺ include lithium ion (Li ⁺ ), sodium ion (Na ⁺ ), alkali metal ions such as potassium ion (K ⁺ ), other metal element ions, ammonium cation, and phosphonium cation. Etc. Of these, lithium ions are preferred.

  Examples of the compound represented by the formula (5) include a compound represented by the formula (5A).

Li [N (SO ₂ R93) (SO ₂ R94)] (5A)
(Wherein R93 and R94 are a halogen group, a monovalent hydrocarbon group, or a monovalent halogenated hydrocarbon group, and at least one of R93 and R94 is a halogen group or a monovalent halogenated hydrocarbon group) Group.)

  The monovalent hydrocarbon group, monovalent halogenated hydrocarbon group, monovalent oxygen-containing hydrocarbon group or monovalent halogenated oxygen-containing hydrocarbon group is, for example, an alkyl group having 1 to 12 carbon atoms, An alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms A group in which two or more of them are bonded, a group in which at least a part of hydrogen groups thereof is substituted with a halogen group, and the like, and the divalent hydrocarbon group or the divalent halogenated carbonization The hydrogen group is an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, an alkynylene group having 2 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, or 3 to 18 carbon atoms. Cycloalkylene groups, they Or a group in which at least a part of the hydrogen groups are substituted with a halogen group.

  Examples of the compound represented by the formula (5A) include a compound represented by the formula (5B), a compound represented by the formula (5C), and the like.

_{LiN (C m F 2m + 1} SO 2) (C n F 2n + 1 SO 2) ··· formula (5B)
(In the formula, m and n are integers of 1 or more.)
_{LiN (C j F 2j + 1} SO 2) (C k F 2k + 1 SO 2) ··· formula (5C)
(In the formula, j and k are integers of 0 or more. At least one of j and k is 0.)

As a compound represented by Formula (5), as a compound represented by Formula (5-B), bis (trifluoromethanesulfonyl) imide lithium (LiN (CF ₃ SO ₂ ) represented by Formula (5-1) ₂ ), bis (pentafluoroethanesulfonyl) imidolithium (LiN (C ₂ F ₅ SO ₂ ) ₂ ), (trifluoromethanesulfonyl) (pentafluoroethanesulfonyl) imide lithium (LiN (CF ₃ SO ₂ ) (C ₂ F ₅ SO _2)), (trifluoromethanesulfonyl) (heptafluoropropanesulfonyl) imide _{(LiN (CF 3 SO 2)} (C 3 F 7 SO 2)), or (trifluoromethanesulfonyl) (nonafluorobutanesulfonyl) lithium imide _{(LiN (CF 3 SO 2)} (C 4 F 9 SO 2)), compounds represented by the formula (5-C) As the formula bis represented by (5-2) (fluorosulfonyl) imide lithium (LiN (FSO _{2) 2),} the formula (5-3) (fluorosulfonyl) (trifluoromethanesulfonyl) imide lithium ( LiN (CF ₃ SO ₂ ) (FSO ₂ )).

Formula (6)
LiC (C _p F _{2p + 1} SO ₂ ) (C _q F _{2q + 1} SO ₂ ) (C _r F _{2r + 1} SO ₂ )
(In the formula, p, q and r are integers of 1 or more.)

  The compound represented by Formula (6) is a chain-like methide compound, and examples thereof include lithium tris (trifluoromethanesulfonyl) methide represented by Formula (6-1).

The electrolyte salt may contain one or more metal salts such as lithium salts other than these metal salts in addition to the metal salts represented by the above formulas (1) to (7). Good. Examples of the lithium salt include lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium perchlorate (LiClO ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), lithium tetraphenylborate _{(LiB (C 6 H 5)} 4), lithium methanesulfonate (LiCH ₃ SO _3), tetrachloroaluminate lithium (LiAlCl _4), dilithium hexafluorosilicate (Li ₂ SiF ₆₎ Lithium chloride (LiCl) or lithium bromide (LiBr). Among these, at least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, and lithium hexafluoroarsenate is preferable, and lithium hexafluorophosphate is more preferable.

(Content of metal salt represented by formula (1) to formula (7))
The content of the metal salt represented by the formula (1) to the formula (7) is 0.01% by mass or more and 2.0% by mass or less with respect to the non-aqueous electrolyte from the point that a more excellent effect is obtained. It is preferable that it is 0.02 mass% or more and 1.8 mass% or less, and it is more preferable that it is 0.03 mass% or more and 1.0 mass% or less.

(Non-aqueous solvent)
Examples of the non-aqueous solvent include lactone solvents such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε-caprolactone, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, Carbonate esters such as diethyl carbonate, ether solvents such as 1,2-dimethoxyethane, 1-ethoxy-2-methoxyethane, 1,2-diethoxyethane, tetrahydrofuran or 2-methyltetrahydrofuran, and nitriles such as acetonitrile Nonaqueous solvents such as solvents, sulfolane-based solvents, phosphoric acids, phosphate ester solvents, and pyrrolidones are exemplified. Any one type of solvent may be used alone, or two or more types may be mixed and used.

(Solid particles)
As the solid particles, for example, at least one of inorganic particles and organic particles can be used. Examples of the inorganic particles include particles of metal oxide, sulfate compound, carbonate compound, metal hydroxide, metal carbide, metal nitride, metal fluoride, phosphate compound, mineral, and the like. As the particles, particles having electrical insulation properties are typically used. However, the surface of the particles (fine particles) of the conductive material is electrically insulated by performing surface treatment with the electrical insulation material. Sedimented particles (fine particles) may be used.

Examples of the metal oxide include silicon oxide (SiO ₂ , silica (silica powder, quartz glass, glass beads, diatomaceous earth, wet or dry synthetic products, etc.), wet synthetic products such as colloidal silica, and dry synthetic products such as fumed silica. Zinc oxide (ZnO), tin oxide (SnO), magnesium oxide (magnesia, MgO), antimony oxide (Sb ₂ O ₃ ), aluminum oxide (alumina, Al ₂ O ₃ ), etc. are preferably used. be able to.

As the sulfate compound, magnesium sulfate (MgSO ₄ ), calcium sulfate (CaSO ₄ ), barium sulfate (BaSO ₄ ), strontium sulfate (SrSO ₄ ) and the like can be suitably used. As the carbonate compound, magnesium carbonate (MgCO ₃ , magnesite), calcium carbonate (CaCO ₃ , calcite), barium carbonate (BaCO ₃ ), lithium carbonate (Li ₂ CO ₃ ) and the like can be suitably used. Examples of metal hydroxides include magnesium hydroxide (Mg (OH) ₂ , brucite), aluminum hydroxide (Al (OH) ₃ (Buyerlite, Gibbsite)), zinc hydroxide (Zn (OH) ₂ ), etc. , Boehmite (Al ₂ O ₃ H ₂ O or AlOOH, diaspore), white carbon (SiO ₂ .nH ₂ O, silica hydrate), zirconium oxide hydrate (ZrO ₂ .nH ₂ O (n = 0.5) To 10)), magnesium oxide hydrate (MgO _a · mH ₂ O (a = 0.8 to 1.2, m = 0.5 to 10)), and other oxide hydroxides, hydrated oxides, Hydroxic hydrates such as magnesium hydroxide octahydrate can be suitably used. As the metal carbide, boron carbide (B ₄ C) or the like can be suitably used. As the metal nitride, silicon nitride (Si ₃ N ₄ ), boron nitride (BN), aluminum nitride (AlN), titanium nitride (TiN), or the like can be suitably used.

As the metal fluoride, lithium fluoride (LiF), aluminum fluoride (AlF ₃ ), calcium fluoride (CaF ₂ ), barium fluoride (BaF ₂ ), magnesium fluoride, or the like can be suitably used. As the phosphate compound, trilithium phosphate (Li ₃ PO ₄ ), magnesium phosphate, magnesium hydrogen phosphate, ammonium polyphosphate, and the like can be suitably used.

  Examples of minerals include silicate minerals, carbonate minerals, and oxide minerals. Silicate minerals are classified based on their crystal structure into nesosilicate minerals, solosilicate minerals, cyclosilicate minerals, inosilicate minerals, layered (phyllo) silicate minerals, and tectosilicate minerals. . Some are classified into fibrous silicate minerals called asbestos based on a classification standard different from the crystal structure.

The nesosilicate mineral is an island-like tetrahedral silicate mineral made of an independent Si—O tetrahedron ([SiO ₄ ] ⁴⁻ ). Examples of the nesosilicate mineral include those corresponding to olivines and meteorites. More specifically, as the nesosilicate mineral, olivine (a continuous solid solution of Mg ₂ SiO ₄ (magnerite olivine) and Fe ₂ SiO ₄ (iron olivine)), magnesium silicate (forsterite (bitter) Earth olivine), Mg ₂ SiO ₄ ), aluminum silicate (Al ₂ SiO ₅ , wilted stone, clinopite, kyanite), zinc silicate (silica zinc mineral, Zn ₂ SiO ₄ ), zirconium silicate ( Zircon, ZrSiO ₄ ), mullite (3Al ₂ O ₃ .2SiO _{2 to} 2Al ₂ O ₃ .SiO ₂ ) and the like.

The solosilicate mineral is a group structure type silicate mineral composed of a Si—O tetrahedral double bond group ([Si ₂ O ₇ ] ⁶⁻ , [Si ₅ O ₁₆ ] ¹²⁻ ). Examples of the silicate mineral include those corresponding to vesuvite and chlorite.

The cyclosilicate mineral is composed of Si—O tetrahedral finite (3-6) bonded rings ([Si ₃ O ₉ ] ⁶⁻ , [Si ₄ O ₁₂ ] ⁸⁻ , [Si ₆ O ₁₈ ] ^{12. -} ) An annular silicate mineral. Examples of the cyclosilicate mineral include beryl and tourmaline.

Inosilicate minerals have an infinite number of Si—O tetrahedral linkages, and are chain-like ([Si ₂ O ₆ ] ⁴⁻ ) and band-like ([Si ₃ O ₉ ] ⁶⁻ , [Si ₄ O ₁₁ ] ^{6 -} , [Si ₅ O ₁₅ ] ^10- , [Si ₇ O ₂₁ ] ^14- ). Examples of the inosilicate mineral include those corresponding to pyroxenes such as calcium silicate (wollastonite, CaSiO ₃ ), and those corresponding to amphibole.

The layered silicate mineral is a layered silicate mineral that forms a network of Si—O tetrahedrons ([SiO ₄ ] ⁴⁻ ). In addition, the specific example of a layered silicate mineral is mentioned later.

The tectosilicate mineral is a three-dimensional network structure type silicate mineral in which a Si—O tetrahedron ([SiO ₄ ] ⁴⁻ ) forms a three-dimensional network bond. The tectosilicates minerals, quartz, feldspars, zeolites, and the like, zeolite _{(M 2 / n O · Al} 2 O 3 · xSiO 2 · yH 2 O, M is a metal element, n represents the valence of M, x ≧ 2, y ≧ 0) = aluminosilicate zeolite such as _{(aM 2 O · bAl 2 O} 3 · cSiO 2 · dH 2 O, M is as defined above .a, b, c, d are each 1 or more And the like.) And the like.

  Examples of asbestos include chrysotile, amosite, and anthophinite.

The carbonate minerals, dolomite _{(dolomite, CaMg (CO 3) 2)} , hydrotalcite _{(Mg 6 Al 2 (CO 3} ) (OH) 16 · 4 (H 2 O)) and the like.

Examples of the oxide mineral include spinel (MgAl ₂ O ₄ ).

Examples of other minerals include strontium titanate (SrTiO ₃ ). The mineral may be a natural mineral or an artificial mineral.

  Some of these minerals are classified as clay minerals. Examples of the clay mineral include a crystalline clay mineral, an amorphous or quasicrystalline clay mineral, and the like. Examples of crystalline clay minerals include layered silicate minerals, those having a structure similar to layered silicates, silicate minerals such as other silicate minerals, and layered carbonate minerals.

  The layered silicate mineral includes a tetrahedral sheet of Si—O and an octahedral sheet of Al—O, Mg—O or the like combined with the tetrahedral sheet. Layered silicates are typically classified by the number of tetrahedral and octahedral sheets, the number of cations in the octahedron, and the layer charge. The layered silicate mineral may be one obtained by substituting all or part of metal ions between layers with organic ammonium ions or the like.

  Specifically, the layered silicate mineral includes a 1: 1 type kaolinite-serpentine group, a 2: 1 type pyrophyllite-talc group, smectite group, vermiculite group, mica group. And those corresponding to the brittle mica (brittle mica) family, chlorite (chlorite group), and the like.

Examples of the kaolinite-serpentine group include chrysotile, antigolite, lizardite, kaolinite (Al ₂ Si ₂ O ₅ (OH) ₄ ), and dickite. Examples of the pyrophyllite-talc family include talc (Mg ₃ Si ₄ O ₁₀ (OH) ₂ ), willemsite, and granite (pyrophyllite, Al ₂ Si ₄ O ₁₀ (OH) _2. ) And the like. Examples of the smectite group include saponite [(Ca / 2, Na) _0.33 (Mg, Fe ²⁺ ) ₃ (Si, Al) ₄ O ₁₀ (OH) ₂ .4H ₂ O], hectorite, Sauconite, montmorillonite {(Na, Ca) _0.33 (Al, Mg) 2Si ₄ O ₁₀ (OH) ₂ .nH ₂ O, where clay containing montmorillonite as a main component is called bentonite}, beidellite, nontrite, etc. . Examples of the mica (mica) family include, for example, moscovite (muscovite, KAl ₂ (AlSi ₃ ) O ₁₀ (OH) ₂ ) sericite (sericite), phlogopite (phlogopite), biotite, lipidite ( Lithia mica) and the like. Examples of those belonging to the brittle mica (brittle mica) family include margarite, clintonite, and anandite. Examples of the chlorite (chlorite) family include kukkeite, sudokuite, clinochlore, chamosite, and nimite.

As a structure close to a layered silicate, a hydrous magnesium silicate having a 2: 1 ribbon structure in which a tetrahedron sheet arranged in a ribbon shape is connected to a tetrahedron sheet arranged in an adjacent ribbon shape while reversing the apex. Etc. Examples of the hydrous magnesium silicate include sepiolite (foamstone: Mg ₉ Si ₁₂ O ₃₀ (OH) ₆ (OH ₂ ) ₄ .6H ₂ O), palygorskite and the like.

Other silicate minerals, zeolites _{(M 2 / n O · Al} 2 O 3 · xSiO 2 · yH 2 O, M is a metal element, n represents the valence of M, x ≧ 2, y ≧ 0) , etc. Porous aluminosilicate, attapulgite [(Mg, Al) 2 Si ₄ O ₁₀ (OH) · 6H ₂ O], and the like.

The layered carbonate minerals, hydrotalcite _{(Mg 6 Al 2 (CO 3} ) (OH) 16 · 4 (H 2 O)) and the like.

Examples of the amorphous or quasicrystalline clay mineral include bingellite, imogolite (Al ₂ SiO ₃ (OH)), and allophane.

  These inorganic particles may be used alone or in combination of two or more. The inorganic particles also have oxidation resistance, and when the electrolyte layer 56 is provided between the positive electrode 53 and the separator 55, the inorganic particles have strong resistance to an oxidizing environment in the vicinity of the positive electrode during charging.

  The solid particles may be organic particles. Materials constituting the organic particles include melamine, melamine cyanurate, melamine polyphosphate, cross-linked polymethyl methacrylate (cross-linked PMMA), polyolefin, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamide, polyimide , Melamine resin, phenol resin, epoxy resin and the like. These materials may be used alone or in combination of two or more.

  Among these solid particles, boehmite, aluminum hydroxide, magnesium hydroxide, and silicate particles are preferable because more excellent effects can be obtained. In these solid particles, the bias of the battery due to —O—H arranged in a sheet form in the crystal structure selectively attracts at least one of the metal salts represented by the formulas (1) to (7), Thereby, at least 1 sort (s) of the metal salt represented by Formula (1)-Formula (7) can be concentrated more intensively in the hollow between active material particles more effectively.

(Battery internal configuration)
3A and 3B are schematic cross-sectional views enlarging a part of the inside of the nonaqueous electrolyte battery according to the first embodiment of the present technology. Note that the binder, the conductive agent, and the like included in the active material layer are not shown.

  As shown in FIG. 3A, in the nonaqueous electrolyte battery according to the first embodiment of the present technology, the solid particles described above are provided between the separator 55 and the negative electrode active material layer 54B and inside the negative electrode active material layer 54B. A certain particle 10 has a configuration in which an appropriate concentration is arranged in an appropriate region. In this configuration, three regions are formed which are divided into a depression-impregnated region A on the negative electrode side, an overcoat region B on the negative electrode side, and a deep region C on the negative electrode side.

  Similarly, as shown in FIG. 3B, in the nonaqueous electrolyte battery according to the first embodiment of the present technology, between the separator 55 and the positive electrode active material layer 53B and inside the positive electrode active material layer 53B, The particles 10 that are the solid particles described above have a configuration in which they are arranged in an appropriate region at an appropriate concentration. In this configuration, three regions are formed which are divided into a depression-impregnated region A on the positive electrode side, an overcoat region B on the positive electrode side, and a deep region C on the positive electrode side.

(Dimple impregnation area A, topcoat area B, deep area C)
For example, the depression-impregnated region A on the negative electrode side and the positive electrode side, the overcoat region B on the negative electrode side and the positive electrode side, and the deep region C on the negative electrode side and the positive electrode side are formed as follows.

(Dimple impregnation region A)
(Dimple impregnation region on the negative electrode side)
The depression-impregnated region A on the negative electrode side is a region including a depression between adjacent negative electrode active material particles 11 located on the outermost surface of the negative electrode active material layer 54B including the negative electrode active material particles 11 that are negative electrode active materials. The hollow impregnation region A is impregnated with an electrolyte containing particles 10 and at least one metal salt represented by the formulas (1) to (7). Thereby, the hollow impregnation area | region A by the side of the negative electrode is satisfy | filled with the electrolyte containing at least 1 sort (s) of the metal salt represented by Formula (1)-Formula (7). Further, the hollow-impregnated region A on the negative electrode side contains particles 10 as solid particles contained in the electrolyte. The electrolyte may be a gel electrolyte or a liquid electrolyte composed of a non-aqueous electrolyte.

  The region excluding the cross section of the negative electrode active material particles 11 in the region between the two parallel lines L1 and L2 shown in FIG. 3A is a depression-impregnated region A on the negative electrode side including a depression in which the electrolyte and the particles 10 are arranged. It is divided. The two parallel lines L1 and L2 are drawn as follows. The cross section of the region between the separator 55 and the negative electrode active material layer 54B and the separator 55 and the negative electrode active material layer 54B is observed with a predetermined visual field width (typically, a visual field width of 50 μm) as shown in FIG. 3A. In this observation field, two parallel lines L1 and L2 perpendicular to the thickness direction of the separator 55 are drawn. The parallel line L1 is a line passing through the position closest to the separator 55 in the cross-sectional image of the negative electrode active material particles 11. The parallel line L2 is a line that passes through the deepest portion of the cross-sectional image of the particle 10 included in the depression between the adjacent negative electrode active material particles 11. The deepest part means a position farthest from the separator 55 in the thickness direction of the separator 55. The cross-sectional observation can be performed using, for example, an SEM (Scanning Electron Microscope).

(Positive area on the positive electrode side)
The dent impregnation region A on the positive electrode side is a region including a dent between adjacent positive electrode active material particles 12 located on the outermost surface of the positive electrode active material layer 53B including the positive electrode active material particles 12 that are positive electrode active materials. The hollow impregnation region A is impregnated with particles 10 that are solid particles and an electrolyte containing at least one metal salt represented by the formulas (1) to (7). Thereby, the dent impregnation area | region A by the side of the positive electrode is satisfy | filled with the electrolyte containing at least 1 sort (s) of the metal salt represented by Formula (1)-Formula (7). Further, the hollow-impregnated region A on the positive electrode side contains particles 10 as solid particles contained in the electrolyte. The electrolyte may be a gel electrolyte or a liquid electrolyte composed of a non-aqueous electrolyte.

  The region excluding the cross section of the positive electrode active material particles 12 in the region between the two parallel lines L1 and L2 shown in FIG. 3B is a dent impregnation region A on the positive electrode side including a dent in which the electrolyte and the particles 10 are arranged. It is divided. The two parallel lines L1 and L2 are drawn as follows. A cross section of the separator 55 and the positive electrode active material layer 53B and a region between the separator 55 and the positive electrode active material layer 53B is observed with a predetermined visual field width (typically, a visual field width of 50 μm) as illustrated in FIG. 3B. In this observation field, two parallel lines L1 and L2 perpendicular to the thickness direction of the separator 55 are drawn. The parallel line L1 is a line passing through a position closest to the separator 55 in the cross-sectional image of the positive electrode active material particles 12. The parallel line L2 is a line that passes through the deepest portion of the cross-sectional image of the particle 10 included in the depression between the adjacent positive electrode active material particles 12. The deepest portion refers to a position farthest from the separator 55 in the thickness direction of the separator 55.

(Overcoating area B)
(Overcoat area on the negative electrode side)
The negative electrode side overcoating region B is a region between the negative electrode side depression-impregnated region A and the separator 55. This overcoating region B is filled with an electrolyte containing at least one metal salt represented by the formulas (1) to (7). The overcoating region B includes particles 10 that are solid particles contained in the electrolyte. The overcoating region B may not include the particles 10. A region between the above-described parallel line L1 and the separator 55 included in the same predetermined observation visual field shown in FIG. 3A is divided as an overcoat region B on the negative electrode side.

(Positive area on the positive electrode side)
The positive electrode side overcoating region B is a region between the positive electrode side depression-impregnated region A and the separator 55. This overcoating region B is filled with an electrolyte containing at least one metal salt represented by the formulas (1) to (7). The overcoating region B includes particles 10 that are solid particles contained in the electrolyte. The overcoating region B may not include the particles 10. A region between the above-described parallel line L1 and the separator 55 included in the same predetermined observation field shown in FIG. 3B is divided as an overcoat region B on the positive electrode side.

(Deep region C)
(Deep region on the negative electrode side)
The deep region C on the negative electrode side is a region inside the negative electrode active material layer 54B on the deeper side than the depression-impregnated region A on the negative electrode side. The voids between the negative electrode active material particles 11 in the deep region C are filled with an electrolyte containing at least one metal salt represented by the formulas (1) to (7). The deep region C includes particles 10 included in the electrolyte. The deep region C may not include the particles 10.

  A region of the negative electrode active material layer 54B other than the recess-impregnated region A and the topcoat region B included in the same predetermined observation field shown in FIG. 3A is divided as a deep region C on the negative electrode side. For example, a region between the above-described parallel line L2 and the negative electrode current collector 54A included in the same predetermined observation visual field shown in FIG. 3A is divided as a deep region C on the negative electrode side.

(Deep region on the positive electrode side)
The deep region C on the positive electrode side is a region inside the positive electrode active material layer 53B on the deeper side than the depression-impregnated region A on the positive electrode side. The space between the positive electrode active material particles 12 in the deep region C on the positive electrode side is filled with an electrolyte containing at least one metal salt represented by the formulas (1) to (7). The deep region C includes particles 10 included in the electrolyte. The deep region C may not include the particles 10.

  A region of the positive electrode active material layer 53B other than the hollow impregnation region A and the overcoating region B included in the same predetermined observation visual field shown in FIG. 3B is divided as a deep region C on the positive electrode side. For example, a region between the above-described parallel line L2 and the positive electrode current collector 53A included in the same predetermined observation visual field illustrated in FIG. 3B is divided as a deep region C on the positive electrode side.

(Concentration of solid particles)
The concentration of solid particles in the depression-impregnated region A on the negative electrode side is 30% by volume or more, preferably 30% by volume or more and 90% by volume or less, and more preferably 40% by volume or more and 80% by volume or less. When the solid particle concentration in the depression-impregnated region A on the negative electrode side is within the above range, more solid particles are arranged in the depression between adjacent particles located on the outermost surface of the negative electrode active material layer. Thereby, at least 1 sort (s) of the metal salt represented by Formula (1)-Formula (7) is capture | acquired by this solid particle, and an additive becomes easy to stagnate in the hollow between adjacent active material particles. For this reason, the abundance ratio of the additive in the dent between adjacent particles can be made higher than other portions. Concentrate at least one of the metal salts represented by the formulas (1) to (7) in the depression, control the metal deposition only in the plane direction, accommodate the deposit inside the depression, and improve overcharge resistance. An excellent battery can be supplied. Moreover, there exists an effect which suppresses having a bad influence on a cycle by at least 1 type of the metal salt represented by Formula (1)-Formula (7) staying in a hollow. It is also possible to achieve both cycle performance and overcharge resistance that have not been realized in the past.

  The concentration of solid particles in the hollow-impregnated region A on the positive electrode side is 30% by volume or more, preferably 30% by volume or more and 90% by volume or less, and more preferably 40% by volume or more and 80% by volume or less. When solid particles are arranged in the depressions between adjacent active material particles on the outermost surface of the positive electrode, most of the lithium ions that have come out of the positive electrode pass through this portion, and therefore, are expressed by the equations (1) to (7). To provide a large amount of at least one anion of the metal salt. As a result, at least one of the metal salts represented by the formulas (1) to (7) is concentrated in the depression, the metal deposition is controlled only in the plane direction, the deposit is accommodated inside the depression, Charge tolerance can be improved.

  It is preferable that the solid particle concentration in the depression-impregnated region A on the negative electrode side is not less than 10 times the solid particle concentration in the deep region C on the negative electrode side. The particle concentration in the deep region C on the negative electrode side is preferably 3% by volume or less. If the concentration of solid particles in the deep region C on the negative electrode side is too high, there are too many solid particles between the active material particles, resulting in resistance, or the trapped metal salt causes a side reaction, resulting in an internal resistance. It will increase.

  For the same reason, the solid particle concentration in the dip-impregnated region A on the positive electrode side is preferably 10 times or more than the solid particle concentration in the deep region C on the positive electrode side. The particle concentration in the deep region C on the positive electrode side is preferably 3% by volume or less. If the concentration of the solid particles in the deep region C on the positive electrode side is too high, too much is present between the active material particles, which causes resistance, or a trapped metal salt causes a side reaction, increasing internal resistance. End up.

(Solid particle concentration)
The above-mentioned solid particle concentration is the area percentage of the total area of the particle cross section when the observation visual field of 2 μm × 2 μm is taken ((“total area of the particle cross section” ÷ “area of the observation visual field”) × 100) (%) The volume concentration (volume%) of the solid particles defined by When the concentration of the depression impregnated region A is defined, for example, the observation visual field is taken near the center in the width direction of the depression formed between adjacent particles. Observation is performed using, for example, an SEM, and each area described above can be calculated by processing an image acquired by photographing.

(Thickness of the depression impregnation region A, topcoat region B, and deep region C)
The thickness of the depression-impregnated region A on the negative electrode side is preferably 10% to 40% of the thickness of the negative electrode active material layer 54B. When the thickness of the depression-impregnated region A on the negative electrode side is in the above range, the necessary solid particle amount to be disposed in the depression is ensured and the state where the solid particles and the additive do not enter the deep region C is maintained. be able to. Further, the thickness of the recess-impregnated region A on the negative electrode side is more preferably within the above range and twice or more the thickness of the overcoat region B on the negative electrode side. This is because the energy density can be further improved by avoiding an increase in the distance between the electrodes. For the same reason, the thickness of the dip-impregnated region A on the positive electrode side is more preferably twice or more the thickness of the overcoat region B on the positive electrode side.

(Measurement method for thickness of each region)
When the thickness of the depression impregnation region A is defined, the average value of the thickness of the depression impregnation region A in four different observation fields is set as the thickness of the depression impregnation region A. When the thickness of the topcoat region B is defined, the average value of the thickness of the topcoat region B in four different observation fields is set as the thickness of the topcoat region B. When the thickness of the deep region C is defined, the average value of the thickness of the deep region C in four different observation fields is set as the thickness of the deep region C.

(Particle size of solid particles)
As the particle diameter of the solid particles, the particle diameter D50 is preferably not more than “2 / √3-1” times the particle diameter D50 of the active material particles. Further, as the particle diameter of the solid particles, the particle diameter D50 is more preferably 0.1 μm or more. As the particle diameter of the solid particles, the particle diameter D95 is preferably “2 / √3-1” times or more the particle diameter D50 of the active material particles. The particle having the larger particle diameter can block the gap between adjacent active material particles at the bottom of the dent, so that excessive solid particles in the deep region C can be prevented from adversely affecting battery characteristics.

(Measurement of particle diameter)
The particle size D50 of the solid particles is calculated from, for example, the particle size distribution measured by the laser diffraction method from the particle side having a small particle size after removing constituents other than the solid particles from the electrolyte containing the solid particles. The particle size is 50% cumulative volume. Further, from the measured particle size distribution, a value of the particle diameter D95 with a volume cumulative of 95% can be obtained. The particle size D50 of the active material is the particle size distribution of the active material particles obtained by removing constituents other than the active material particles from the active material layer containing the active material particles by the laser diffraction method. The particle diameter is 50% of the cumulative volume calculated from

(Specific surface area of solid particles)
The specific surface area (m ² / g) is a BET specific surface area (m ² / g) measured by a BET method which is a specific surface area measurement method. The BET specific surface area of the solid particles is preferably 1 m ² / g or more and 60 m ² / g or less. In the case where the BET specific surface area is in the above numerical range, it is preferable because the action of the solid particles capturing at least one of the metal salts represented by the formulas (1) to (7) is enhanced. On the other hand, when the BET specific surface area is too large, even lithium ions are trapped, and the output characteristics tend to be lowered. The specific surface area of the solid particles can be obtained, for example, by measuring the solid particles after removing components other than the solid particles from the electrolyte containing the solid particles in the same manner as described above.

(Addition amount of solid particles)
The addition amount of the solid particles is preferably 1% by mass or more and 60% by mass or less, and more preferably 2% by mass or more and 50% by mass or less with respect to the electrolyte from the viewpoint of obtaining a more excellent effect. More preferably, it is 5 mass% or more and 40 mass% or less.

(Configuration having a dip-impregnated region A, topcoat region B, and deep region C only on the negative electrode side or the positive electrode side)
Note that the electrolyte layer 56 containing solid particles may be formed only on both main surfaces of the negative electrode 54, and the electrolyte layer 56 not containing solid particles is applied and formed on both main surfaces of the positive electrode 53. May be. Similarly, the electrolyte layer 56 containing solid particles may be formed only on both main surfaces of the positive electrode 53. In addition, an electrolyte layer 56 that does not contain solid particles may be applied and formed on both main surfaces of the negative electrode 54. In these cases, only the depression-impregnated region A on the negative electrode side, the overcoating region B on the negative electrode side, and the deep region C on the negative electrode side are formed, and these regions are not formed on the positive electrode side. Only the depression-impregnated region A on the positive electrode side, the overcoating region B on the positive electrode side, and the deep region C on the positive electrode side are formed, and these regions are not formed on the negative electrode side.

(1-2) An example of a manufacturing method of a nonaqueous electrolyte battery An example of this nonaqueous electrolyte battery can be manufactured as follows, for example.

(Production method of positive electrode)
A positive electrode active material, a conductive agent, and a binder are mixed to prepare a positive electrode mixture, and the positive electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to obtain a paste-like positive electrode mixture slurry Is made. Next, the positive electrode mixture slurry is applied to the positive electrode current collector 53A, the solvent is dried, and the positive electrode active material layer 53B is formed by compression molding with a roll press or the like, and the positive electrode 53 is manufactured.

(Method for producing negative electrode)
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 prepare a paste-like negative electrode mixture slurry. Next, this negative electrode mixture slurry is applied to the negative electrode current collector 54A, the solvent is dried, and the negative electrode active material layer 54B is formed by compression molding with a roll press machine or the like, and the negative electrode 54 is manufactured.

(Preparation of non-aqueous electrolyte)
The nonaqueous electrolytic solution is prepared by dissolving an electrolyte salt containing at least one metal salt represented by the formulas (1) to (7) in a nonaqueous solvent.

(Solution application)
A coating solution containing a nonaqueous electrolytic solution, a matrix polymer compound, solid particles, and a diluting solvent (such as dimethyl carbonate) was applied to both main surfaces of the positive electrode 53 and the negative electrode 54 in a heated state. Thereafter, the electrolyte layer 56 is formed by volatilizing the diluting solvent.

  By applying the coating solution in a heated state, the electrolyte containing the solid particles is formed in the depressions between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer 54B or in the deep region C inside the negative electrode active material layer 54B. Can be soaked. At this time, the solid particles are scraped by the dents between adjacent particles, so that the particle concentration in the dent impregnation region A on the negative electrode side increases. Thereby, a difference can be provided in the particle | grain density | concentration of the hollow impregnation area | region A and the deep part area | region C. FIG. Similarly, by applying the coating solution in a heated state, the electrolyte containing the solid particles is recessed between adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer 53B or deep inside the positive electrode active material layer 53B. The region C can be soaked. At this time, solid particles are rubbed in the dents between adjacent particles, so that the particle concentration in the dent impregnation region A on the positive electrode side increases. Thereby, a difference can be provided in the particle | grain density | concentration of the hollow impregnation area | region A and the deep part area | region C. FIG.

  It should be noted that the distance between the electrodes can be prevented from inadvertently spreading by scraping off the excess coating solution after coating the coating solution. Further, by scraping the surface of the coating solution, more solid particles can be arranged in the recesses between adjacent active material particles, and the ratio of the solid particles in the topcoat region A is lowered. As a result, most of the solid particles are intensively arranged in the depression-impregnated region A, and more additive can be collected in the depression-impregnated region A.

  The following may be used. Both main surfaces of the positive electrode 53 are coated with a coating solution (a coating solution excluding particles) containing a nonaqueous electrolytic solution, a matrix polymer compound, and a diluting solvent (such as dimethyl carbonate), and contain solid particles. Alternatively, the electrolyte layer 56 may be formed. Alternatively, the electrolyte layer 56 including the same solid particles may be formed only on both main surfaces of the negative electrode 54 without forming the electrolyte layer 56 on one main surface or both main surfaces of the positive electrode 53. . Both main surfaces of the negative electrode 54 are coated with a coating solution (a coating solution excluding particles) containing a non-aqueous electrolyte, a matrix polymer compound, and a diluting solvent (such as dimethyl carbonate), and contains solid particles. Alternatively, the electrolyte layer 56 may be formed. Alternatively, the electrolyte layer 56 including the same solid particles may be formed only on both main surfaces of the positive electrode 53 without forming the electrolyte layer 56 on one main surface or both main surfaces of the negative electrode 54. .

(Assembly of non-aqueous electrolyte battery)
Next, the positive electrode lead 51 is attached to the end of the positive electrode current collector 53A by welding, and the negative electrode lead 52 is attached to the end of the negative electrode current collector 54A by welding.

  Next, the positive electrode 53 on which the electrolyte layer 56 is formed and the negative electrode 54 on which the electrolyte layer 56 is formed are laminated through a separator 55 to form a laminate, and then the laminate is wound in the longitudinal direction, A wound electrode body 50 is formed by adhering a protective tape 57 to the outermost periphery.

  Finally, for example, the wound electrode body 50 is sandwiched between the exterior members 60, and the outer edges of the exterior members 60 are sealed and sealed by thermal fusion or the like. At that time, an adhesion film 61 is inserted between the positive electrode lead 51 and the negative electrode lead 52 and the exterior member 60. Thereby, the nonaqueous electrolyte battery shown in FIGS. 1 and 2 is completed.

[Modification 1-1]
The nonaqueous electrolyte battery according to the first embodiment may be manufactured as follows. In this manufacturing method, instead of applying the coating solution to both surfaces of at least one of the positive electrode 53 and the negative electrode 54 in the solution coating step of the manufacturing method of an example of the nonaqueous electrolyte battery, the coating solution is used for both of the separators 55. This is the same as the manufacturing method of the example of the non-aqueous electrolyte battery described above except that it is formed on at least one of the main surfaces and then further heated and pressurized.

[Method for Producing Nonaqueous Electrolyte Battery of Modification 1-1]
(Preparation of positive electrode, negative electrode, separator, preparation of non-aqueous electrolyte)
In the same manner as the manufacturing method of an example of the nonaqueous electrolyte battery, the positive electrode 53, the negative electrode 54, and the separator 55 are manufactured and the nonaqueous electrolytic solution is prepared.

(Solution application)
After applying a coating solution containing a nonaqueous electrolytic solution, a resin, solid particles, and a diluent solvent (dimethyl carbonate, etc.) on at least one of both surfaces of the separator 55, the diluent solvent is volatilized and the electrolyte is removed. Layer 56 is formed.

(Assembly of non-aqueous electrolyte battery)
Next, the positive electrode lead 51 is attached to the end of the positive electrode current collector 53A by welding, and the negative electrode lead 52 is attached to the end of the negative electrode current collector 54A by welding.

  Next, after laminating the positive electrode 53 and the negative electrode 54 through the separator 55 on which the electrolyte layer 56 is formed to form a laminated body, the laminated body is wound in the longitudinal direction, and the protective tape 57 is provided on the outermost peripheral portion. Are wound to form the wound electrode body 50.

(Warming and pressurization process)
Next, the wound electrode body 50 is sealed in a packaging material such as a latex tube and heated under a hydrostatic pressure. As a result, the solid particles are moved to the depressions between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer 54B, and the solid particle concentration in the depression-impregnated region A on the negative electrode side is increased. The solid particles are moved to the depressions between the adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer 53B, and the solid particle concentration in the depression-impregnated region A on the positive electrode side is increased.

  Finally, a recess is formed by deep drawing the exterior member 60 made of a laminate film, the wound electrode body 50 is inserted into the recess, an unprocessed portion of the exterior member 60 is folded back to the upper portion of the recess, and the outer periphery of the recess Heat weld. At that time, an adhesion film 61 is inserted between the positive electrode lead 51 and the negative electrode lead 52 and the exterior member 60. As a result, the intended nonaqueous electrolyte battery is obtained.

[Modification 1-2]
In the first embodiment described above, the configuration example using the gel electrolyte has been described. However, instead of the gel electrolyte, an electrolyte solution that is a liquid electrolyte may be used. In this case, the exterior member 60 is filled with a non-aqueous electrolyte, and a wound body having a configuration in which the electrolyte layer 56 is omitted from the wound electrode body 50 is impregnated with the non-aqueous electrolyte. In this case, the nonaqueous electrolyte battery is manufactured as follows, for example.

[Method for Producing Nonaqueous Electrolyte Battery of Modification 1-2]
(Preparation of positive electrode, negative electrode, non-aqueous electrolyte)
In the same manner as the manufacturing method of an example of the nonaqueous electrolyte battery, the positive electrode 53 and the negative electrode 54 are manufactured and the nonaqueous electrolyte solution is prepared.

(Coating formation of solid particle layer)
Next, a paint is applied on at least one main surface of both main surfaces of the negative electrode 54 by a coating method or the like, and then dried to remove the solvent, thereby forming a solid particle layer. As the paint, for example, a mixture of solid particles, a binder polymer compound (resin) and a solvent can be used. On the outermost surface of the negative electrode active material layer 54B on which the solid particle layer is applied and formed, the solid particles are scraped by the dents between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer 54B, and the dents on the negative electrode side The particle concentration in the impregnation region A increases. Similarly, a coating similar to that described above is applied to both main surfaces of the positive electrode 53 by a coating method or the like, and then dried to remove the solvent and form a solid particle layer. On the outermost surface of the positive electrode active material layer 53B on which the solid particle layer is applied and formed, the solid particles are scraped by the depressions between adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer 54B, and the depression on the positive electrode side. The particle concentration in the impregnation region A increases. As the solid particles, for example, those adjusted so that the particle diameter D95 of the solid particles is equal to or greater than a predetermined magnification of the particle diameter D50 of the active material particles are preferably used. For example, as the solid particles, solid particles having a particle size D95 of 2 / √3-1 times or more of the particle size D50 of the active material particles are added to a part of the solid particles, and the particle size D95 of the solid particles is the particle size D50 of the active material particles. It is preferable to use one adjusted to be 2 / √3-1 times or more. As a result, the solid particles having a larger particle diameter can fill the gaps between the particles at the bottom of the depression and make it easier to scrape the solid particles.

  In addition, when the solid particle layer is applied and formed, the distance between the electrodes can be prevented from being inadvertently widened by scraping excess paint. Further, by scraping the surface of the paint, more solid particles can be arranged in the recesses between adjacent active material particles, and the ratio of the solid particles in the topcoat region B is lowered. As a result, most of the solid particles are concentrated in the depression-impregnated region, and at least one of the metal salts represented by the formulas (1) to (7) is concentrated in the depression-impregnated region A. be able to.

(Assembling of non-aqueous electrolyte battery)
Next, the positive electrode lead 51 is attached to the end of the positive electrode current collector 53A by welding, and the negative electrode lead 52 is attached to the end of the negative electrode current collector 54A by welding.

  Next, the positive electrode 53 and the negative electrode 54 are laminated and wound via the separator 55, and the protective tape 57 is adhered to the outermost peripheral portion to form a wound body that is a precursor of the wound electrode body 50. Next, the wound body is sandwiched between the exterior members 60, and the outer peripheral edge portion excluding one side is heat-sealed to form a bag shape, and is stored inside the exterior member 60.

  Next, after injecting a non-aqueous electrolyte into the exterior member 60 and impregnating the wound body with the non-aqueous electrolyte, the opening of the exterior member 60 is heat-sealed in a vacuum atmosphere and sealed. As a result, the intended non-electrolyte secondary battery is obtained.

[Modification 1-3]
The nonaqueous electrolyte battery according to the first embodiment may be manufactured as follows.

[Method for Producing Nonaqueous Electrolyte Battery of Modification 1-3]
(Preparation of positive and negative electrodes)
The positive electrode 53 and the negative electrode 54 are produced in the same manner as in the manufacturing method of an example of the nonaqueous electrolyte battery.

(Coating formation of solid particle layer)
Next, in the same manner as in Modification 1-2, a solid particle layer is formed on at least one main surface of both main surfaces of the negative electrode. Similarly, a solid particle layer is formed on at least one main surface of both main surfaces of the positive electrode.

(Preparation of composition for electrolyte)
Next, an electrolyte composition containing a non-aqueous electrolyte, a monomer that is a raw material for the polymer compound, a polymerization initiator, and other materials such as a polymerization inhibitor as necessary is prepared.

(Assembling of non-aqueous electrolyte battery)
Next, a wound body that is a precursor of the wound electrode body 50 is formed in the same manner as in Modification 1-2. Next, the wound body is sandwiched between the exterior members 60, and the outer peripheral edge portion excluding one side is heat-sealed to form a bag shape, and is stored inside the exterior member 60.

  Next, after injecting the electrolyte composition into the bag-shaped exterior member 60, the exterior member 60 is sealed using a heat fusion method or the like. Subsequently, the monomer is polymerized by thermal polymerization or the like. Thereby, since a high molecular compound is formed, the electrolyte layer 56 is formed. As a result, the intended nonaqueous electrolyte battery is obtained.

[Modification 1-4]
The nonaqueous electrolyte battery according to the first embodiment may be manufactured as follows.

[Method for Producing Nonaqueous Electrolyte Battery of Modification 1-4]
(Preparation of positive and negative electrodes, preparation of non-aqueous electrolyte)
First, the positive electrode 53 and the negative electrode 54 are prepared and the nonaqueous electrolyte solution is prepared in the same manner as in the example of the method for manufacturing the nonaqueous electrolyte battery.

(Formation of solid particle layer)
Next, in the same manner as in Modification 1-2, a solid particle layer is formed on at least one main surface of both main surfaces of the negative electrode 54. Similarly, a solid particle layer is formed on at least one main surface of both main surfaces of the positive electrode 53.

(Coating formation of matrix resin layer)
Next, a coating solution containing a nonaqueous electrolytic solution, a matrix polymer compound, and a dispersion solvent such as N-methyl-2-pyrrolidone is applied to at least one of the main surfaces of the separator 55. Then, drying and the like are performed to form a matrix resin layer.

(Assembling of non-aqueous electrolyte battery)
Next, after the positive electrode 53 and the negative electrode 54 are laminated via the separator 55 to form a laminated body, the laminated body is wound in the longitudinal direction, and the protective tape 57 is adhered to the outermost peripheral portion to thereby form the wound electrode. The body 50 is produced.

  Next, the exterior member 60 made of a laminate film is deep-drawn to form a recess, the wound electrode body 50 is inserted into the recess, the unprocessed portion of the exterior member 60 is folded back to the upper portion of the recess, and the outer periphery of the recess Heat welding is performed except for a part (for example, one side). At that time, an adhesion film 61 is inserted between the positive electrode lead 51 and the negative electrode lead 52 and the exterior member 60.

  Subsequently, after injecting the non-aqueous electrolyte from the unwelded portion of the exterior member 60 into the interior, the unwelded portion of the exterior member 60 is sealed by thermal fusion or the like. At this time, by vacuum sealing, the matrix resin layer is impregnated with the nonaqueous electrolytic solution, and the matrix polymer compound swells to form the electrolyte layer 56. Thereby, the target nonaqueous electrolyte battery is obtained.

[Modification 1-5]
In the first embodiment described above, the configuration example using the gel electrolyte has been described. However, instead of the gel electrolyte, an electrolyte solution that is a liquid electrolyte may be used. In this case, the exterior member 60 is filled with a non-aqueous electrolyte, and a wound body having a configuration in which the electrolyte layer 56 is omitted from the wound electrode body 50 is impregnated with the non-aqueous electrolyte. In this case, the nonaqueous electrolyte battery is manufactured as follows, for example.

[Method for Producing Nonaqueous Electrolytic Battery of Modification 1-5]
(Preparation of positive and negative electrodes, preparation of non-aqueous electrolyte)
First, the positive electrode 53 and the negative electrode 54 are prepared and the nonaqueous electrolytic solution is prepared in the same manner as in the example of the method for manufacturing the nonaqueous electrolyte battery.

(Formation of solid particle layer)
Next, a solid particle layer is formed on at least one main surface of both main surfaces of the separator 55 by a coating method or the like.

(Assembling of non-aqueous electrolyte battery)
Next, the positive electrode 53 and the negative electrode 54 are laminated and wound via the separator 55, and the protective tape 57 is adhered to the outermost peripheral portion to form a wound body that is a precursor of the wound electrode body 50.

(Warming and pressurization process)
Next, before injecting the electrolyte into the exterior member 60, the wound body is put in a packaging material such as a latex tube and sealed, and heated under hydrostatic pressure. As a result, the solid particles are moved to the depressions between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer 54B, and the solid particle concentration in the depression-impregnated region A on the negative electrode side is increased. The solid particles are moved to the depressions between the adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer 53B, and the solid particle concentration in the depression-impregnated region A on the positive electrode side is increased.

  Next, the wound body is sandwiched between the exterior members 60, and the outer peripheral edge portion excluding one side is heat-sealed to form a bag shape, and is stored inside the exterior member 60. Next, a non-aqueous electrolyte is prepared, poured into the exterior member 60, the wound body is impregnated with the non-aqueous electrolyte, and the opening of the exterior member 60 is heat-sealed in a vacuum atmosphere. Seal. As a result, the intended nonaqueous electrolyte battery is obtained.

[Modification 1-6]
The nonaqueous electrolyte battery according to the first embodiment may be manufactured as follows.

[Method for Producing Nonaqueous Electrolyte Battery of Modification 1-6]
(Preparation of positive and negative electrodes)
First, the positive electrode 53 and the negative electrode 54 are produced in the same manner as in the example of the method for manufacturing the nonaqueous electrolyte battery.

(Preparation of composition for electrolyte)
Next, an electrolyte composition containing a non-aqueous electrolyte, a monomer that is a raw material for the polymer compound, a polymerization initiator, and other materials such as a polymerization inhibitor as necessary is prepared.

(Formation of solid particle layer)
Next, a solid particle layer is formed on at least one main surface of both main surfaces of the separator 55 by a coating method or the like.

(Assembling of non-aqueous electrolyte battery)
Next, a wound body that is a precursor of the wound electrode body 50 is formed in the same manner as in Modification 1-2.

(Warming and pressurization process)
Next, before injecting the non-aqueous electrolyte into the exterior member 60, the wound body is sealed in a packaging material such as a latex tube and heated under hydrostatic pressure. As a result, the solid particles are moved to the depressions between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer 54B, and the solid particle concentration in the depression-impregnated region A on the negative electrode side is increased. The solid particles are moved to the depressions between the adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer 53B, and the solid particle concentration in the depression-impregnated region A on the positive electrode side is increased.

  Next, the wound body is sandwiched between the exterior members 60, and the outer peripheral edge portion excluding one side is heat-sealed to form a bag shape, and is stored inside the exterior member 60.

  Next, after injecting the electrolyte composition into the bag-shaped exterior member 60, the exterior member 60 is sealed using a heat fusion method or the like. Subsequently, the monomer is polymerized by thermal polymerization or the like. Thereby, since a high molecular compound is formed, the electrolyte layer 56 is formed. As a result, the intended nonaqueous electrolyte battery is obtained.

[Modification 1-7]
The nonaqueous electrolyte battery according to the first embodiment may be manufactured as follows.

[Method for Producing Nonaqueous Electrolyte Battery of Modification 1-7]
(Preparation of positive and negative electrodes)
First, the positive electrode 53 and the negative electrode 54 are produced in the same manner as in the manufacturing method of an example of the nonaqueous electrolyte battery. Next, solid particles and a matrix polymer compound are applied to at least one main surface of both main surfaces of the separator 55, and then dried to form a matrix resin layer.

(Assembling of non-aqueous electrolyte battery)
Next, after the positive electrode 53 and the negative electrode 54 are laminated via the separator 55 to form a laminated body, the laminated body is wound in the longitudinal direction, and the protective tape 57 is adhered to the outermost peripheral portion to thereby form the wound electrode. The body 50 is produced.

(Warming and pressurization process)
Next, the wound electrode body 50 is sealed in a packaging material such as a latex tube and heated under a hydrostatic pressure. As a result, the solid particles are moved to the depressions between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer 54B, and the solid particle concentration in the depression-impregnated region A on the negative electrode side is increased. The solid particles are moved to the depressions between the adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer 53B, and the solid particle concentration in the depression-impregnated region A on the positive electrode side is increased.

  Next, the exterior member 60 made of a laminate film is deep-drawn to form a recess, the wound electrode body 50 is inserted into the recess, the unprocessed portion of the exterior member 60 is folded back to the upper portion of the recess, and the outer periphery of the recess Heat welding is performed except for a part (for example, one side). At that time, an adhesion film 61 is inserted between the positive electrode lead 51 and the negative electrode lead 52 and the exterior member 60.

  Subsequently, after injecting the non-aqueous electrolyte from the unwelded portion of the exterior member 60 into the interior, the unwelded portion of the exterior member 60 is sealed by thermal fusion or the like. At this time, by vacuum sealing, the matrix resin layer is impregnated with the nonaqueous electrolytic solution, and the matrix polymer compound swells to form the electrolyte layer 56. Thereby, the target nonaqueous electrolyte battery is obtained.

[Modification 1-8]
In the above-described example of the first embodiment and Modifications 1-1 to 1-7, the nonaqueous electrolyte battery in which the wound electrode body 50 is sheathed with the exterior member 60 has been described. As shown in FIG. 4C, a laminated electrode body 70 may be used instead of the wound electrode body 50. FIG. 4A is an external view of a nonaqueous electrolyte battery in which the laminated electrode body 70 is accommodated. FIG. 4B is an exploded perspective view showing a state in which the laminated electrode body 70 is accommodated in the exterior member 60. 4C is an external view showing an external appearance from the bottom surface side of the nonaqueous electrolyte battery shown in FIG. 4A.

  The laminated electrode body 70 uses a laminated electrode body 70 in which a rectangular positive electrode 73 and a rectangular negative electrode 74 are laminated via a rectangular separator 75 and fixed by a fixing member 76. Although not shown, when the electrolyte layer is formed, the electrolyte layer is provided in contact with the positive electrode 73 and the negative electrode 74. For example, an electrolyte layer (not shown) is provided between the positive electrode 73 and the separator 75 and between the negative electrode 74 and the separator 75. This electrolyte layer is the same as the electrolyte layer 56 described above. A positive electrode lead 71 connected to the positive electrode 73 and a negative electrode lead 72 connected to the negative electrode 74 are led out from the laminated electrode body 70, and the positive electrode lead 71, the negative electrode lead 72, and the exterior member 60 are in close contact with each other. A film 61 is provided.

  In addition, the manufacturing method of a nonaqueous electrolyte battery produces a laminated electrode body instead of the wound electrode body 70, and a laminated body (a structure in which the electrolyte layer is omitted from the laminated electrode body 70) instead of the wound body. Is the same as the manufacturing method of the nonaqueous electrolyte battery according to the example of the first embodiment and the modifications 1-1 to 1-7.

2. Second Embodiment In a second embodiment of the present technology, a cylindrical nonaqueous electrolyte battery (battery) will be described. This nonaqueous electrolyte battery is, for example, a nonaqueous electrolyte secondary battery that can be charged and discharged, and is, for example, a lithium ion secondary battery.

(2-1) Configuration of an Example of Nonaqueous Electrolyte Battery FIG. 5 is a cross-sectional view showing an example of a nonaqueous electrolyte battery according to the second embodiment. The nonaqueous electrolyte battery is a nonaqueous electrolyte secondary battery that can be charged and discharged, for example. This non-aqueous electrolyte battery is a so-called cylindrical type, and is formed in a substantially hollow cylindrical battery can 81 with a non-illustrated liquid non-aqueous electrolyte (hereinafter appropriately referred to as a non-aqueous electrolyte) and a belt-like shape. A positive electrode 91 and a negative electrode 92 have a wound electrode body 90 in which a separator 93 is wound.

  The battery can 81 is made of, for example, iron plated with nickel, and has one end closed and the other end open. Inside the battery can 81, a pair of insulating plates 82a and 82b are respectively arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 90 therebetween.

  Examples of the material of the battery can 81 include iron (Fe), nickel (Ni), stainless steel (SUS), aluminum (Al), titanium (Ti), and the like. The battery can 81 may be plated with, for example, nickel or the like in order to prevent corrosion due to an electrochemical non-aqueous electrolyte accompanying charging / discharging of the non-aqueous electrolyte battery. At the open end of the battery can 81, a battery lid 83, which is a positive electrode lead plate, and a safety valve mechanism and a thermal resistance element (PTC element: Positive Temperature Coefficient) 87 provided inside the battery lid 83 are insulated and sealed. It is attached by caulking through a gasket 88 for

  The battery lid 83 is made of the same material as the battery can 81, for example, and is provided with an opening for discharging gas generated inside the battery. In the safety valve mechanism, a safety valve 84, a disc holder 85, and a shut-off disc 86 are sequentially stacked. The protruding portion 84a of the safety valve 84 is connected to the positive electrode lead 95 led out from the wound electrode body 90 through a sub disk 89 disposed so as to cover a hole 86a provided at the center of the shutoff disk 86. . By connecting the safety valve 84 and the positive electrode lead 95 via the sub disk 89, the positive electrode lead 95 is prevented from being drawn from the hole 86a when the safety valve 84 is reversed. Further, the safety valve mechanism is electrically connected to the battery lid 83 via the heat sensitive resistance element 87.

  The safety valve mechanism reverses the safety valve 84 when the internal pressure of the nonaqueous electrolyte battery exceeds a certain level due to internal short circuit of the battery or heating from the outside of the battery, etc., and the protrusion 84a, the battery lid 83, the wound electrode body 90, This disconnects the electrical connection. That is, when the safety valve 84 is reversed, the positive electrode lead 95 is pressed by the shut-off disk 86 and the connection between the safety valve 84 and the positive electrode lead 95 is released. The disc holder 85 is made of an insulating material, and when the safety valve 84 is reversed, the safety valve 84 and the shut-off disc 86 are insulated.

  Further, when further gas is generated inside the battery and the internal pressure of the battery further increases, a part of the safety valve 84 is broken and the gas can be discharged to the battery lid 83 side.

  In addition, for example, a plurality of gas vent holes (not shown) are provided around the hole 86a of the shut-off disk 86. When gas is generated from the wound electrode body 90, the gas is effectively removed from the battery lid. It is set as the structure which can discharge | emit to 83 side.

  The heat sensitive resistance element 87 increases in resistance value when the temperature rises, interrupts the current by disconnecting the electrical connection between the battery lid 83 and the wound electrode body 90, and generates abnormal heat due to an excessive current. To prevent. The gasket 88 is made of, for example, an insulating material, and asphalt is applied to the surface.

  The wound electrode body 90 accommodated in the nonaqueous electrolyte battery is wound around the center pin 94. The wound electrode body 90 is formed by sequentially laminating a positive electrode 91 and a negative electrode 92 with a separator 93 interposed therebetween and wound in the longitudinal direction. A positive electrode lead 95 is connected to the positive electrode 91, and a negative electrode lead 96 is connected to the negative electrode 92. As described above, the positive electrode lead 95 is welded to the safety valve 84 and electrically connected to the battery lid 83, and the negative electrode lead 96 is welded to and electrically connected to the battery can 81.

  6 shows an enlarged part of the spirally wound electrode body 90 shown in FIG.

  Hereinafter, the positive electrode 91, the negative electrode 92, and the separator 93 will be described in detail.

[Positive electrode]
In the positive electrode 91, a positive electrode active material layer 91B containing a positive electrode active material is formed on both surfaces of the positive electrode current collector 91A. As the positive electrode current collector 91A, for example, a metal foil such as an aluminum (Al) foil, a nickel (Ni) foil, or a stainless steel (SUS) foil can be used.

  The positive electrode active material layer 91 </ b> B is configured to include any one or more of positive electrode materials capable of inserting and extracting lithium as a positive electrode active material. Or other materials such as a conductive agent. The positive electrode active material, the conductive agent, and the binder can be the same as those in the first embodiment.

  The positive electrode 91 has a positive electrode lead 95 connected to one end of the positive electrode current collector 91A by spot welding or ultrasonic welding. The positive electrode lead 95 is preferably a metal foil or a mesh-like one, but there is no problem even if it is not a metal as long as it is electrochemically and chemically stable and can conduct electricity. Examples of the material of the positive electrode lead 95 include aluminum (Al) and nickel (Ni).

[Negative electrode]
The negative electrode 92 has, for example, a structure in which a negative electrode active material layer 92B is provided on both surfaces of a negative electrode current collector 92A having a pair of opposed surfaces. Although not shown, the negative electrode active material layer 92B may be provided only on one surface of the negative electrode current collector 92A. The negative electrode current collector 92A is made of, for example, a metal foil such as a copper foil.

  The negative electrode active material layer 92B includes one or more negative electrode materials capable of occluding and releasing lithium as the negative electrode active material, and the positive electrode active material layer 91B as necessary. Other materials such as a binder and a conductive agent similar to those described above may be included. The negative electrode active material, the conductive agent, and the binder can be the same as those in the first embodiment.

[Separator]
The separator 93 is the same as the separator 55 according to the first embodiment.

[Non-aqueous electrolyte]
The non-aqueous electrolyte is the same as in the first embodiment.

(Internal configuration of non-aqueous electrolyte battery)
Although illustration is omitted, the inside of the nonaqueous electrolyte battery has a configuration similar to the configuration in which the electrolyte layer 56 is omitted from the configuration shown in FIGS. 3A and 3B described in the first embodiment. That is, the negative electrode side impregnation region A, the negative electrode side overcoating region B, and the negative electrode side deep region C are formed. An impregnation region A on the positive electrode side, an overcoat region B on the positive electrode side, and a deep region C on the positive electrode side are formed. Note that the negative electrode side impregnation region A, the negative electrode side overcoating region B, and the negative electrode side deep region C may be formed only on the negative electrode side. The positive electrode side impregnation region A, the positive electrode side overcoating region B, and the positive electrode side deep region C may be formed only on the positive electrode side.

(2-2) Nonaqueous electrolyte battery manufacturing method (positive electrode manufacturing method, negative electrode manufacturing method)
The positive electrode 91 and the negative electrode 92 are produced in the same manner as in the first embodiment.

(Formation of solid particle layer)
Next, a coating material is applied on at least one main surface of both main surfaces of the negative electrode 92 by a coating method or the like, and then the solvent is removed by drying to form a solid particle layer. As the paint, for example, a mixture of solid particles, a binder polymer compound and a solvent can be used. On the outermost surface of the negative electrode active material layer 92B on which the solid particle layer is applied and formed, the solid particles are scraped by the depressions between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer 92B, and the depression on the negative electrode side The particle concentration in the impregnation region A increases. Similarly, a solid particle layer is formed on both main surfaces of the positive electrode 91 by a coating method or the like. On the outermost surface of the positive electrode active material layer 91B on which the solid particle layer is applied and formed, the solid particles are scraped by the depressions between adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer 91B, and the depression on the positive electrode side The particle concentration in the impregnation region A increases. As the solid particles, those adjusted so that the particle diameter D95 of the solid particles is not less than a predetermined magnification of the particle diameter D50 of the active material particles are preferably used. For example, as the solid particles, solid particles having a particle size D95 of 2 / √3-1 times or more of the particle size D50 of the active material particles are added to a part of the solid particles, and the particle size D95 of the solid particles is the particle size D50 of the active material particles. It is preferable to use one adjusted to be 2 / √3-1 times or more. Thereby, it is possible to fill the gap at the bottom of the depression with the solid particles having a larger particle diameter, and to easily scrape the solid particles.

  In addition, when the solid particle layer is applied and formed, the distance between the electrodes can be prevented from being inadvertently widened by scraping excess paint. Further, by scraping the surface of the paint, more solid particles are fed into the recesses between the adjacent active material particles, and the ratio of the overcoat region B is lowered. Thereby, most of the solid particles are concentratedly arranged in the depression-impregnated region, and at least one of the metal salts represented by the formulas (1) to (7) is gathered more in the depression-impregnated region A. Can do.

(Manufacturing method of separator)
Next, a separator 93 is prepared.

(Preparation of non-aqueous electrolyte)
The nonaqueous electrolytic solution is prepared by dissolving an electrolyte salt in a nonaqueous solvent.

(Assembly of non-aqueous electrolyte battery)
A positive electrode lead 95 is attached to the positive electrode current collector 91A by welding or the like, and a negative electrode lead 96 is attached to the negative electrode current collector 92A by welding or the like. Thereafter, the positive electrode 91 and the negative electrode 92 are wound through a separator 93 to form a wound electrode body 90.

  The tip of the positive electrode lead 95 is welded to the safety valve mechanism, and the tip of the negative electrode lead 96 is welded to the battery can 81. Thereafter, the wound surface of the wound electrode body 90 is sandwiched between the pair of insulating plates 82 and 83 and stored in the battery can 81. After the wound electrode body 90 is accommodated in the battery can 81, a non-aqueous electrolyte is injected into the battery can 81 and impregnated in the separator 93. After that, the safety valve mechanism including the battery lid 83 and the safety valve 84 and the heat sensitive resistance element 87 are fixed to the opening end of the battery can 81 by caulking through the gasket 88. Thereby, the nonaqueous electrolyte battery of the present technology shown in FIG. 5 is formed.

  In this non-aqueous electrolyte battery, when charged, for example, lithium ions are released from the positive electrode active material layer 91B and inserted into the negative electrode active material layer 92B through the non-aqueous electrolyte impregnated in the separator 93. When discharging is performed, for example, lithium ions are released from the negative electrode active material layer 92 </ b> B and inserted into the positive electrode active material layer 91 </ b> B through the nonaqueous electrolytic solution impregnated in the separator 93.

[Modification 2-1]
The nonaqueous electrolyte battery according to the second embodiment may be manufactured as follows.

(Preparation of positive and negative electrodes)
First, the positive electrode 91 and the negative electrode 92 are produced in the same manner as in the example of the nonaqueous electrolyte battery.

(Formation of solid particle layer)
Next, a paint is applied on at least one main surface of both main surfaces of the separator 93 by a coating method or the like, and then dried to remove the solvent, thereby forming a solid particle layer. As the paint, for example, a mixture of solid particles, a binder polymer compound and a solvent can be used.

(Assembling of non-aqueous electrolyte battery)
Next, the wound electrode body 90 is formed in the same manner as in the example of the nonaqueous electrolyte battery.

(Warming and pressurization process)
Before the spirally wound electrode body 90 is housed in the battery can 81, the spirally wound electrode body 90 is sealed in a packaging material such as a latex tube and heated under hydrostatic pressure. Thereby, the solid particles are moved to the depressions between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer 92B, and the solid particle concentration in the depression impregnation region A on the negative electrode side is increased. The solid particles are moved to the depressions between adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer 91B, and the solid particle concentration in the depression-impregnated region A on the positive electrode side is increased.

  Subsequent steps can be performed in the same manner as the above-described example to obtain a target nonaqueous electrolytic battery.

3. Third Embodiment In a third embodiment, a rectangular nonaqueous electrolyte battery will be described.

(3-1) Configuration of an Example of Nonaqueous Electrolyte Battery FIG. 7 illustrates an exemplary configuration of a nonaqueous electrolyte battery according to the third embodiment. This non-aqueous electrolyte battery is a so-called square battery, in which the wound electrode body 120 is accommodated in a square outer can 111.

  The nonaqueous electrolyte battery includes a rectangular tube-shaped outer can 111, a wound electrode body 120 that is a power generation element housed in the outer can 111, a battery lid 112 that closes an opening of the outer can 111, and a battery lid The electrode pin 113 is provided at a substantially central portion of 112.

  The outer can 111 is formed, for example, as a hollow, bottomed rectangular tube with a conductive metal such as iron (Fe). The inner surface of the outer can 111 is preferably configured to increase the conductivity of the outer can 111 by, for example, applying nickel plating or applying a conductive paint. Further, the outer peripheral surface of the outer can 111 may be covered with an outer label formed of, for example, a plastic sheet or paper, or may be protected by applying an insulating paint. The battery lid 112 is formed of a conductive metal such as iron (Fe), for example, like the outer can 111.

  The wound electrode body 120 is obtained by laminating a positive electrode and a negative electrode with a separator interposed between them and winding them in an oval shape. Since the positive electrode, the negative electrode, the separator, and the nonaqueous electrolytic solution are the same as those in the first embodiment, detailed description thereof is omitted.

  The wound electrode body 120 having such a configuration is provided with a number of positive terminals 121 connected to the positive current collector and a number of negative terminals connected to the negative current collector. All the positive terminals 121 and the negative terminals are led to one end of the spirally wound electrode body 120 in the axial direction. The positive terminal 121 is connected to the lower end of the electrode pin 113 by fixing means such as welding. The negative electrode terminal is connected to the inner surface of the outer can 111 by fixing means such as welding.

  The electrode pin 113 is made of a conductive shaft member, and is held by an insulator 114 with its head protruding to the upper end. The electrode pin 113 is fixed to a substantially central portion of the battery lid 112 through the insulator 114. The insulator 114 is made of a highly insulating material and is fitted into a through hole 115 provided on the surface side of the battery lid 112. Further, the electrode pin 113 is penetrated through the through hole 115, and the tip end portion of the positive electrode terminal 121 is fixed to the lower end surface thereof.

  The battery lid 112 provided with such electrode pins 113 and the like is fitted in the opening of the outer can 111, and the contact surface between the outer can 111 and the battery lid 112 is joined by a fixing means such as welding. Yes. Thereby, the opening part of the armored can 111 is sealed by the battery cover 112, and is comprised airtight and liquid-tight. The battery lid 112 is provided with an internal pressure release mechanism 116 that breaks a part of the battery lid 112 to release (release) the internal pressure to the outside when the pressure in the outer can 111 rises to a predetermined value or more. ing.

  The internal pressure release mechanism 116 has two first opening grooves 116a (one first opening groove 116a not shown) linearly extending in the longitudinal direction on the inner surface of the battery lid 112, and the same as the battery. The inner surface of the lid 32 includes a second opening groove 116b extending in the width direction orthogonal to the longitudinal direction and having both ends communicating with the two first opening grooves 116a. The two first opening grooves 116a are provided in parallel to each other along the outer edge of the long side of the battery lid 112 in the vicinity of the inner side of the two long sides positioned so as to face the width direction of the battery lid 112. ing. Further, the second opening groove 116 b is provided so as to be positioned at a substantially central portion between one short side outer edge and the electrode pin 113 on one side in the longitudinal direction of the electrode pin 113.

  Both the first opening groove 116a and the second opening groove 116b have, for example, a V shape in which the cross-sectional shape is opened to the lower surface side. Note that the shapes of the first opening groove 116a and the second opening groove 116b are not limited to the V-shape shown in this embodiment. For example, the shapes of the first opening groove 116a and the second opening groove 116b may be U-shaped or semicircular.

  The electrolyte injection port 117 is provided so as to penetrate the battery lid 112. The electrolyte injection port 117 is used to inject the non-aqueous electrolyte after the battery lid 112 and the outer can 111 are caulked, and is sealed by the sealing member 118 after the non-aqueous electrolyte is injected. The For this reason, when forming a wound electrode body by previously forming a gel electrolyte between the positive electrode, the negative electrode, and the separator, the electrolyte solution inlet 117 and the sealing member 118 may not be provided.

[Separator]
As the separator, the same separator as in the first embodiment is used.

[Non-aqueous electrolyte]
The non-aqueous electrolyte is the same as in the first embodiment.

(Internal configuration of non-aqueous electrolyte battery)
Although not shown, the inside of the nonaqueous electrolyte battery has a configuration similar to the configuration in which the electrolyte layer 56 is omitted from the configuration shown in FIGS. 3A and 3B described in the first embodiment. That is, the negative electrode side impregnation region A, the negative electrode side overcoating region B, and the negative electrode side deep region C are formed. An impregnation region A on the positive electrode side, an overcoat region B on the positive electrode side, and a deep region C on the positive electrode side are formed. The impregnation region A, the overcoating region B, and the deep region C on the negative electrode side may be formed only on the negative electrode side. The positive electrode side impregnation region A, the positive electrode side overcoating region B, and the positive electrode side deep region C may be formed only on the positive electrode side.

(3-2) Manufacturing Method of Nonaqueous Electrolyte Battery This nonaqueous electrolyte battery can be manufactured as follows, for example.

[Method for producing positive electrode and negative electrode]
The positive electrode and the negative electrode can be produced by the same method as in the third embodiment.
(Formation of solid particle layer)
Next, a paint is applied on at least one main surface of both main surfaces of the negative electrode by a coating method or the like, and then the solvent is removed by drying to form a solid particle layer. As the paint, for example, a mixture of solid particles, a binder polymer compound and a solvent can be used. On the outermost surface of the negative electrode active material layer on which the solid particle layer is applied and formed, the solid particles are scraped by the dents between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer, and the dent impregnation region on the negative electrode side The particle concentration of A increases. Similarly, a solid particle layer is formed on both main surfaces of the positive electrode by a coating method or the like. On the outermost surface of the positive electrode active material layer on which the solid particle layer is applied and formed, the solid particles are rubbed by the dents between adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer, and the dent impregnation region on the positive electrode side The particle concentration of A increases. As the solid particles, those adjusted so that the particle diameter D95 of the solid particles is not less than a predetermined magnification of the particle diameter D50 of the active material particles are preferably used. For example, as the solid particles, solid particles having a particle size D95 of 2 / √3-1 times or more of the particle size D50 of the active material particles are added to a part of the solid particles, and the particle size D95 of the solid particles is the particle size D50 of the active material particles. It is preferable to use one adjusted to be 2 / √3-1 times or more. Thereby, it is possible to fill the gap at the bottom of the depression with the solid particles having a larger particle diameter, and to easily scrape the solid particles. In addition, when the solid particle layer is applied and formed, the distance between the electrodes can be prevented from being inadvertently widened by scraping excess paint. Further, by scraping the surface of the paint, more solid particles can be arranged in the depressions between adjacent active material particles, and the ratio of the particles in the topcoat region B is lowered. As a result, most of the solid particles are intensively arranged in the depression impregnation region A, and at least one of the metal salts represented by the formulas (1) to (7) is concentrated in the depression impregnation region A. can do.

(Assembly of non-aqueous electrolyte battery)
A positive electrode, a negative electrode, and a separator (having a particle-containing resin layer formed on at least one surface of a base material) are sequentially laminated and wound to produce a wound electrode body 120 that is wound in an oblong shape. Subsequently, the wound electrode body 120 is accommodated in the outer can 111.

  And the electrode pin 113 provided in the battery cover 112 and the positive electrode terminal 121 derived | led-out from the winding electrode body 120 are connected. Although not shown, the negative electrode terminal led out from the wound electrode body 120 and the battery can are connected. Thereafter, the outer can 111 and the battery lid 112 are fitted, and for example, a non-aqueous electrolyte is injected from the electrolyte injection port 117 under reduced pressure, and the sealing member 118 is sealed. As described above, a nonaqueous electrolyte battery can be obtained.

[Modification 3-1]
The nonaqueous electrolyte battery according to the third embodiment may be manufactured as follows.

(Preparation of positive and negative electrodes)
First, a positive electrode and a negative electrode are produced in the same manner as in the example of the nonaqueous electrolyte battery.

(Formation of solid particle layer)
Next, a coating material is applied on at least one main surface of both main surfaces of the separator by a coating method or the like, and then the solvent is removed by drying to form a solid particle layer. As the paint, for example, a mixture of solid particles, a binder polymer compound and a solvent can be used.

(Assembling of non-aqueous electrolyte battery)
Next, the wound electrode body 120 is formed in the same manner as in the example of the nonaqueous electrolyte battery. Next, before the wound electrode body 120 is accommodated in the outer can 111, the wound electrode body 120 is sealed in a packaging material such as a latex tube and heated under hydrostatic pressure. As a result, the solid particles are moved (pushed) into the depressions between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer, and the solid particle concentration in the depression-impregnated region A on the negative electrode side is increased. The solid particles are moved to the depressions between adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer, and the solid particle concentration in the depression-impregnated region A on the positive electrode side is increased.

  Thereafter, the target nonaqueous electrolytic battery can be obtained in the same manner as the above-described example.

4). Fourth Embodiment FIG. 8 shows a perspective configuration of a battery pack using a single battery, and FIG. 9 shows a block configuration of the battery pack shown in FIG. In addition, in FIG. 8, the state which decomposed | disassembled the battery pack is shown.

  The battery pack described here is a simple battery pack (so-called soft pack) using one secondary battery, and is incorporated in, for example, an electronic device typified by a smartphone. For example, as shown in FIG. 9, the battery pack includes a power source 211 that is a laminated film type secondary battery having the same configuration as that of the first embodiment, and a circuit board 216 connected to the power source 211. And.

  A pair of adhesive tapes 218 and 219 are attached to both side surfaces of the power source 211. On the circuit board 216, a protection circuit (PCM: Protection Circuit Circuit Module) is formed. The circuit board 216 is connected to the positive lead 212 and the negative lead 213 of the power supply 211 via a pair of tabs 214 and 215 and is connected to a lead wire 217 with a connector for external connection. In the state where the circuit board 216 is connected to the power supply 211, the circuit board 216 is protected from above and below by the label 220 and the insulating sheet 231. By attaching the label 220, the circuit board 216, the insulating sheet 231 and the like are fixed.

  Further, the battery pack includes a power source 211 and a circuit board 216 as shown in FIG. 9, for example. The circuit board 216 includes, for example, a control unit 221, a switch unit 222, a PTC 223, and a temperature detection unit 224. Since the power source 211 can be connected to the outside through the positive terminal 225 and the negative terminal 227, the power source 211 is charged / discharged through the positive terminal 225 and the negative terminal 227. The temperature detection unit 224 can detect the temperature using a temperature detection terminal (so-called T terminal) 226.

  The control unit 221 controls the operation of the entire battery pack (including the usage state of the power supply 211), and includes, for example, a central processing unit (CPU) and a memory.

  For example, when the battery voltage reaches the overcharge detection voltage, the control unit 221 disconnects the switch unit 222 to prevent the charging current from flowing through the current path of the power supply 211. For example, when a large current flows during charging, the control unit 221 disconnects the charging current by cutting the switch unit 222.

  In addition, for example, when the battery voltage reaches the overdischarge detection voltage, the control unit 221 disconnects the switch unit 222 to prevent the discharge current from flowing through the current path of the power supply 211. For example, when a large current flows during discharge, the control unit 221 cuts off the discharge current by cutting the switch unit 222.

  The overcharge detection voltage of the secondary battery is, for example, 4.20V ± 0.05V, and the overdischarge detection voltage is, for example, 2.4V ± 0.1V.

  The switch unit 222 switches the usage state of the power source 211 (whether the power source 211 can be connected to an external device) in accordance with an instruction from the control unit 221. The switch unit 222 includes, for example, a charge control switch and a discharge control switch. The charge control switch and the discharge control switch are semiconductor switches such as a field effect transistor (MOSFET) using a metal oxide semiconductor, for example. The charging / discharging current is detected based on the ON resistance of the switch unit 222, for example.

  The temperature detection unit 224 measures the temperature of the power supply 211 and outputs the measurement result to the control unit 221. For example, the temperature detection unit 224 includes a temperature detection element such as a thermistor. The measurement result by the temperature detection unit 224 is used when the control unit 221 performs charge / discharge control during abnormal heat generation or when the control unit 221 performs correction processing when calculating the remaining capacity.

  The circuit board 216 may not include the PTC 223. In this case, a PTC element may be attached to the circuit board 216 separately.

5). Fifth Embodiment FIG. 10 is a block diagram illustrating a circuit configuration example when the batteries according to the first to third embodiments of the present technology (hereinafter, appropriately referred to as secondary batteries) are applied to a battery pack. FIG. 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.

  The battery pack also includes a positive electrode terminal 321 and a negative electrode lead 322, and charging is performed by connecting the positive electrode terminal 321 and the negative electrode lead 322 to the positive electrode terminal and the negative electrode terminal of the charger, respectively, during charging. Further, when the electronic device is used, the positive electrode terminal 321 and the negative electrode lead 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 addition, in FIG. 10, although the case where the six secondary batteries 301a are connected to 2 parallel 3 series (2P3S) is shown as an example, other 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 electrode terminal 321 in the direction of the assembled battery 301 and the forward polarity with respect to the discharging current flowing from the negative electrode lead 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 unit 304 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 charging control switch 302a is turned off, only discharging is possible via 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 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, 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.

<6. Sixth Embodiment>
The batteries according to the first to third embodiments and the battery packs according to the fourth to fifth embodiments of the present technology described above are, for example, devices such as electronic devices, electric vehicles, and power storage devices. Can be used to mount or power.

  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.

  Further, 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 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 is supplied with power 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.

  Furthermore, 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.

(6-1) Residential Power Storage System as an Application Example An example in which a power storage device using a battery of the present technology is applied to a residential power storage system 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 power generation device 404 in the home. 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 battery of the present technology is applied to the power storage device 403. The battery of the present technology may be configured 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 apparatus 410 can transmit the information regarding the house 401 to an external electric power company etc. via the internet.

  The power hub 408 performs processing such as branching of the power line and DC / AC conversion. Communication methods of the information network 412 connected to the control device 410 include 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 domestic 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 to do. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.

  As described above, not only the centralized power system 402 such as the thermal power generation 402a, the nuclear power generation 402b, and the hydroelectric power generation 402c but also the power generation device 404 (solar power generation, wind power generation) in the home is used as the power storage device 403. Can be stored. Therefore, even if the generated power of the power generation device 404 in the home fluctuates, it is possible to perform control such that the amount of power transmitted to the outside is constant or discharge is performed 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.

(6-2) 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. 12 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 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 apparatus 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 battery remaining amount based on information on the remaining amount of the battery.

  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, the present technology will be described in detail by way of examples. In addition, this technique is not limited to the structure of the following Example.

<Example 1-1>
[Production of positive electrode]
91% by mass of lithium cobaltate (LiCoO ₂ ) particles (particle diameter D50: 10 μm) as a positive electrode active material, 6% by mass of carbon black as a conductive agent, and 3% by mass of polyvinylidene fluoride (PVdF) as a binder To prepare a positive electrode mixture, and this positive electrode mixture was dispersed in N-methyl-2-pyrrolidone (NMP) as a dispersion medium to obtain a positive electrode mixture slurry.

This positive electrode mixture slurry was applied to both surfaces of a positive electrode current collector made of a strip-shaped aluminum foil having a thickness of 12 μm so that a part of the positive electrode current collector was exposed. Thereafter, the dispersion medium of the applied positive electrode mixture slurry was evaporated and dried, and compression-molded with a roll press to form a positive electrode active material layer. Finally, the positive electrode terminal was attached to the exposed portion of the positive electrode current collector to form the positive electrode. The area density of the positive electrode active material layer was adjusted to 30 mg / cm ² .

[Production of negative electrode]
96% by mass of granular graphite particles (particle diameter D50: 20 μm) as a negative electrode active material, 1.5% by mass of an acrylic acid-modified product of a styrene-butadiene copolymer as a binder, and carboxymethylcellulose as a thickener. 5% by mass was mixed to obtain a negative electrode mixture, and an appropriate amount of water was further added and stirred to prepare a negative electrode mixture slurry.

This negative electrode mixture slurry was applied to both sides of a negative electrode current collector made of a strip-shaped copper foil having a thickness of 15 μm so that a part of the negative electrode current collector was exposed. Then, the dispersion medium of the apply | coated negative mix slurry was evaporated and dried, and the negative electrode active material layer was formed by compression molding with a roll press. Finally, the negative electrode terminal was attached to the exposed portion of the positive electrode current collector to form a negative electrode. The area density of the negative electrode active material layer was adjusted to 15 mg / cm ² .

[Preparation of separator]
As a separator, a polyethylene (PE) microporous film (polyethylene separator) having a thickness of 5 μm was prepared.

[Formation of electrolyte layer]
For a non-aqueous solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed, as an electrolyte salt, a compound (addition component) represented by the formula (5-1) and lithium hexafluorophosphate (LiPF) ₆ ) was dissolved, thereby preparing a non-aqueous electrolyte. The composition of the non-aqueous electrolyte was adjusted to EC / DEC / compound represented by formula (5-1) / LiPF ₆ = 20/70 / 0.1 / 9.9 by mass ratio. Content of the compound represented by Formula (5-1) of this non-aqueous electrolyte is a mass percentage with respect to the whole quantity of a non-aqueous electrolyte, and is 0.1 mass%.

  Subsequently, polyvinylidene fluoride (PVdF) is used as the matrix polymer compound (resin) for holding the non-aqueous electrolyte, the non-aqueous electrolyte, polyvinylidene fluoride, and dimethyl carbonate (DMC: dimethyl carbonate) as a diluting solvent. Then, boehmite particles (particle diameter D50: 1 μm) were mixed as solid particles to prepare a sol coating solution. The composition of the coating solution is 10% by mass of solid particles, 5% by mass of resin, 35% by mass of non-aqueous electrolyte, and 50% by mass of diluting solvent with respect to the total amount of the coating solution.

Subsequently, the coating solution is applied to both the positive electrode and the negative electrode in a heated state, dried to remove the diluting solvent (DMC), and the surface density of the positive electrode and the negative electrode is 3 mg / cm ² per side. The electrolyte layer was formed. By applying the coating solution in a heated state, the electrolyte containing the boehmite particles that are solid particles can be infiltrated into the recesses between adjacent active material particles located on the outermost surface of the negative electrode active material layer or inside the active material layer. it can. At this time, the solid particles are rubbed in the depressions between adjacent particles, so that the particle concentration in the depression area A on the negative electrode side increases. Thereby, a difference can be provided in the particle | grain density | concentration of the hollow area A and the deep area C. By scraping a part of the coating solution, the thickness of the recess impregnation region A and the top coating region B is adjusted to those shown in Table 1, and more solid particles are fed into the recess impregnation region A. Remained in the depression-impregnated region A. In addition, as a solid particle, the solid particle more than 2 / √3-1 times the particle diameter D50 of the negative electrode active material is added to a part of the solid particle, and the particle diameter D95 of the solid particle is the particle diameter of the negative electrode active material particle. What was prepared so that it might become 2 / √3-1 times or more (3.5 μm) of D50 was used. Thus, the solid particles can be easily scraped by filling the gaps between the particles at the bottom of the depression with some solid particles having a larger particle diameter.

[Assembly of laminated film type battery]
A positive electrode and a negative electrode having electrolyte layers formed on both sides and a separator were laminated in the order of the positive electrode, the separator, the negative electrode, and the separator, and then wound in a flat shape many times in the longitudinal direction. Then, the winding electrode part was formed by fixing a winding end part with an adhesive tape.

  Next, the wound electrode body is covered with a laminate film having a soft aluminum layer, and the lead-out side of the positive electrode terminal and the negative electrode terminal around the wound electrode body and the other two sides are thermally fused under reduced pressure. Sealed and sealed. Thus, a laminated film type battery shown in FIG. 1 having a battery shape of 4.5 mm in thickness, 30 mm in width, and 50 mm in height was produced.

<Example 1-2> to <Example 1-57>
In Example 1-2 to Example 1-57, as shown in Table 1 below, a laminate film type battery was produced in the same manner as in Example 1-1 except that the particles used were changed.

<Example 1-58>
In Example 1-58, when preparing a coating solution to be applied to the negative electrode, the content of solid particles was reduced to 7% by mass, and the amount of solid particles decreased DMC was increased except that Example 1- In the same manner as in Example 1, a laminate film type battery was produced.

<Example 1-59>
In Example 1-59, when preparing a coating solution to be applied to the negative electrode, Example 1- 1 except that the content of solid particles was increased to 18% by mass and the amount of increase in solid particles DMC was reduced. In the same manner as in Example 1, a laminate film type battery was produced.

<Example 1-60>
In Example 1-59, when preparing a coating solution to be applied to the negative electrode, Example 1- 1 except that the content of solid particles was increased to 20% by mass and the amount of increase in solid particles DMC was reduced. In the same manner as in Example 1, a laminate film type battery was produced.

<Example 1-61>
In Example 1-61, a laminate film type battery was produced in the same manner as in Example 1-1 except that when the gel electrolyte layer was formed on the negative electrode, it was weakened to scrape off the coating solution.

<Example 1-62>
In Example 1-62, as solid particles, solid particles having a particle diameter D50 of 2 / √3-1 of the negative electrode active material are added to a part of the solid particles, and the particle size D95 of the solid particles is the negative electrode active material particle size. What was prepared to become 2 / √3-1 times (3.1 μm) of the particle diameter D50 was used. Except for the above, a laminate film type battery was produced in the same manner as in Example 1-1.

<Comparative Example 1-1>
A laminate film type battery was produced in the same manner as in Example 1-1 except that the compound represented by the formula (5-1) was not added to the nonaqueous electrolytic solution.

<Comparative Example 1-2>
A laminated film type battery in the same manner as in Example 1-1 except that 1% by mass of vinyl ethylene carbonate (VEC) was added to the non-aqueous electrolyte instead of the compound represented by the formula (5-1). Was made.

<Comparative Example 1-3>
A laminated film type battery was produced in the same manner as in Example 1-1 except that the boehmite particles were not added to the coating solution.

<Comparative Example 1-4>
Instead of forming a gel electrolyte layer on the electrode, a laminate film type battery was produced in the same manner as in Example 1-1 except that a gel electrolyte layer was formed on both main surfaces of the separator. did. In this example, since most of the solid particles contained in the electrolyte layer formed on the surface of the separator do not enter the recesses between adjacent active material particles located on the outermost surface of the active material layer, the recess impregnation region A The solid particle concentration of is low.

<Comparative Example 1-5>
No boehmite particles were added to the coating solution. The compound represented by Formula (5-1) was not added to the nonaqueous electrolytic solution. Except for the above, a laminate film type battery was produced in the same manner as in Example 1-1.

(Measurement of particle diameter of particles, measurement of BET specific surface area)
In the above-mentioned Examples and Comparative Examples, the particle diameter and the BET specific surface area of the particles are measured or evaluated as follows. (The same applies to Examples described later)

(Measurement of particle diameter)
In the particle size distribution measured by the laser diffraction method for the solid particles after removing the electrolyte components and the like from the electrolyte layer, the particle size of 50% cumulative volume calculated from the particle side of the small particle size is defined as the particle size D50 of the particles. . In addition, the value of the particle diameter D95 of 95% of the cumulative volume was obtained from the measured particle size distribution as necessary. Similarly, the active material particles were measured in the same manner for particles obtained by removing components other than the active material from the active material layer.

(Measurement of BET specific surface area)
The BET specific surface area was calculated | required about the solid particle after removing an electrolyte component etc. from an electrolyte layer using the BET specific surface area measuring apparatus.

(Measurement of solid particle concentration and recess impregnation region A, topcoat region B, and deep region C)
Using SEM, four observations were made in an observation field with a field width of 50 μm. In each observation field, each thickness of the impregnation region A, the overcoating region B, and the deep region C and the particle concentration in each region were measured. For each observation field of 2 μm × 2 μm in each region, the particle concentration was obtained by calculating the area percentage of the total area of the particle cross section ((“total area of the particle cross section” ÷ “area of the observation field”) × 100%). .

(Battery evaluation: Overcharge limit test)
The following overcharge limit tests were performed on each of the fabricated batteries. After 5 hours of constant current / constant voltage charging at 1 A / 4.2 V, charging corresponding to 50% of capacity (30 minutes) is added at a constant current of 1 A. A battery that can maintain the voltage without causing an internal short circuit is accepted, and additional charging is performed up to 150% in increments of 50%. A battery that cannot maintain the voltage due to an internal short circuit does not perform additional charging. In additional charging, those that could not reach 50% (overcharge resistance test limit capacity <150%) failed, those that could reach 50% (150% ≤ overcharge resistance test limit capacity <200%) are acceptable Those that could reach 100% (200% ≦ overcharge resistance test limit capacity <250%) were good, and those that could reach 150% (250% ≦ overcharge resistance test limit capacity) were excellent. In the table, more than 250% means more than 250%.

  Table 1 shows the evaluation results.

  As shown in Table 1, in Example 1-1 to Example 1-62, the solid particles were arranged at an appropriate concentration in an appropriate region inside the battery, so that the overcharge resistance was excellent.

<Example 2-20>
A laminated film type battery was produced in the same manner as Example 1-1.

<Example 2-1 to Example 2-19, Example 2-21 to Example 2-24>
In Example 2-1 to Example 2-19 and Example 2-21 to Example 2-24, instead of the compound represented by the formula (5-1) as the electrolyte salt when forming the electrolyte layer, A laminated film type battery was produced in the same manner as in Example 2-20 except that the compounds shown in Table 2 below were added.

(Battery evaluation: Overcharge limit test)
About the produced laminate film type battery of each Example, it carried out similarly to Example 1-1, and performed the overcharge limit test.

  Table 2 shows the evaluation results.

  As shown in Table 2, in Example 2-1 to Example 2-24, the solid particles were arranged at an appropriate concentration in an appropriate region inside the battery, so that the overcharge resistance was excellent.

<Example 3-1 to Example 3-9>
Example 3-1 to Example 3-9 were the same as Example 1-1 except that the amount of the compound represented by formula (5-1) was changed as shown in Table 3 below. Thus, a laminate film type battery was produced.

<Comparative Example 3-1>
A laminated film type battery was produced in the same manner as in Example 3-9, except that the boehmite particles were not added to the coating solution.

(Battery evaluation: Overcharge limit test)
About the produced laminate film type battery of each Example, it carried out similarly to Example 1-1, and performed the overcharge limit test.

(Battery evaluation: charge / discharge cycle test)
The following charging / discharging cycle test was done about the produced laminate film type battery of each Example. After performing constant current and constant voltage charging at 23 ° C. with a charging voltage of 4.2 V and 1 A until the total charging time reaches 5 hours, constant current discharging to 3.0 V with a constant current of 0.5 A went. The discharge capacity at this time was defined as the initial capacity of the battery. Thereafter, charging / discharging was repeated 500 times under the same conditions, and [discharge capacity at 500th cycle / initial discharge capacity] × 100 (%) was determined as a capacity retention rate.
The determination was made as follows according to the capacity retention rate.
Fail: Less than 40% Possible: 40% or more and less than 50% Good: 50% or more and less than 60% Excellent: 60% or more and 100% or less

  Table 3 shows the evaluation results.

  As shown in Table 3, in Example 3-1 to Example 3-9, the solid particles were arranged at an appropriate concentration in an appropriate region inside the battery, so that the overcharge resistance was excellent.

<Example 4-1 to Example 4-9>
In Example 4-1 to Example 4-9, a laminated film type battery was manufactured in the same manner as in Example 1-1 except that the amount of solid particles added to the electrolyte was changed as shown in Table 4 below. Produced.

(Battery evaluation: Overcharge limit test)
About the produced laminate film type battery of each Example, it carried out similarly to Example 1-1, and performed the overcharge limit test.

  Table 4 shows the evaluation results.

  As shown in Table 4, in Example 4-1 to Example 4-9, the solid particles were arranged at an appropriate concentration in an appropriate region inside the battery, so that the overcharge resistance was excellent.

<Example 5-1 to Example 5-11>
In Example 5-1 to Example 5-11, the same procedure as in Example 1-1 was performed except that the particle size and specific surface area of boehmite particles, which were solid particles, were changed as shown in Table 5 below. A laminated film type battery was produced.

(Battery evaluation: Overcharge limit test)
About the produced laminate film type battery of each Example, it carried out similarly to Example 1-1, and performed the overcharge limit test.

  Table 5 shows the evaluation results.

  As shown in Table 5, in Example 5-1 to Example 5-11, the solid particles were arranged at an appropriate concentration in an appropriate region inside the battery, and thus the overcharge resistance was excellent.

<Example 6-1>
A laminated film type battery was produced in the same manner as Example 1-1.

<Example 6-2>
First, a positive electrode and a negative electrode were produced in the same manner as in Example 6-1, and a separator was prepared.

  Next, in the same manner as in Example 1-1, the same coating solution as in Example 1-1 was applied to both sides of the separator, dried to remove the diluted solvent, and a gel electrolyte layer was formed on the surface of the separator. Formed.

  Thereafter, the positive electrode and the negative electrode and the separator on which the gel electrolyte layer was formed on both sides were laminated in the order of the positive electrode, the separator, the negative electrode, and the separator, and then wound many times in the longitudinal direction into a flat shape. Then, the winding electrode part was formed by fixing a winding end part with an adhesive tape.

  Next, the wound electrode body was packed in a bag and subjected to isostatic pressing. As a result, the solid particles were pushed into the depressions between the adjacent positive electrode active material particles on the outermost surface of the positive electrode active material layer and the depressions between the adjacent negative electrode active material particles on the outermost surface of the negative electrode active material layer.

  Thereafter, the wound electrode body is covered with a laminate film having a soft aluminum layer, and the lead-out side of the positive electrode terminal and the negative electrode terminal around the wound electrode body and the other two sides are heat-sealed under reduced pressure and sealed. Stopped and sealed. Thus, a laminated film type battery shown in FIG. 1 having a battery shape of 4.5 mm in thickness, 30 mm in width, and 50 mm in height was produced.

<Example 6-3>
First, a positive electrode and a negative electrode were produced in the same manner as in Example 6-1, and a separator was prepared.

(Formation of solid particle layer)
Next, a coating material prepared by mixing 22% by mass of solid particles, 3% by mass of PVdF as a binder polymer compound, and 75% by mass of NMP as a solvent was applied to both surfaces of the separator, and then the solvent was removed by drying. Thereby, the solid particle layer was formed so that the solid content was 0.5 mg / cm ² per side.

  Next, the positive electrode, the negative electrode, and the separator having the solid particle layer formed on both surfaces were laminated in the order of the positive electrode, the separator, the negative electrode, and the separator, and then wound in a flat shape many times in the longitudinal direction. Then, the winding body was formed by fixing the winding end part with an adhesive tape.

  Next, a wound electric body packed in a bag of warmed oil was put in and hydrostatic press was performed. Thus, the solid particles are pushed into the depressions between adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer and the depressions between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer. .

  Next, this wound body was sandwiched between laminate films having a soft aluminum layer, and the outer peripheral edge except one side was heat-sealed to form a bag shape, which was stored inside the laminate film. Next, a non-aqueous electrolyte was poured into the exterior member, and the wound body was impregnated with the non-aqueous electrolyte, and then the opening of the laminate film was heat-sealed in a vacuum atmosphere and sealed. Thus, a laminated film type battery shown in FIG. 1 having a battery shape of 4.5 mm in thickness, 30 mm in width, and 50 mm in height was produced.

<Example 6-4>
A positive electrode and a negative electrode were produced in the same manner as in Example 6-1, and a separator was prepared.

  After applying the coating solution on both sides of the separator as described below, this was dried to form a matrix resin layer.

  First, boehmite particles and polyvinylidene fluoride (PVdF) as a matrix polymer compound were dispersed in N-methyl-2-pyrrolidone (NMP) to prepare a coating solution. At this time, the content of boehmite particles is 10% by mass with respect to the total amount of paint, the content of PVdF is 10% by mass with respect to the total amount of paint, and the content of NMP is with respect to the total amount of paint. 80% by mass.

  Next, this coating solution was applied to both sides of the separator, and then passed through a drier to remove NMP, thereby obtaining a separator on which a matrix resin layer was formed.

[Assembly of laminated film type battery]
Next, the positive electrode, the negative electrode, and the separator on which the matrix resin layer is formed on both sides are laminated in the order of the positive electrode, the separator, the negative electrode, and the separator, wound many times in the longitudinal direction into a flat shape, A wound electrode body was formed by fixing with an adhesive tape.

  Next, a wound electrode body packed in warmed oil was put in and hydrostatic pressure press was performed. Thereby, the solid particles were pushed into the depression on the outermost surface of the positive electrode active material layer and the depression on the outermost surface of the negative electrode active material layer.

  Next, the wound electrode body was sandwiched between the exterior members, and the three sides were heat-sealed. Note that a laminate film having a soft aluminum layer was used for the exterior member.

  After that, an electrolytic solution was poured into this, and the remaining one side was heat-sealed under reduced pressure and sealed. At this time, the electrolyte solution was impregnated into the particle-containing resin layer, and the matrix polymer compound was swollen to form a gel electrolyte (gel electrolyte layer). As the electrolytic solution, the same one as in Example 1-1 was used. Thus, a laminated film type battery shown in FIG. 1 having a thickness of 4.5 mm, a width of 30 mm, and a height of 50 mm was produced.

<Example 6-5>
First, a positive electrode and a negative electrode were produced in the same manner as in Example 6-1, and a separator was prepared.

(Formation of solid particle layer)
A coating prepared by mixing 22% by mass of solid particles, 3% by mass of PVdF as a binder polymer compound, and 75% by mass of NMP as a solvent was applied to both surfaces of the positive electrode and the negative electrode, and then the surface was scraped. As a result, solid particles were put into the respective depression-impregnated areas A on the positive electrode side and the negative electrode side, and the thickness of the depression-impregnated area A was set to be twice or more the thickness of the topcoat area B. Thereafter, NMP was removed by drying, and a solid particle layer was formed so that the solid content was 0.5 mg / cm ^{2 on} one side.

  Next, the positive electrode and the negative electrode on which the solid particle layers were formed on both surfaces, and the separator were laminated in the order of the positive electrode, the separator, the negative electrode, and the separator, and then wound many times in the longitudinal direction into a flat shape. Then, the winding body was formed by fixing the winding end part with an adhesive tape.

Next, this wound body was sandwiched between laminate films having a soft aluminum layer, and the outer peripheral edge except one side was heat-sealed to form a bag shape, which was stored inside the laminate film. Next, a non-aqueous electrolyte was poured into the exterior member, and the wound body was impregnated with the non-aqueous electrolyte, and then the opening of the laminate film was heat-sealed in a vacuum atmosphere and sealed. Thus, a laminated film type battery shown in FIG. 1 having a battery shape of 4.5 mm in thickness, 30 mm in width, and 50 mm in height was produced.
<Example 6-6>
A laminated film type battery was produced in the same manner as in Example 6-1 except that the gel electrolyte layer was formed only on both sides of the positive electrode.

<Example 6-7>
A laminated film type battery was produced in the same manner as in Example 6-1 except that the gel electrolyte layer was formed only on both sides of the negative electrode.

(Battery evaluation: Overcharge limit test)
About the produced laminate film type battery of each Example, it carried out similarly to Example 1-1, and performed the overcharge limit test.

  Table 6 shows the evaluation results.

  As shown in Table 6, in Example 6-1 to Example 6-7, the solid particles were arranged at an appropriate concentration in an appropriate region inside the battery, and thus the overcharge resistance was excellent.

<Example 7-1>
A rectangular positive electrode, a rectangular negative electrode, and a rectangular separator having the same configuration as in Example 1-1 except that the rectangular separator was used.

(Formation of solid particle layer)
Next, a solid particle layer was formed on both sides of the separator in the same manner as in Example 6-3.

(Formation of laminated electrode body)
Next, a positive electrode, a separator, a negative electrode, and a separator were laminated in this order to form a laminated electrode body.

  Next, the laminated electrode body packaged in warmed oil was placed and subjected to isostatic pressing. Thereby, the solid particles were pushed into the depression on the outermost surface of the positive electrode active material layer and the depression on the outermost surface of the negative electrode active material.

  Next, the laminated electrode body was covered with a laminate film having a soft aluminum layer, and three sides around the laminated electrode body were heat-sealed and sealed, and sealed. After that, the same electrolytic solution as in Example 1-1 was poured into this, and the remaining one side was thermally fused and sealed under reduced pressure. Thereby, the laminated film type battery shown in FIGS. 4A to 4C having a battery shape of 4.5 mm in thickness, 30 mm in width, and 50 mm in height was manufactured.

<Example 7-2>
In the same manner as in Example 6-1, a laminated electrode body was formed, and the laminated electrode body packed in warmed oil was put in and hydrostatic press was performed. As a result, it was pushed into the depression on the outermost surface of the positive electrode active material layer and the depression on the outermost surface of the negative electrode active material.

  Next, the positive terminal was joined to a safety valve joined to the battery lid, and the negative terminal was connected to the negative can. The laminated electrode body was sandwiched between a pair of insulating plates and housed inside the battery can.

  Subsequently, a non-aqueous electrolyte was injected into the cylindrical battery can from above the insulating plate. Finally, the battery lid was sealed by caulking the open part of the battery can via an insulating sealing gasket. Thereby, a cylindrical battery having a battery shape of 18 mm in diameter and 65 mm in height (ICR18650 size) was produced.

<Example 7-3>
In the same manner as in Example 7-1, a laminated electrode body was formed, and the laminated electrode body packaged in warmed oil was put in and subjected to isostatic pressing. As a result, it was pushed into the depression on the outermost surface of the positive electrode active material layer and the depression on the outermost surface of the negative electrode active material.

[Assembly of square battery]
Next, the laminated electrode body was accommodated in a rectangular battery can. Subsequently, after connecting the electrode pin provided on the battery lid and the positive electrode terminal derived from the laminated electrode body, the battery can is sealed with the battery lid, and the non-aqueous electrolyte is injected from the electrolyte inlet. Sealed with a sealing member and sealed. As a result, a rectangular battery having a thickness of 4.5 mm, a width of 30 mm, and a height of 50 mm (453050 size) was produced.

<Example 7-4 to Example 7-6>
Instead of the polyethylene separator, a non-woven fabric was prepared, and the same application solution as in Example 7-1 was applied to both sides of the non-woven fabric, and then the solvent was removed by drying, whereby the solid content was 0.5 mg / cm per side. ^A solid particle layer was formed to be ² . Except for the above, a laminate film type battery was produced in the same manner as in Example 7-1 to Example 7-3.

<Example 7-7>
In Example 7-7, a simple battery pack (soft pack) shown in FIGS. 8 and 9 using a laminate film type battery similar to that in Example 1-1 was produced.

(Battery evaluation: Overcharge limit test)
About the produced laminate film type battery of each Example, it carried out similarly to Example 1-1, and performed the overcharge limit test. In Example 7-7, the voltage is adjusted assuming the voltage actually applied to the battery included in the battery pack.

  Table 7 shows the evaluation results.

  As shown in Table 7, in Example 7-1 to Example 7-7, the solid particles were arranged at an appropriate concentration in an appropriate region inside the battery, so that the overcharge resistance was excellent.

7). Other Embodiments The present technology has been described above with reference to the embodiments and examples. However, the present technology is not limited thereto, and various modifications can be made within the scope of the gist of the present technology.

  For example, the numerical values, structures, shapes, materials, raw materials, manufacturing processes and the like given in the above-described embodiments and examples are merely examples, and different numerical values, structures, shapes, materials, raw materials, and the like as necessary. A manufacturing process or the like may be used.

  The configurations, methods, processes, shapes, materials, numerical values, and the like of the above-described embodiments and examples can be combined with each other without departing from the gist of the present technology. For example, the nonaqueous electrolyte battery may be a primary battery.

  In addition, the electrolyte layer of the present technology can be similarly applied to a case of having another battery structure such as a coin type or a button type. In the second to third embodiments, a stacked electrode body may be used instead of the wound electrode body.

（式中、Ｘ３１は長周期型周期表における１族元素または２族元素、またはＡｌである。Ｍ３１は遷移金属、または長周期型周期表における１３族元素、１４族元素または１５族元素である。Ｒ７１はハロゲン基である。Ｙ３１は−Ｃ（＝Ｏ）−Ｒ７２−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＣＲ７３₂−、または−Ｃ（＝Ｏ）−Ｃ（＝Ｏ）−である。ただし、Ｒ７２はアルキレン基、ハロゲン化アルキレン基、アリーレン基またはハロゲン化アリーレン基である。Ｒ７３はアルキル基、ハロゲン化アルキル基、アリール基またはハロゲン化アリール基である。なお、ａ３は１〜４の整数であり、ｂ３は０、２または４の整数であり、ｃ３、ｄ３、ｍ３およびｎ３は１〜３の整数である。）

（式中、Ｘ４１は長周期型周期表における１族元素または２族元素である。Ｍ４１は遷移金属、または長周期型周期表における１３族元素、１４族元素または１５族元素である。Ｙ４１は−Ｃ（＝Ｏ）−（ＣＲ８１₂）_b4−Ｃ（＝Ｏ）−、−Ｒ８３₂Ｃ−（ＣＲ８２₂）_c4−Ｃ（＝Ｏ）−、−Ｒ８３₂Ｃ−（ＣＲ８２₂）_c4−ＣＲ８３₂−、−Ｒ８３₂Ｃ−（ＣＲ８２₂）_c4−Ｓ（＝Ｏ）₂−、−Ｓ（＝Ｏ）₂−（ＣＲ８２₂）_d4−Ｓ（＝Ｏ）₂−、または−Ｃ（＝Ｏ）−（ＣＲ８２₂）_d4−Ｓ（＝Ｏ）₂−である。ただし、Ｒ８１およびＲ８３は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基であり、それぞれのうちの少なくとも１つはハロゲン基またはハロゲン化アルキル基である。Ｒ８２は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基である。なお、ａ４、ｅ４およびｎ４は１または２の整数であり、ｂ４およびｄ４は１〜４の整数であり、ｃ４は０〜４の整数であり、ｆ４およびｍ４は１〜３の整数である。）

（式中、Ｘ５１は長周期型周期表における１族元素または２族元素である。Ｍ５１は遷移金属、または長周期型周期表における１３族元素、１４族元素または１５族元素である。Ｒｆはフッ素化アルキル基またはフッ素化アリール基であり、いずれの炭素数も１〜１０である。Ｙ５１は−Ｃ（＝Ｏ）−（ＣＲ９１₂）_d5−Ｃ（＝Ｏ）−、−Ｒ９２₂Ｃ−（ＣＲ９１₂）_d5−Ｃ（＝Ｏ）−、−Ｒ９２₂Ｃ−（ＣＲ９１₂）_d5−ＣＲ９２₂−、−Ｒ９２₂Ｃ−（ＣＲ９１₂）_d5−Ｓ（＝Ｏ）₂−、−Ｓ（＝Ｏ）₂−（ＣＲ９１₂）_e5−Ｓ（＝Ｏ）₂−、または−Ｃ（＝Ｏ）−（ＣＲ９１₂）_e5−Ｓ（＝Ｏ）₂−である。ただし、Ｒ９１は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基である。Ｒ９２は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基であり、そのうちの少なくとも１つはハロゲン基またはハロゲン化アルキル基である。なお、ａ５、ｆ５およびｎ５は１または２の整数であり、ｂ５、ｃ５およびｅ５は１〜４の整数であり、ｄ５は０〜４の整数であり、ｇ５およびｍ５は１〜３の整数である。）

（式中、Ｒ９２は、２価のハロゲン化炭化水素基である。）

（式中、Ｍ⁺は１価のカチオンであり、ＹはＳＯ₂またはＣＯであり、Ｚはそれぞれ独立してハロゲン基または有機基である。）

ＬｉＣ（Ｃ_pＦ_2p+1ＳＯ₂）（Ｃ_qＦ_2q+1ＳＯ₂）（Ｃ_rＦ_2r+1ＳＯ₂）・・・（６）
（式中、ｐ、ｑおよびｒは１以上の整数である。）

［２］
前記負極側の窪み含浸領域および負極側の深部領域、並びに、正極側の窪み含浸領域および正極側の深部領域を有する［１］に記載の電池。
［３］
前記負極側の窪み含浸領域および前記負極側の深部領域、または、前記正極側の窪み含浸領域および前記正極側の深部領域を有する［１］に記載の電池。
［４］
前記少なくとも一方の深部領域の固体粒子濃度は、３体積％以下である［１］〜［３］の何れかに記載の電池。
［５］
前記少なくとも一方の窪み含浸領域の前記固体粒子濃度は、前記少なくとも一方の窪み含浸領域と同一電極側の前記深部領域の固体粒子濃度の１０倍以上である［１］〜［４］の何れかに記載の電池。
［６］
前記負極側の窪み含浸領域の厚さは、前記負極活物質層の厚さの１０％以上４０%以下である［１］〜［５］の何れかに記載の電池。
［７］
前記少なくとも一方の窪み含浸領域に含まれる前記固体粒子の粒子径Ｄ９５は、活物質粒子の粒子径Ｄ５０の２／√３−１倍以上である［１］〜［６］の何れかに記載の電池。
［８］
前記少なくとも一方の窪み含浸領域に含まれる前記固体粒子の粒子径Ｄ５０は、活物質粒子の粒子径Ｄ５０の２／√３−１倍以下である［１］〜［７］の何れかに記載の電池。
［９］
前記固体粒子のＢＥＴ比表面積は、１ｍ²／ｇ以上６０ｍ²／ｇ以下である［１］〜［８］の何れかに記載の電池。
［１０］
前記式（１）〜式（７）で表される金属塩の含有量は、０．０１質量％以上２質量％以下である［１］〜［９］の何れかに記載の電池。
［１１］
前記固体粒子は、無機粒子および有機粒子の少なくとも何れかである［１］〜［１０］の何れかに記載の電池。
［１２］
前記無機粒子は、酸化ケイ素、酸化亜鉛、酸化スズ、酸化マグネシウム、酸化アンチモン、酸化アルミニウム、硫酸マグネシウム、硫酸カルシウム、硫酸バリウム、硫酸ストロンチウム、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、炭酸リチウム、水酸化マグネシウム、水酸化アルミニウム、水酸化亜鉛、ベーマイト、ホワイトカーボン、酸化ジルコニウム水和物、酸化マグネシウム水和物、水酸化マグネシウム８水和物、炭化ホウ素、窒化ケイ素、窒化ホウ素、窒化アルミニウム、窒化チタン、フッ化リチウム、フッ化アルミニウム、フッ化カルシウム、フッ化バリウム、フッ化マグネシウム、リン酸トリリチウム、リン酸マグネシウム、リン酸水素マグネシウム、ポリリン酸アンモニウム、ケイ酸塩鉱物、炭酸塩鉱物、酸化鉱物からなる群から選ばれた少なくとも何れかの粒子であり、
前記有機粒子は、メラミン、メラミンシアヌレート、ポリリン酸メラミン、架橋ポリメタクリル酸メチル、ポリオレフィン、ポリエチレン、ポリプロピレン、ポリスチレン、ポリテトラフルオロエチレン、ポリビニリデンフルオリド、ポリアミド、ポリイミド、メラミン樹脂、フェノール樹脂、エポキシ樹脂からなる群から選ばれた少なくとも何れかの粒子である［１１］に記載の電池。
［１３］
前記ケイ酸塩鉱物は、タルク、ケイ酸カルシウム、ケイ酸亜鉛、ケイ酸ジルコニウム、ケイ酸アルミニウム、ケイ酸マグネシウム、カオリナイト、セピオライト、イモゴライト、セリサイト、パイロフィライト、雲母、ゼオライト、ムライト、サポナイト、アタパルジャイト、モンモリロナイトからなる群から選ばれた少なくとも１種であり、
前記炭酸塩鉱物は、ハイドロタルサイト、ドロマイトからなる群から選ばれた少なくとも１種であり、
前記酸化鉱物は、スピネルである［１２］に記載の電池。
［１４］
前記電解質は、前記電解液を保持した高分子化合物をさらに含む［１］〜［１３］の何れかに記載の電池
［１５］
［１］〜［１４］の何れかに記載の電池と、
前記電池を制御する制御部と、
前記電池を内包する外装と
を有する電池パック。
［１６］
［１］〜［１４］の何れかに記載の電池を有し、前記電池から電力の供給を受ける電子機器。
［１７］
［１］〜［１４］の何れかに記載の電池と、
前記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、
前記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］〜［１４］の何れかに記載の電池を有し、前記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、
前記電力情報制御装置が受信した情報に基づき、前記電池の充放電制御を行う［１８］に記載の蓄電装置。
［２０］
［１］〜［１４］の何れかに記載の電池から電力の供給を受け、または、発電装置もしくは電力網から前記電池に電力が供給される電力システム。 In addition, this technique can also take the following structures.
[1]
A positive electrode having a positive electrode active material layer containing positive electrode active material particles;
A negative electrode having a negative electrode active material layer containing negative electrode active material particles;
A separator between the positive electrode active material layer and the negative electrode active material layer;
An electrolyte containing an electrolyte solution;
With solid particles,
A negative electrode side depression impregnation region and a negative electrode side deep region, and a positive electrode side depression impregnation region and a positive electrode side deep region at least one of the depression impregnation region and the deep region;
The depression-impregnated region on the negative electrode side is a region including a depression between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer, in which the electrolyte and the solid particles are arranged,
The deep region on the negative electrode side is a region inside the negative electrode active material layer on the deeper side than the depression-impregnated region on the negative electrode side where the electrolyte or the electrolyte and the solid particles are arranged,
The depression-impregnated region on the positive electrode side is a region including a depression between adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer where the electrolyte and the solid particles are arranged,
The deep region on the positive electrode side is a region inside the positive electrode active material layer on the deeper side than the depression-impregnated region on the positive electrode side where the electrolyte or the electrolyte and the solid particles are arranged.
The concentration of the solid particles in the at least one depression-impregnated region is 30% by volume or more;
The battery includes at least one metal salt represented by the following formulas (1) to (7).

(In the formula, X31 is a group 1 element or group 2 element in the long-period periodic table, or Al. M31 is a transition metal, or a group 13 element, group 14 element, or group 15 element in the long-period periodic table. R71 is a halogen group Y31 is —C (═O) —R72—C (═O) —, —C (═O) —CR73 ₂ —, or —C (═O) —C (═O) Where R72 is an alkylene group, a halogenated alkylene group, an arylene group or a halogenated arylene group, R73 is an alkyl group, a halogenated alkyl group, an aryl group or a halogenated aryl group, wherein a3 is (It is an integer of 1 to 4, b3 is an integer of 0, 2 or 4, and c3, d3, m3 and n3 are integers of 1 to 3.)

(In the formula, X41 is a group 1 element or group 2 element in the long-period periodic table. M41 is a transition metal, or a group 13, element, or group 15 element in the long-period periodic table. Y41 is -C (= O) - (CR81 2) b4 -C (= O) -, - R83 2 C- (CR82 2) c4 -C (= O) -, - R83 2 C- (CR82 2) c4 -CR83 ₂ −, —R83 ₂ C— (CR82 ₂ ) _c4 —S (═O) ₂ —, —S (═O) ₂ — (CR82 ₂ ) _d4 —S (═O) ₂ —, or —C (═O ) — (CR82 ₂ ) _d4 —S (═O) ₂ —, wherein R81 and R83 are a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group, and at least one of each is a halogen group Or a halogenated alkyl group, wherein R82 represents a hydrogen group, an alkyl group, A4, e4 and n4 are integers of 1 or 2, b4 and d4 are integers of 1 to 4, c4 is an integer of 0 to 4, f4 and m4 is an integer of 1 to 3.)

(In the formula, X51 is a group 1 element or a group 2 element in the long-period periodic table. M51 is a transition metal, or a group 13, element, or group 15 element in the long-period periodic table. Rf is A fluorinated alkyl group or a fluorinated aryl group, each having 1 to 10 carbon atoms, Y51 is —C (═O) — (CR91 ₂ ) _d5 —C (═O) —, —R92 ₂ C— _{(CR91 2) d5 -C (=} O) -, - R92 2 C- (CR91 2) d5 -CR92 2 -, - R92 2 C- (CR91 2) d5 -S (= O) 2 -, - S ( ═O) ₂ — (CR91 ₂ ) _e5 —S (═O) ₂ —, or —C (═O) — (CR91 ₂ ) _e5 —S (═O) ₂ —, wherein R91 is a hydrogen group, An alkyl group, a halogen group or a halogenated alkyl group, and R92 represents a hydrogen group, an alkyl group, A gen group or a halogenated alkyl group, at least one of which is a halogen group or a halogenated alkyl group, wherein a5, f5 and n5 are integers of 1 or 2, and b5, c5 and e5 are from 1 to 2, 4 is an integer, d5 is an integer of 0 to 4, and g5 and m5 are integers of 1 to 3.)

(In the formula, R92 is a divalent halogenated hydrocarbon group.)

(Wherein M ⁺ is a monovalent cation, Y is SO ₂ or CO, and Z is independently a halogen group or an organic group.)

LiC (C _p F _{2p + 1} SO ₂ ) (C _q F _{2q + 1} SO ₂ ) (C _r F _{2r + 1} SO ₂ ) (6)
(In the formula, p, q and r are integers of 1 or more.)

[2]
[1] The battery according to [1], including the negative electrode side depression-impregnated region and the negative electrode side deep region, and the positive electrode side depression-impregnated region and positive electrode side deep region.
[3]
[1] The battery according to [1], wherein the battery has a dip-impregnated region on the negative electrode side and a deep region on the negative electrode side, or a dip-impregnated region on the positive electrode side and a deep region on the positive electrode side.
[4]
The battery according to any one of [1] to [3], wherein the solid particle concentration in the at least one deep region is 3% by volume or less.
[5]
In any one of [1] to [4], the solid particle concentration in the at least one depression-impregnated region is 10 times or more of the solid particle concentration in the deep region on the same electrode side as the at least one depression-impregnated region. The battery described.
[6]
The battery according to any one of [1] to [5], wherein a thickness of the depression-impregnated region on the negative electrode side is 10% or more and 40% or less of a thickness of the negative electrode active material layer.
[7]
The particle diameter D95 of the solid particles contained in the at least one hollow impregnation region is 2 / √3-1 times or more of the particle diameter D50 of the active material particles, according to any one of [1] to [6]. battery.
[8]
The particle diameter D50 of the solid particles contained in the at least one hollow impregnation region is 2 / √3-1 times or less of the particle diameter D50 of the active material particles, according to any one of [1] to [7]. battery.
[9]
The battery according to any one of [1] to [8], wherein the solid particles have a BET specific surface area of 1 m ² / g or more and 60 m ² / g or less.
[10]
The battery according to any one of [1] to [9], wherein the content of the metal salt represented by the formula (1) to the formula (7) is 0.01% by mass or more and 2% by mass or less.
[11]
The battery according to any one of [1] to [10], wherein the solid particles are at least one of inorganic particles and organic particles.
[12]
The inorganic particles are silicon oxide, zinc oxide, tin oxide, magnesium oxide, antimony oxide, aluminum oxide, magnesium sulfate, calcium sulfate, barium sulfate, strontium sulfate, magnesium carbonate, calcium carbonate, barium carbonate, lithium carbonate, magnesium hydroxide. , Aluminum hydroxide, zinc hydroxide, boehmite, white carbon, zirconium oxide hydrate, magnesium oxide hydrate, magnesium hydroxide octahydrate, boron carbide, silicon nitride, boron nitride, aluminum nitride, titanium nitride, fluorine Lithium fluoride, aluminum fluoride, calcium fluoride, barium fluoride, magnesium fluoride, trilithium phosphate, magnesium phosphate, magnesium hydrogen phosphate, ammonium polyphosphate, silicate mineral, carbonate mineral, oxide mineral At least one of particles selected from Ranaru group,
The organic particles include melamine, melamine cyanurate, melamine polyphosphate, cross-linked polymethyl methacrylate, polyolefin, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamide, polyimide, melamine resin, phenol resin, epoxy The battery according to [11], which is at least one particle selected from the group consisting of resins.
[13]
The silicate mineral is talc, calcium silicate, zinc silicate, zirconium silicate, aluminum silicate, magnesium silicate, kaolinite, sepiolite, imogolite, sericite, pyrophyllite, mica, zeolite, mullite, saponite. At least one selected from the group consisting of attapulgite and montmorillonite,
The carbonate mineral is at least one selected from the group consisting of hydrotalcite and dolomite,
The battery according to [12], wherein the oxide mineral is spinel.
[14]
The battery according to any one of [1] to [13], wherein the electrolyte further includes a polymer compound that holds the electrolytic solution.
The battery according to any one of [1] to [14];
A control unit for controlling the battery;
A battery pack having an exterior housing the battery.
[16]
[1] An electronic apparatus comprising the battery according to any one of [14] and receiving supply of electric power from the battery.
[17]
The battery according to any one of [1] to [14];
A conversion device that receives supply of electric power from the battery and converts it into driving force of a vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the battery.
[18]
A power storage device that includes the battery according to any one of [1] to [14] and supplies power to an electronic device connected to the 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 battery is performed based on information received by the power information control device.
[20]
[1] A power system that receives supply of power from the battery according to any one of [14], or that supplies power to the battery from a power generation device or a power network.

  50 ... wound electrode body, 51 ... positive electrode lead, 52 ... negative electrode lead, 53 ... positive electrode, 53A ... positive electrode current collector, 53B ... positive electrode active material layer, 54 ... Negative electrode, 54A ... negative electrode current collector, 54B ... negative electrode active material layer, 55 ... separator, 56 ... electrolyte layer, 57 ... protective tape, 60 ... exterior member, 61 ..Adhesive film, 70 ... Laminated electrode body, 71 ... Positive electrode lead, 72 ... Negative electrode lead, 73 ... Positive electrode, 74 ... Negative electrode, 75 ... Separator, 76 ... Fixed 81, battery can, 82a, 82b, insulating plate, 83, battery lid, 84, safety valve, 84a, convex, 85, disc holder, 86 Disk 86a ... Hole, 87 ... Heat sensitive resistance element, 88 ... Gasket, 89 Sub disk, 90 ... wound electrode body, 91 ... positive electrode, 91A ... positive electrode current collector, 91B ... positive electrode active material layer, 92 ... negative electrode, 92A ... negative electrode current collector Body, 92B ... negative electrode active material layer, 93 ... separator, 94 ... center pin, 95 ... positive electrode lead, 96 ... negative electrode lead, 111 ... outer can, 112 ... battery Lid, 113 ... electrode pin, 114 ... insulator, 115 ... through hole, 116 ... internal pressure release mechanism, 116a ... first opening groove, 116b ... second opening groove DESCRIPTION OF SYMBOLS 117 ... Electrolyte injection port, 118 ... Sealing member, 120 ... Winding electrode body, 101 ... Battery cell, 101a ... Terrace part, 102a, 102b ... Lead, 103a ˜103c ... insulating tape, 104 ... insulating plate, 105 Circuit board 106: Connector 211 ... Power source 212 ... Positive electrode lead 213 ... Negative electrode lead 214, 215 ... Tab 216 ... Circuit board 217 ... Connector Lead wire, 218, 219 ... adhesive tape, 220 ... label, 221 ... control unit, 222 ... switch unit, 224 ... temperature detection unit, 225 ... positive electrode terminal, 227 ... .. Negative electrode terminal, 231... Insulating sheet 301... Assembled battery, 301 a... Secondary battery, 302 a... Charge control switch, 302 b. .. Diode, 304 ... Switch unit, 307 ... Current detection resistor, 308 ... Temperature detection element, 310 ... Control unit, 311 ... Voltage detection unit, 313 ... Current measurement Fixed unit, 314 ... Switch control unit, 317 ... Memory, 318 ... Temperature detection unit, 321 ... Positive terminal, 322 ... Negative terminal, 400 ... Power storage system, 401 ... Housing 402 ... Centralized power system 402a Thermal power generation 402b Nuclear power generation 402c Hydroelectric power generation 403 Power storage device 404 Power generation device 405 Power consumption device, 405a ... refrigerator, 405b ... air conditioner, 405c ... television receiver, 405d ... bath, 406 ... electric vehicle, 406a ... electric vehicle, 406b ... Hybrid car, 406c ... electric motorcycle, 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 ... Drive wheel, 505a ... wheel, 505b ... wheel, 508 ... battery, 509 ... vehicle control device, 510 ... sensor, 511 ... charging port

Claims (20)

A positive electrode having a positive electrode active material layer containing positive electrode active material particles;
A negative electrode having a negative electrode active material layer containing negative electrode active material particles;
A separator between the positive electrode active material layer and the negative electrode active material layer;
An electrolyte containing an electrolyte solution;
With solid particles,
A negative electrode side depression impregnation region and a negative electrode side deep region, and a positive electrode side depression impregnation region and a positive electrode side deep region at least one of the depression impregnation region and the deep region;
The depression-impregnated region on the negative electrode side is a region including a depression between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer, in which the electrolyte and the solid particles are arranged,
The deep region on the negative electrode side is a region inside the negative electrode active material layer on the deeper side than the depression-impregnated region on the negative electrode side where the electrolyte or the electrolyte and the solid particles are arranged,
The depression-impregnated region on the positive electrode side is a region including a depression between adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer where the electrolyte and the solid particles are arranged,
The deep region on the positive electrode side is a region inside the positive electrode active material layer on the deeper side than the depression-impregnated region on the positive electrode side where the electrolyte or the electrolyte and the solid particles are arranged.
The concentration of the solid particles in the at least one depression-impregnated region is 30% by volume or more;
The battery includes at least one metal salt represented by the following formulas (1) to (7).

(In the formula, X31 is a group 1 element or group 2 element in the long-period periodic table, or Al. M31 is a transition metal, or a group 13 element, group 14 element, or group 15 element in the long-period periodic table. R71 is a halogen group Y31 is —C (═O) —R72—C (═O) —, —C (═O) —CR73 ₂ —, or —C (═O) —C (═O) Where R72 is an alkylene group, a halogenated alkylene group, an arylene group or a halogenated arylene group, R73 is an alkyl group, a halogenated alkyl group, an aryl group or a halogenated aryl group, wherein a3 is (It is an integer of 1 to 4, b3 is an integer of 0, 2 or 4, and c3, d3, m3 and n3 are integers of 1 to 3.)

(In the formula, X41 is a group 1 element or group 2 element in the long-period periodic table. M41 is a transition metal, or a group 13, element, or group 15 element in the long-period periodic table. Y41 is -C (= O) - (CR81 2) b4 -C (= O) -, - R83 2 C- (CR82 2) c4 -C (= O) -, - R83 2 C- (CR82 2) c4 -CR83 ₂ −, —R83 ₂ C— (CR82 ₂ ) _c4 —S (═O) ₂ —, —S (═O) ₂ — (CR82 ₂ ) _d4 —S (═O) ₂ —, or —C (═O ) — (CR82 ₂ ) _d4 —S (═O) ₂ —, wherein R81 and R83 are a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group, and at least one of each is a halogen group Or a halogenated alkyl group, wherein R82 represents a hydrogen group, an alkyl group, A4, e4 and n4 are integers of 1 or 2, b4 and d4 are integers of 1 to 4, c4 is an integer of 0 to 4, f4 and m4 is an integer of 1 to 3.)

(In the formula, X51 is a group 1 element or a group 2 element in the long-period periodic table. M51 is a transition metal, or a group 13, element, or group 15 element in the long-period periodic table. Rf is A fluorinated alkyl group or a fluorinated aryl group, each having 1 to 10 carbon atoms, Y51 is —C (═O) — (CR91 ₂ ) _d5 —C (═O) —, —R92 ₂ C— _{(CR91 2) d5 -C (=} O) -, - R92 2 C- (CR91 2) d5 -CR92 2 -, - R92 2 C- (CR91 2) d5 -S (= O) 2 -, - S ( ═O) ₂ — (CR91 ₂ ) _e5 —S (═O) ₂ —, or —C (═O) — (CR91 ₂ ) _e5 —S (═O) ₂ —, wherein R91 is a hydrogen group, An alkyl group, a halogen group or a halogenated alkyl group, and R92 represents a hydrogen group, an alkyl group, A gen group or a halogenated alkyl group, at least one of which is a halogen group or a halogenated alkyl group, wherein a5, f5 and n5 are integers of 1 or 2, and b5, c5 and e5 are from 1 to 2, 4 is an integer, d5 is an integer of 0 to 4, and g5 and m5 are integers of 1 to 3.)

(In the formula, R92 is a divalent halogenated hydrocarbon group.)

(Wherein M ⁺ is a monovalent cation, Y is SO ₂ or CO, and Z is independently a halogen group or an organic group.)

LiC (C _p F _{2p + 1} SO ₂ ) (C _q F _{2q + 1} SO ₂ ) (C _r F _{2r + 1} SO ₂ ) (6)
(In the formula, p, q and r are integers of 1 or more.)

  2. The battery according to claim 1, wherein the battery has a dip-impregnated region on the negative electrode side and a deep region on the negative electrode side, and a pit-impregnated region on the positive electrode side and a deep region on the positive electrode side.   2. The battery according to claim 1, wherein the battery has a dip-impregnated region on the negative electrode side and a deep region on the negative electrode side, or a dip-impregnated region on the positive electrode side and a deep region on the positive electrode side.   The battery according to claim 1, wherein the concentration of solid particles in the at least one deep region is 3% by volume or less.   2. The battery according to claim 1, wherein the solid particle concentration in the at least one depression-impregnated region is 10 times or more the solid particle concentration in the deep region on the same electrode side as the at least one depression-impregnation region.   2. The battery according to claim 1, wherein the thickness of the depression-impregnated region on the negative electrode side is 10% or more and 40% or less of the thickness of the negative electrode active material layer.   2. The battery according to claim 1, wherein a particle diameter D95 of the solid particles included in the at least one depression-impregnated region is 2 / √3−1 or more times a particle diameter D50 of the active material particles.   2. The battery according to claim 1, wherein a particle diameter D50 of the solid particles included in the at least one depression-impregnated region is 2 / √3-1 times or less of a particle diameter D50 of the active material particles. The battery according to claim 1, wherein the solid particles have a BET specific surface area of 1 m ² / g or more and 60 m ² / g or less.   2. The battery according to claim 1, wherein the content of the metal salt represented by the formula (1) to the formula (7) is 0.01% by mass or more and 2% by mass or less.   The battery according to claim 1, wherein the solid particles are at least one of inorganic particles and organic particles. The inorganic particles are silicon oxide, zinc oxide, tin oxide, magnesium oxide, antimony oxide, aluminum oxide, magnesium sulfate, calcium sulfate, barium sulfate, strontium sulfate, magnesium carbonate, calcium carbonate, barium carbonate, lithium carbonate, magnesium hydroxide. , Aluminum hydroxide, zinc hydroxide, boehmite, white carbon, zirconium oxide hydrate, magnesium oxide hydrate, magnesium hydroxide octahydrate, boron carbide, silicon nitride, boron nitride, aluminum nitride, titanium nitride, fluorine Lithium fluoride, aluminum fluoride, calcium fluoride, barium fluoride, magnesium fluoride, trilithium phosphate, magnesium phosphate, magnesium hydrogen phosphate, ammonium polyphosphate, silicate mineral, carbonate mineral, oxide mineral At least one of particles selected from Ranaru group,
The organic particles include melamine, melamine cyanurate, melamine polyphosphate, cross-linked polymethyl methacrylate, polyolefin, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamide, polyimide, melamine resin, phenol resin, epoxy The battery according to claim 11, wherein the battery is at least one particle selected from the group consisting of resins. The silicate mineral is talc, calcium silicate, zinc silicate, zirconium silicate, aluminum silicate, magnesium silicate, kaolinite, sepiolite, imogolite, sericite, pyrophyllite, mica, zeolite, mullite, saponite. At least one selected from the group consisting of attapulgite and montmorillonite,
The carbonate mineral is at least one selected from the group consisting of hydrotalcite and dolomite,
The battery according to claim 12, wherein the oxide mineral is spinel.   The battery according to claim 1, wherein the electrolyte further includes a polymer compound that holds the electrolytic solution. A battery according to claim 1;
A control unit for controlling the battery;
A battery pack having an exterior housing the battery.   An electronic device comprising the battery according to claim 1 and receiving power supply from the battery. A battery according to claim 1;
A conversion device that receives supply of electric power from the battery and converts it into driving force of a vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the battery.   A power storage device that has the battery according to claim 1 and supplies electric power to an electronic device connected to the 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 18, wherein charge / discharge control of the 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 battery of Claim 1, or supplies electric power to the said battery from an electric power generating apparatus or an electric power network.

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