JP6540011B2 - Battery, battery pack, electronic device, electric vehicle, power storage device and power system - Google Patents

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.

  2. Description of the Related Art In recent years, electronic devices typified by mobile phones and portable information terminal devices are widely used, and further miniaturization, weight reduction and life extension are strongly demanded. Along with this, as a power source, development of a battery, in particular, a small and lightweight secondary battery capable of obtaining high energy density has been promoted.

  Recently, the secondary battery is not limited to the above-described electronic devices, but is applied to various applications represented by electric tools such as electric drills, electric vehicles such as electric vehicles, and electric power storage systems such as household electric power servers. Is also being considered. High power and high capacity secondary batteries are being developed as these power sources.

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

JP, 2013-134859, A

  The battery is required to have a high capacity and to suppress the capacity deterioration when the charge and discharge are repeated by the high output discharge.

  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 having high capacity and capable of suppressing capacity deterioration when charging and discharging are repeated with high output discharge. It is to do.

(式（１）中、Ｘは、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−Ｃ（＝Ｒ３）−、−Ｃ（＝Ｒ１）−Ｃ（Ｒ４）（Ｒ５）−、−Ｃ（＝Ｒ１）−Ｃ（Ｒ４）（Ｒ５）−Ｃ（Ｒ６）（Ｒ７）−、−Ｃ（Ｒ４）（Ｒ５）−Ｃ（＝Ｒ１）−Ｃ（Ｒ６）（Ｒ７）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−Ｃ（Ｒ４）（Ｒ５）−、−Ｃ（＝Ｒ１）−Ｃ（Ｒ４）（Ｒ５）−Ｃ（＝Ｒ２）−、−Ｃ（＝Ｒ１）−Ｏ−Ｃ（Ｒ４）（Ｒ５）−、−Ｃ（＝Ｒ１）−Ｏ−Ｃ（＝Ｒ２）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ８）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−Ｃ（＝Ｒ８）−からなる群から選ばれた何れか一の２価の基である。Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、炭素数１の２価の炭化水素基または炭素数１の２価のハロゲン化炭化水素基である。Ｒ４、Ｒ５、Ｒ６およびＲ７は、それぞれ独立して、１価の水素基（−Ｈ）、炭素数１以上８以下の１価の炭化水素基、炭素数１以上８以下の１価のハロゲン化炭化水素基または炭素数１以上６以下の１価の酸素含有炭化水素基である。Ｒ８は、炭素数２以上５以下のアルキレン基または炭素数２以上５以下のハロゲン化アルキレン基である。)

（式（２）中、Ｒ２１〜Ｒ２４は、それぞれ独立して、水素基、ハロゲン基、アルキル基またはハロゲン化アルキル基であり、Ｒ２１〜Ｒ２４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。）

（式（３）中、Ｒ２５〜Ｒ３０は、それぞれ独立して、水素基、ハロゲン基、アルキル基またはハロゲン化アルキル基であり、Ｒ２５〜Ｒ３０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。） In order to solve the problems described above, the present technology provides 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 positive electrode active material layer and a negative electrode active A separator between the substance layers, an electrolyte containing an electrolytic solution, and solid particles, and the depression impregnation region on the negative electrode side and the deep region on the negative electrode side, and the depression impregnation region on the positive electrode side and the deep region on the positive electrode side The hollow impregnation region on the negative electrode side is a region including depressions 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 disposed, and the deep region on the negative electrode side is And an area inside the negative electrode active material layer which is located deeper than the depression impregnation area on the negative electrode side where the electrolyte or the electrolyte and solid particles are arranged, and the depression impregnation area on the positive electrode side is where the electrolyte and solid particles are arranged. Of the positive electrode active material layer It is a region including depressions between adjacent positive electrode active material particles located on the surface, and the deep region on the positive electrode side is a positive electrode active material deeper than the depression impregnation region on the positive electrode side where the electrolyte or electrolyte and solid particles are arranged. a layer inside the region, the concentration of solid particles in the recess impregnation zone of the negative electrode side is 30% by volume or more, the concentration of solid particles in the recess impregnation zone of the positive electrode side is 30% by volume or more, the negative electrode side The solid particle concentration in the deep region is 3% by volume or less, the solid particle concentration in the deep region on the positive electrode side is 3% by volume or less, and the solid particles are boehmite, talc, zinc oxide, tin oxide, silicon oxide , Magnesium oxide, antimony oxide, aluminum oxide, magnesium sulfate, calcium sulfate, barium sulfate, strontium sulfate, magnesium carbonate, calcium carbonate, Barium, lithium carbonate, magnesium hydroxide, aluminum hydroxide, zinc hydroxide, boron carbide, silicon carbide, silicon nitride, boron nitride, aluminum nitride, titanium nitride, lithium fluoride, lithium fluoride, aluminum fluoride, calcium fluoride, fluoride Barium, magnesium fluoride, diamond, trilithium phosphate, magnesium phosphate, magnesium hydrogen phosphate, calcium silicate, zinc silicate, zirconium silicate, aluminum silicate, magnesium silicate, spinel, hydrotalcite, dolomite, Kaolinite, sepiolite, imogolite, sericite, pyrophyllite, mica, zeolite, mullite, saponite, attapulgite, montmorillonite, ammonium polyphosphate, melamine cyanurate, melami polyphosphate And the electrolyte is an unsaturated cyclic carbonate represented by the following formula (1) and an electrolyte represented by the formulas (2) and (3): It is a lithium ion secondary battery containing at least one kind of halogenated carbonate ester.

(In formula (1), X is -C (= R1) -C (= R2)-, -C (= R1) -C (= R2) -C (= R3)-, -C (= R1) -C (R4) (R5)-, -C (= R1) -C (R4) (R5) -C (R6) (R7)-, -C (R4) (R5) -C (= R1) -C (R6) (R7)-, -C (= R1) -C (= R2) -C (R4) (R5)-, -C (= R1) -C (R4) (R5) -C (= R2) -, -C (= R1) -O-C (R4) (R5)-, -C (= R1) -O-C (= R2)-, -C (= R1) -C (= R8)-, It is any one divalent group selected from the group consisting of -C (= R1) -C (= R2) -C (= R8)-R1, R2 and R3 are each independently carbon Number 1 divalent hydrocarbon group or carbon number 1 divalent halogenated hydrocarbon group R4, R5, R6 and R7 are each independently a monovalent hydrogen group (-H), a monovalent hydrocarbon group having 1 to 8 carbon atoms, a monovalent having 1 to 8 carbon atoms Or a monovalent oxygen-containing hydrocarbon group having 1 to 6 carbon atoms, R 8 is an alkylene group having 2 to 5 carbon atoms or a halogenated alkylene group having 2 to 5 carbon atoms. is there.)

(In formula (2), R 21 to R 24 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of R 21 to R 24 is a halogen group or a halogenated alkyl group Is)

(In formula (3), R 25 to R 30 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of R 25 to R 30 is a halogen group or a halogenated alkyl group Is)

（式（１）中、Ｘは、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−Ｃ（＝Ｒ３）−、−Ｃ（＝Ｒ１）−Ｃ（Ｒ４）（Ｒ５）−、−Ｃ（＝Ｒ１）−Ｃ（Ｒ４）（Ｒ５）−Ｃ（Ｒ６）（Ｒ７）−、−Ｃ（Ｒ４）（Ｒ５）−Ｃ（＝Ｒ１）−Ｃ（Ｒ６）（Ｒ７）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−Ｃ（Ｒ４）（Ｒ５）−、−Ｃ（＝Ｒ１）−Ｃ（Ｒ４）（Ｒ５）−Ｃ（＝Ｒ２）−、−Ｃ（＝Ｒ１）−Ｏ−Ｃ（Ｒ４）（Ｒ５）−、−Ｃ（＝Ｒ１）−Ｏ−Ｃ（＝Ｒ２）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ８）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−Ｃ（＝Ｒ８）−からなる群から選ばれた何れか一の２価の基である。Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、炭素数１の２価の炭化水素基または炭素数１の２価のハロゲン化炭化水素基である。Ｒ４、Ｒ５、Ｒ６およびＲ７は、それぞれ独立して、１価の水素基（−Ｈ）、炭素数１以上８以下の１価の炭化水素基、炭素数１以上８以下の１価のハロゲン化炭化水素基または炭素数１以上６以下の１価の酸素含有炭化水素基である。Ｒ８は、炭素数２以上５以下のアルキレン基または炭素数２以上５以下のハロゲン化アルキレン基である。）

（式（２）中、Ｒ２１〜Ｒ２４は、それぞれ独立して、水素基、ハロゲン基、アルキル基またはハロゲン化アルキル基であり、Ｒ２１〜Ｒ２４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。）

（式（３）中、Ｒ２５〜Ｒ３０は、それぞれ独立して、水素基、ハロゲン基、アルキル基またはハロゲン化アルキル基であり、Ｒ２５〜Ｒ３０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。）

(In formula (1), X is -C (= R1) -C (= R2)-, -C (= R1) -C (= R2) -C (= R3)-, -C (= R1) -C (R4) (R5)-, -C (= R1) -C (R4) (R5) -C (R6) (R7)-, -C (R4) (R5) -C (= R1) -C (R6) (R7)-, -C (= R1) -C (= R2) -C (R4) (R5)-, -C (= R1) -C (R4) (R5) -C (= R2) -, -C (= R1) -O-C (R4) (R5)-, -C (= R1) -O-C (= R2)-, -C (= R1) -C (= R8)-, It is any one divalent group selected from the group consisting of -C (= R1) -C (= R2) -C (= R8)-R1, R2 and R3 are each independently carbon Number 1 divalent hydrocarbon group or carbon number 1 divalent halogenated hydrocarbon R4, R5, R6 and R7 are each independently a monovalent hydrogen group (-H), a monovalent hydrocarbon group having 1 to 8 carbon atoms, a monovalent having 1 to 8 carbon atoms Or a monovalent oxygen-containing hydrocarbon group having 1 to 6 carbon atoms, R 8 is an alkylene group having 2 to 5 carbon atoms or a halogenated alkylene group having 2 to 5 carbon atoms. is there.)

(In formula (2), R 21 to R 24 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of R 21 to R 24 is a halogen group or a halogenated alkyl group Is)

(In formula (3), R 25 to R 30 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of R 25 to R 30 is a halogen group or a halogenated alkyl group Is)

  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, it is possible to obtain the effect of having high capacity and suppressing capacity deterioration when charging and discharging are repeated by high output discharge.

FIG. 1 is an exploded perspective view showing a configuration of a laminate film type non-aqueous electrolyte battery according to an embodiment of the present technology. FIG. 2 is a cross-sectional view showing a cross-sectional configuration along a line I-I of the wound electrode body shown in FIG. FIG. 3 is a schematic cross-sectional view showing the internal configuration of the non-aqueous electrolyte battery. 4A to 4C are exploded perspective views showing the configuration of a laminate film type non-aqueous electrolyte battery using a laminated electrode body. FIG. 5 is a cross-sectional view showing a configuration of a cylindrical non-aqueous electrolyte battery according to an embodiment of the present technology. FIG. 6 is a cross-sectional view showing an enlarged part of a wound electrode body accommodated in a cylindrical non-aqueous electrolyte battery. FIG. 7 is a perspective view showing a configuration of a rectangular non-aqueous electrolyte battery according to an embodiment of the present technology. FIG. 8 is a perspective view showing a configuration of an application example (battery pack: single cell) of a secondary battery. FIG. 9 is a block diagram showing the configuration of the battery pack shown in FIG. FIG. 10 is a block diagram showing an example of a circuit configuration of the battery pack according to the embodiment of the present technology. FIG. 11 is a schematic view showing an example applied to a residential power storage system using the non-aqueous electrolyte battery of the present technology. FIG. 12 is a schematic diagram schematically showing an example of a configuration of a hybrid vehicle adopting a series hybrid system to which the present technology is applied.

(Summary of this technology)
First, in order to facilitate understanding of the present technology, an outline of the present technology will be described. As described above, in the secondary battery, an additive is added to the electrolytic solution to improve the battery performance.

  However, as described below, the cycle characteristics, the output characteristics, and the capacity are in a trade-off relationship in which the performance of one of them is improved while the other performance is sacrificed. For this reason, it has been difficult to make all the battery performances of the cycle characteristics, the output characteristics and the capacity excellent in improving the battery performance by the additive.

  For example, an additive can be added to the electrolytic solution to form a film derived from the additive on the surface of the electrode active material, and decomposition of the electrolytic solution due to a side reaction can be suppressed, and capacity deterioration due to charge and discharge cycles can be suppressed. On the other hand, this film becomes resistance and causes the deterioration of output characteristics. The reduced output characteristics can be compensated by thinning the electrode mixture layer and reducing the resistance. On the other hand, in this case, the ratio of the foil (current collector) and the separator which do not add to the capacity increases, which causes the capacity to be reduced.

  The film derived from the additive suppresses side reactions that occur mainly in cracks that occur in the active material particles during electrode pressing. Therefore, the coating derived from the additive may be formed on the cracked surface. Since the film derived from the additive which can be formed on the portion other than the cracked surface is a factor which increases the resistance at the time of insertion and desorption of Li ions, it has been avoided to add an excessive amount of the additive. In addition, depending on the type of additive, there is also one that effectively forms a thick film, but in areas other than the cracks of the active material, the film becomes a resistor and there are many materials that are practically difficult to use. In addition, when the additive amount of the additive is reduced, the resistance decreases but the action of the crack portion becomes insufficient.

  As a result of intensive investigations, the inventors of the present invention form an effective film against a crack, but as an additive that causes deterioration of high output characteristics in portions other than the crack, the following formula (1) It was found that at least one kind of unsaturated cyclic carbonate represented by the formula (2) and halogenated carbonate represented by the formula (2) and the formula (3) is used.

  If only a necessary amount of this additive is supplied intensively to the cracked part, a small amount of addition is sufficient and no extra thick coating can be made, thus providing a battery with high capacity and high capacity with less capacity deterioration due to cycles. it can.

  With the aim of obtaining such effects, the inventors of the present application have found out the following as a result of intensive studies. That is, the cracks are mainly generated in the active material particles located on the outermost surface of the electrode by performing the pressing process at the time of forming the electrode. In particular, many cracks appear in the vicinity of the particle surface forming a depression between adjacent active material particles located on the outermost surface of the electrode. By arranging specific solid particles in the depression, at least one of the unsaturated cyclic carbonate represented by the formula (1) described below and the halogenated carbonate represented by the formula (2) and the formula (3) The effect of being able to selectively collect the seeds in the crack portion is obtained.

  The battery of the present technology obtained as a result of the above-mentioned intensive studies has the minimum necessary for the intensively required places in the battery by arranging specific solid particles in the depressions between adjacent active material particles in the battery. An amount of film forming agent is arranged. As a result, in the present technology, it is possible to have high capacity and to suppress capacity deterioration when charging and discharging are repeated with high output discharge.

Hereinafter, embodiments of the present technology will be described with reference to the drawings. The description will be made in the following order.
1. First Embodiment (Example of Laminated Film Type Battery)
2. Second Embodiment (Example of Cylindrical Battery)
3. Third embodiment (example of rectangular battery)
4. Fourth Embodiment (Example of Battery Pack)
5. Fifth Embodiment (Example of Battery Pack)
6. Sixth embodiment (example of power storage system etc.)
7. Other Embodiments (Modifications)
Note that the embodiments and the like described below are preferred specific examples of the present technology, and the contents of the present technology are not limited to these embodiments and the like. Further, the effects described in the present specification are merely examples and are not limited, and it is not to be denied that effects different from the effects illustrated are present.

1. First Embodiment In a 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 capable of charging and discharging, 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 battery, in which the wound electrode body 50 to which the positive electrode lead 51 and the negative electrode lead 52 are attached is accommodated inside a film-shaped exterior member 60.

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

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

  The metal layer plays the most important role of preventing the ingress of moisture, oxygen and light and protects the contents, and aluminum (Al) is most often used because of its lightness, extensibility, cost and ease of processing. The outer resin layer has appearance beauty, 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 suitable, and non-oriented polypropylene (CPP) is often used. An adhesive layer may be provided as needed between the metal layer and the outer resin layer and the inner resin layer.

  The exterior member 60 is provided with a recess for accommodating the wound electrode body 50 formed, for example, by deep drawing from the inner resin layer side toward the outer resin layer, and the inner resin layer is a wound electrode body 50. It is disposed to face the The opposing inner resin layers of the exterior member 60 are in close contact with each other by fusion or the like at the outer edge portion of the recess. An adhesive film 61 is provided between the package member 60 and the positive electrode lead 51 and the negative electrode lead 52 for improving the adhesion between the inner resin layer of the package member 60 and the positive electrode lead 51 and the negative electrode lead 52 made of a metal material. It is arranged. The adhesive film 61 is made of a resin material having high adhesiveness 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 in which the metal layer is made of aluminum (Al).

  FIG. 2 shows a cross-sectional structure along a line I-I of the spirally wound electrode body 50 shown in FIG. As shown in FIG. 1, the wound electrode body 50 is formed by laminating and winding a strip-shaped positive electrode 53 and a strip-shaped negative electrode 54 via a strip-shaped separator 55 and an electrolyte layer 56, and the outermost peripheral portion 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 side or both sides of a positive electrode current collector 53A.

  The positive electrode 53 is formed by forming a positive electrode active material layer 53B containing a positive electrode active material 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 side of the positive electrode current collector 53A. As the positive electrode current collector 53A, for example, a metal foil such as aluminum (Al) foil, nickel (Ni) foil, or stainless steel (SUS) foil can be used.

  The positive electrode active material layer 53B contains, for example, a positive electrode active material, a conductive agent, and a binder. As the positive electrode active material, any one or two or more of positive electrode materials capable of inserting and extracting lithium can be used, and if necessary, other materials such as a binder and a conductive agent can be used. 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 phosphoric acid compound containing lithium and a transition metal element. Among them, those containing at least one selected from the group consisting of cobalt (Co), nickel (Ni), manganese (Mn) and iron (Fe) as a transition metal element are preferable. It is because a higher voltage can be obtained.

As a positive electrode material, for example, a lithium-containing compound represented by Li _x M ₁ O ₂ or Li _y M ₂ PO 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 usually, 0.05 ≦ x ≦ 1.10 and 0.05 ≦ y ≦ 1.10. Examples of composite oxides containing lithium and a transition metal element include a lithium cobalt complex oxide (Li _x CoO _2), lithium nickel composite oxide (Li _x NiO _2), lithium nickel cobalt composite oxide (Li _x Ni _{1-z Co z O 2 (} 0 <z <1)), a lithium nickel cobalt manganese complex oxide _{(Li x Ni (1-vw} ) Co v Mn w O 2 (0 <v + w <1, v> 0, w > 0)), lithium manganese complex oxide (LiMn ₂ O ₄ ) having a spinel structure, lithium manganese nickel complex oxide (LiMn _2-t Ni _t O ₄ (0 <t <2)), etc. . Among them, composite oxides containing cobalt are preferred. This is because a high capacity can be obtained and also excellent cycle characteristics can be obtained. Moreover, as a phosphoric acid compound containing lithium and a transition metal element, for example, lithium iron phosphoric acid compound (LiFePO ₄ ) or lithium iron manganese phosphoric acid compound (LiFe _1-u Mn _u PO ₄ (0 <u <1) Etc.).

Specific examples of such lithium composite oxides include lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), lithium manganate (LiMn ₂ O ₄ ), and the like. In addition, a solid solution in which part of the transition metal element is replaced with another element can also be used. For example, nickel-cobalt composite lithium oxide (LiNi _0.5 Co _0.5 O ₂ , LiNi _0.8 Co _0.2 O ₂ or the like) is mentioned as an example. These lithium composite oxides can generate high voltage and have excellent energy density.

  Furthermore, also from the viewpoint of obtaining higher electrode filling properties and cycle characteristics, it is possible to use as a composite particle the surface of the particle made of any of the above lithium-containing compounds covered with fine particles made of any of the other lithium containing compounds. Good.

In addition, as a positive electrode material capable of storing and releasing lithium, for example, oxides such as vanadium oxide (V ₂ O ₅ ), titanium dioxide (TiO ₂ ), manganese dioxide (MnO ₂ ), iron disulfide Disulfides such as (FeS ₂ ), titanium disulfide (TiS ₂ ), molybdenum disulfide (MoS ₂ ), lithium-free chalcogenides such as niobium diselenide (NbSe ₂ ) (especially layered compounds and spinel compounds And lithium-containing compounds containing lithium, and conductive polymers such as sulfur, polyaniline, polythiophene, polyacetylene or polypyrrole. Of course, positive electrode materials capable of inserting and extracting lithium may be other than those described above. Moreover, 2 or more types of above-mentioned series positive electrode materials may be mixed by arbitrary combinations.

  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 copolymers having as a main component 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 in the form of metal foil or mesh, but it is electrochemically and chemically stable, and it is not a metal as long as it can be conducted without problems. 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 the negative electrode active material layer 54B is provided on one side or both sides of the negative electrode current collector 54A, and the negative electrode active material layer 54B and the positive electrode active material layer 53B are disposed to face each other. There is.

  Although not shown, the negative electrode active material layer 54B may be provided only on one side 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 is configured to include, as a negative electrode active material, any one or two or more negative electrode materials capable of inserting and extracting lithium, and as necessary, the positive electrode active material layer 53B. And other materials such as a binder and a conductive agent may be included.

  In this non-aqueous electrolyte battery, the electrochemical equivalent of the negative electrode material capable of inserting and extracting lithium is larger than the electrochemical equivalent of the positive electrode 53, and theoretically, the negative electrode 54 is used during charging. Lithium metal is not deposited.

In addition, this non-aqueous electrolyte battery is designed such that the open circuit voltage (that is, the battery voltage) in the fully charged state is in the 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 at about 0 V with respect to Li / Li ⁺ or a material that occludes lithium is used as the negative electrode active material, the open circuit voltage in the fully charged state is, for example, 4.20 V or more. It is designed to be within the range of 00 V or less. In this case, the open circuit voltage in the fully charged state is preferably set to 4.25 V or more and 6.00 V or less. When the open circuit voltage in the fully charged state is set to 4.25 V or more, the amount of lithium released per unit mass is large even with the same positive electrode active material as compared with the 4.20 V battery, Accordingly, the amounts of the positive electrode active material and the negative electrode active material are adjusted. Thereby, high energy density can be obtained.

  Examples of negative electrode materials capable of inserting and extracting lithium include non-graphitizable carbon, non-graphitizable carbon, graphite, pyrolytic carbons, cokes, glassy carbons, organic polymer compound fired body And carbon materials such as carbon fiber or activated carbon. Among these, cokes include pitch coke, needle coke, and petroleum coke. An organic polymer compound fired body is a material obtained by firing and carbonizing a polymer material such as a phenol resin or furan resin at an appropriate temperature, and in part, non-graphitizable carbon or graphitizable carbon Some are classified as These carbon materials are preferable because the change of the crystal structure occurring during charge and discharge is very small, high charge and discharge capacity can be obtained, and good cycle characteristics can be obtained. In particular, graphite is preferable because it has a large electrochemical equivalent and can obtain high energy density. Further, non-graphitizable carbon is preferable because excellent cycle characteristics can be obtained. Furthermore, one having a low charge / discharge potential, specifically one having a charge / discharge potential close to that of lithium metal is preferable because high energy density of the battery can be easily realized.

  As another negative electrode material capable of inserting and extracting lithium and capable of increasing the capacity, it is possible to insert and extract lithium, and at least one of a metal element and a metalloid element There is also a material containing as a constituent element. With such a material, high energy density can be obtained. In particular, when used together with a carbon material, a high energy density can be obtained, and excellent cycle characteristics can be obtained, which is more preferable. The negative electrode material may be a single metal element or semimetal element, an alloy or a compound, or may have at least a part of one or more of these phases. In the present technology, alloys include alloys containing one or more metal elements and one or more metalloid elements in addition to an alloy composed of two or more metal elements. Moreover, you may contain the nonmetallic element. The structure includes a solid solution, a eutectic (eutectic mixture), an intermetallic compound or a mixture of two or more of them.

  As a metal element or semimetal element which comprises this negative electrode material, the metal element or semimetal element which can form an alloy with lithium is mentioned, for example. 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) It can be mentioned. These may be crystalline or amorphous.

  The negative electrode material preferably contains a metal element or metalloid element of Group 4B in the short period periodic table as a constituent element, and more preferably contains at least one of silicon (Si) and tin (Sn) as a constituent element And particularly preferably at least silicon. Silicon (Si) and tin (Sn) have a large ability to insert and extract lithium and can obtain high energy density. As a negative electrode material having at least one of silicon and tin, for example, a simple substance, alloy or compound of silicon, simple substance, alloy or compound of tin, or at least a part of one or more phases thereof The material which it has to is mentioned.

  As an alloy of silicon, for example, as a second component element other than silicon, tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc ( Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr) containing at least one of the group consisting of It can be mentioned. As an alloy of tin, for example, silicon (Si), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn) as a second constituent element other than tin (Sn) At least one member selected from the group consisting of zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr) Include.

  Examples of compounds of tin (Sn) or compounds of silicon (Si) include those containing oxygen (O) or carbon (C), and in addition to tin (Sn) or silicon (Si), the above-described compounds It may contain two constituent elements.

  Above all, the negative electrode material contains cobalt (Co), tin (Sn) and carbon (C) as constituent elements, and the content of carbon is 9.9% by mass or more and 29.7% by mass or less And the SnCoC containing material whose ratio of cobalt (Co) to the sum total of tin (Sn) and cobalt (Co) is 30 mass% or more and 70 mass% or less is preferable. While being able to obtain high energy density in such a composition range, it is because excellent cycling characteristics can be obtained.

  The SnCoC-containing material may further contain other constituent elements as needed. Other constituent elements include, for example, silicon (Si), iron (Fe), nickel (Ni), chromium (Cr), indium (In), niobium (Nb), germanium (Ge), titanium (Ti), molybdenum (Mo), aluminum (Al), phosphorus (P), gallium (Ga) or bismuth (Bi) is preferable, and may contain two or more kinds. This is because the capacity or cycle characteristics can be further improved.

  The SnCoC-containing material has a phase containing tin (Sn), cobalt (Co), and carbon (C), and this phase has a low crystalline or amorphous structure. Is preferred. Further, in the SnCoC-containing material, it is preferable that at least a part of carbon (C) which is a constituent element is bonded to a metal element or a metalloid element which is another constituent element. The decrease in cycle characteristics is considered to be caused by aggregation or crystallization of tin (Sn) or the like, but the carbon (C) is combined with other elements to suppress such aggregation or crystallization. Because you can do it.

  An X-ray photoelectron spectroscopy (XPS) may, for example, be mentioned as a measurement method for examining the bonding state of elements. In XPS, the peak of 1s orbital (C1s) of carbon appears at 284.5 eV in an apparatus whose energy is calibrated so that the peak of 4f orbital (Au4f) of a gold atom 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 is high, for example, when carbon is bonded to the metal element or the metalloid element, the peak of C1s appears in a region lower than 284.5 eV. That is, when the peak of the C1s synthetic wave obtained for the SnCoC-containing material appears in a region lower than 284.5 eV, at least a part of carbon contained in the SnCoC-containing material is a metal element or a half of which is another constituent element. Bonded with metal elements.

  In XPS measurement, for example, a peak of C1s is used for correction of the energy axis of the spectrum. In general, since surface contaminating carbon is present on the surface, the C1s peak of the surface contaminating carbon is 284.8 eV, which is used as an energy standard. In XPS measurement, the waveform of the C1s peak is obtained as a form including the surface contaminating carbon peak and the carbon peak in the SnCoC-containing material. Therefore, the surface contamination can be determined, for example, by using commercially available software. The peak of carbon and the peak of carbon in the SnCoC-containing material are separated. In the analysis of the waveform, the position of the main peak present on the lowest binding energy side is used as the energy reference (284.8 eV).

The negative electrode material capable of inserting and extracting lithium also includes, for example, a metal oxide or a polymer compound capable of inserting and extracting 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, and polypyrrole.

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

  The separator 55 is, for example, a porous film made of a resin. The porous membrane made of a resin is a thinly stretched material such as a resin and has a porous structure. For example, a porous membrane made of a resin is obtained by molding a material such as a resin according to a stretching pore method or a phase separation method. For example, in the draw-opening method, first, a molten polymer is extruded from a T die or a circular die, and heat treatment is further performed to form a highly ordered crystal structure. Thereafter, low temperature drawing and further high temperature drawing are performed to peel off the crystal interface to form a gap between lamellas to form a porous structure. In the phase separation method, a homogeneous 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 to form 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. As a resin material constituting such a separator 55, for example, a polyolefin resin such as polypropylene or polyethylene, an acrylic resin, a styrene resin, a polyester resin, a nylon resin, or the like is preferably used. In particular, polyethylenes such as low density polyethylene, high density polyethylene, linear polyethylene, or low molecular weight wax components thereof, or polyolefin resins such as polypropylene are suitably used because they have suitable melting temperatures and are easy to obtain. In addition, a structure in which two or more types of porous membranes are laminated, or a porous membrane formed by melt-kneading two or more types of resin materials may be used. Those including a porous film made of a polyolefin resin are excellent in the separation between the positive electrode 53 and the negative electrode 54, and can further reduce the decrease in internal short circuit.

  The separator 55 may be an unemployed cloth. A non-woven fabric is a structure formed by joining or entanglement between fibers, or joining and entanglement, without weaving or knitting fibers, mechanically, chemically, or a solvent, or a combination thereof. Most materials that can be processed into fibers can be used as raw materials for non-woven fabrics, and by adjusting shapes such as fiber length and thickness, it is possible to have functions according to the purpose and application. The non-woven fabric manufacturing method typically includes two steps: forming an integrated layer of fibers called a fleece, and bonding between the fibers of the fleece. At each stage, there are various manufacturing methods, which are selected according to the raw material, purpose and application of the non-woven fabric. For example, as the step of 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 bonding method, a chemical bonding method, a needle punching method, a spunlace method (water flow junction method), a stitch bonding method, a steam jet method or the like can be used.

  As a non-woven fabric, for example, a polyethylene terephthalate gas-permeable membrane (polyethylene terephthalate non-woven fabric) using polyethylene terephthalate (PET) fibers, etc. may be mentioned. In addition, an air permeable film means the film which has air permeability. In addition, examples of the non-woven fabric include those using aramid fibers, glass fibers, cellulose fibers, polyolefin fibers, nylon fibers, and the like. The non-woven fabric may use two or more types of fibers.

  The thickness of the separator 55 can be set arbitrarily as long as it can maintain the required strength. The separator 55 insulates between the positive electrode 53 and the negative electrode 54 to prevent a short circuit etc., and has ion permeability for suitably performing a battery reaction through the separator 55, and the battery reaction in the battery The thickness of the active material layer is preferably set to a thickness that 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 non-aqueous electrolyte, and solid particles. The electrolyte layer 56 is, for example, a layer in which a non-aqueous electrolytic solution 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 contained in the inside of the negative electrode active material layer 53B and / or in the inside of the positive electrode active material layer 54. Further, the details will be described in the following modified example, but instead of the electrolyte layer 56, a non-aqueous electrolytic solution which is a liquid electrolyte may be used. In this case, the non-aqueous electrolyte battery includes a wound body having a configuration in which the electrolyte layer 56 is omitted from the wound electrode body 50, instead of the wound electrode body 50. The non-aqueous electrolyte, which is a liquid electrolyte filled in the exterior member 60, is impregnated in the wound body.

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

(Non-aqueous electrolyte)
The non-aqueous electrolyte contains an electrolyte salt, a non-aqueous solvent that dissolves the electrolyte salt, and an additive.

(Electrolyte salt)
The electrolyte salt contains, for example, one or more light metal compounds such as a lithium salt. 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 ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), lithium tetrachloroaluminate (LiAlCl ₄ ), six fluorinated silicate dilithium (Li ₂ SiF _6), lithium (LiCl) or lithium bromide chloride (LiBr) and the like. Among them, at least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate and lithium hexafluoroarsenate is preferred, and lithium hexafluorophosphate is more preferred.

(Non-aqueous solvent)
Examples of the non-aqueous solvent include lactone solvents such as γ-butyrolactone, γ-valerolactone, δ-valerolactone or ε-caprolactone, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate or Carbonate solvents such as diethyl carbonate, ether such as 1,2-dimethoxyethane, 1-ethoxy-2-methoxyethane, 1,2-diethoxyethane, tetrahydrofuran or 2-methyltetrahydrofuran, nitriles such as acetonitrile Nonaqueous solvents such as solvents, sulfolane solvents, phosphoric acids, phosphoric ester solvents, or pyrrolidones may be mentioned. The solvents may be used singly or in combination of two or more.

(Additive)
The non-aqueous electrolyte contains an unsaturated cyclic carbonate represented by the following formula (1). An unsaturated cyclic carbonate is a cyclic carbonate having one or more carbon-carbon double bonds (> C = C <).

（式（１）中、Ｘは、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−Ｃ（＝Ｒ３）−、−Ｃ（＝Ｒ１）−Ｃ（Ｒ４）（Ｒ５）−、−Ｃ（＝Ｒ１）−Ｃ（Ｒ４）（Ｒ５）−Ｃ（Ｒ６）（Ｒ７）−、−Ｃ（Ｒ４）（Ｒ５）−Ｃ（＝Ｒ１）−Ｃ（Ｒ６）（Ｒ７）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−Ｃ（Ｒ４）（Ｒ５）−、−Ｃ（＝Ｒ１）−Ｃ（Ｒ４）（Ｒ５）−Ｃ（＝Ｒ２）−、−Ｃ（＝Ｒ１）−Ｏ−Ｃ（Ｒ４）（Ｒ５）−、−Ｃ（＝Ｒ１）−Ｏ−Ｃ（＝Ｒ２）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ８）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−Ｃ（＝Ｒ８）−からなる群から選ばれた何れか一の２価の基である。Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、炭素数１の２価の炭化水素基または炭素数１の２価のハロゲン化炭化水素基である。Ｒ４、Ｒ５、Ｒ６およびＲ７は、それぞれ独立して、１価の水素基（−Ｈ）、炭素数１以上８以下の１価の炭化水素基、炭素数１以上８以下の１価のハロゲン化炭化水素基または炭素数１以上６以下の１価の酸素含有炭化水素基である。Ｒ８は、炭素数２以上５以下のアルキレン基または炭素数２以上５以下のハロゲン化アルキレン基である。）

(In formula (1), X is -C (= R1) -C (= R2)-, -C (= R1) -C (= R2) -C (= R3)-, -C (= R1) -C (R4) (R5)-, -C (= R1) -C (R4) (R5) -C (R6) (R7)-, -C (R4) (R5) -C (= R1) -C (R6) (R7)-, -C (= R1) -C (= R2) -C (R4) (R5)-, -C (= R1) -C (R4) (R5) -C (= R2) -, -C (= R1) -O-C (R4) (R5)-, -C (= R1) -O-C (= R2)-, -C (= R1) -C (= R8)-, It is any one divalent group selected from the group consisting of -C (= R1) -C (= R2) -C (= R8)-R1, R2 and R3 are each independently carbon Number 1 divalent hydrocarbon group or carbon number 1 divalent halogenated hydrocarbon R4, R5, R6 and R7 are each independently a monovalent hydrogen group (-H), a monovalent hydrocarbon group having 1 to 8 carbon atoms, a monovalent having 1 to 8 carbon atoms Or a monovalent oxygen-containing hydrocarbon group having 1 to 6 carbon atoms, R 8 is an alkylene group having 2 to 5 carbon atoms or a halogenated alkylene group having 2 to 5 carbon atoms. is there.)

  Such unsaturated cyclic carbonates have a structure of -C = R1, R2, R3 or R8 and are thus easily attracted to solid particles. In addition, since the monovalent group -R4, R5, R6 or R7 is a group having a predetermined carbon number, or a group containing a hydrogen group or a halogen, it is more effective.

The “hydrocarbon group” is a generic term for a group composed of C and H, and may be linear or branched having one or more side chains. The monovalent hydrocarbon group is, for example, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, and 6 to 8 carbon atoms. Or a cycloalkyl group having 3 to 8 carbon atoms. The divalent C 1 hydrocarbon group is, for example, a methylene group (= CH ₂ ). Examples of the alkylene group having 2 to 5 carbon atoms include ethylene group (-CH _2- , n-propylene group (-CH ₂ CH ₂ CH _2- ) and the like.

More specifically, the alkyl group, for example, methyl group (-CH _3), ethyl group (-C ₂ H ₅₎ or propyl (-C ₃ H _7), and the like. Alkenyl group includes, for example, a vinyl group (-CH = CH ₂₎ or an allyl group _{(-CH 2 -CH = CH 2)} . The alkynyl group is, for example, an ethynyl group (—C≡CH) and the like. The aryl group is, for example, a phenyl group, a benzyl group and the like. The cycloalkyl group is, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group or cyclooctyl group.

An "oxygen containing hydrocarbon group" is a group comprised by O with C and H. The monovalent oxygen-containing hydrocarbon group is, for example, an alkoxy group having 1 to 12 carbon atoms. This is because the advantages described above can be obtained while securing the solubility, compatibility, and the like of the unsaturated cyclic carbonate ester. More specifically, the alkoxy group include a methoxy group (-OCH ₃₎ or ethoxy group (-OC ₂ H _5), and the like.

  The "monovalent halogenated hydrocarbon group" is one in which at least a part of hydrogen groups (-H) of the above-mentioned monovalent hydrocarbon groups are substituted (halogenated) by a halogen group, The type of halogen group is as described above. Similarly, “a monovalent halogenated oxygen-containing hydrocarbon group” is one in which at least a part of the hydrogen groups of the above-described monovalent oxygen-containing hydrocarbon groups are substituted by a halogen group, and the halogen thereof The type of group is as described above. The “divalent C 1 halogenated hydrocarbon group” is a halogenated methylene group (= CH (X ′) or CXCX ′, where X ′ is a halogen group).

More specifically, a group such as an alkyl group is halogenated, for example, trifluoromethyl group (-CF ₃₎ or a pentafluoroethyl group (-C ₂ F _5), and the like. In addition, the monovalent halogenated oxygen-containing hydrocarbon group is, for example, one in which at least a part of hydrogen groups among the above-mentioned alkoxy groups etc. are substituted by a halogen group. More specifically, a group such as alkoxy group is halogenated, for example, a trifluoromethoxy group (-OCF ₃₎ or penta full ethoxy (-OC ₂ F _5), and the like.

  Specific examples of the unsaturated cyclic carbonate represented by the formula (1) are represented by the following formulas (1-1) to (1-56), and the unsaturated cyclic carbonate also has a geometric isomer included. However, specific examples of the unsaturated cyclic carbonate are not limited to those listed below.

(Content of unsaturated cyclic carbonate)
The content of the unsaturated cyclic carbonate represented by the formula (1) is 0.01% by mass or more and 10% by mass or less with respect to the non-aqueous electrolytic solution, from the viewpoint that a more excellent effect is obtained. The content is preferably 0.02% by mass to 9% by mass, and more preferably 0.03% by mass to 8% by mass.

(Halogenated carbonate ester)
The non-aqueous electrolyte may contain at least one of halogenated carbonates represented by Formula (2) and Formula (3) in place of the unsaturated cyclic carbonate represented by Formula (1). . In addition, the non-aqueous electrolyte may contain at least one of halogenated carbonates represented by Formula (2) and Formula (3), together with the unsaturated cyclic carbonate represented by Formula (1). . That is, the non-aqueous electrolytic solution contains at least one of the unsaturated cyclic carbonate represented by the formula (1) and the halogenated carbonate represented by the formulas (2) and (3).

（式（２）中、Ｒ２１〜Ｒ２４は、それぞれ独立して、水素基、ハロゲン基、アルキル基またはハロゲン化アルキル基であり、Ｒ２１〜Ｒ２４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。）

(In formula (2), R 21 to R 24 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of R 21 to R 24 is a halogen group or a halogenated alkyl group Is)

（式（３）中、Ｒ２５〜Ｒ３０は、それぞれ独立して、水素基、ハロゲン基、アルキル基またはハロゲン化アルキル基であり、Ｒ２５〜Ｒ３０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。）

(In formula (3), R 25 to R 30 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of R 25 to R 30 is a halogen group or a halogenated alkyl group Is)

  The halogenated carbonate represented by Formula (2) is a cyclic carbonate (halogenated cyclic carbonate) containing one or more halogens as a constituent element. The halogenated carbonate represented by Formula (3) is a chain carbonate (halogenated chain carbonate) containing one or more halogens as constituent elements.

  The type of halogen is not particularly limited, but among them, fluorine (F), chlorine (Cl) or bromine (Br) is preferable, and fluorine is more preferable. It is because a higher effect is obtained than other halogens. However, the number of halogens is preferably two rather than one, and may be three or more. This is because the ability to form a protective film is increased, and a stronger and stable protective film is formed, so that the decomposition reaction of the electrolytic solution is further suppressed.

  The halogenated cyclic carbonate represented by Formula (2) is, for example, a compound represented by the following Formula (2-1) to Formula (2-21). However, specific examples of the halogenated carbonate are not limited to those listed below. The halogenated cyclic carbonates also include geometric isomers. Among them, 4-fluoro-1,3-dioxolan-2-one represented by the formula (2-1) or 4,5-difluoro-1,3-dioxolane-2-one represented by the formula (2-3) On is preferred, the latter is more preferred. In addition, as 4,5-difluoro-1,3-dioxolan-2-one, a trans isomer is preferable to a cis isomer. It is because it is easily available and a high effect can be obtained. The halogenated chain carbonate is, for example, fluoromethyl methyl carbonate, bis (fluoromethyl) carbonate or difluoromethyl methyl carbonate. However, specific examples of the halogenated linear carbonate ester are not limited to these.

(Content of halogenated carbonate ester)
The content of the halogenated carbonate represented by the formula (2) and the formula (3) is 0.01% by mass or more and 50% by mass or less with respect to the non-aqueous electrolytic solution, from the viewpoint that a more excellent effect is obtained. Is preferably 0.02 to 25% by mass, and more preferably 0.03 to 10% by mass.

(Solid particles)
As 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 oxides, sulfate compounds, carbonate compounds, metal hydroxides, metal carbides, metal nitrides, metal fluorides, phosphate compounds, minerals and the like. Although particles having electrical insulating properties are typically used as the particles, the surface of the particles (fine particles) of the conductive material is subjected to surface treatment with the electrical insulating material to have electrical insulating properties. You may use the particle (fine particle) made to

As metal oxides, silicon oxide (SiO ₂ , silica (silica powder, silica glass, glass beads, diatomaceous earth, wet or dry synthetic products, etc., wet synthetic products, colloidal silica, dry synthetic products, fumed silica) And 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 a sulfate compound, magnesium sulfate (MgSO ₄ ), calcium sulfate (CaSO ₄ ), barium sulfate (BaSO ₄ ), strontium sulfate (SrSO ₄ ) or the like can be suitably used. The carbonate compound, magnesium carbonate (MgCO _3, magnesite), calcium carbonate (CaCO _3, calcite), barium carbonate (BaCO _3), lithium carbonate (Li ₂ CO ₃₎ or the like can be suitably used. Examples of metal hydroxides include magnesium hydroxide (Mg (OH) ₂ , brucite), aluminum hydroxide (Al (OH) ₃ (Bayerite, 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, hydrated silica), zirconium oxide hydrate _{(ZrO 2 · nH 2 O (} n = 0.5 Hydroxides, such as magnesium oxide hydrate (MgO _a · mH ₂ O (a = 0.8 to 1.2, m = 0.5 to 10)), hydrated oxides, Hydroxide hydrates such as magnesium hydroxide octahydrate can be suitably used. Boron carbide (B ₄ C) or the like can be suitably used as the metal carbide. 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 and the like can be suitably used. As a phosphate compound, trilithium phosphate (Li ₃ PO ₄ ), magnesium phosphate, magnesium hydrogen phosphate, ammonium polyphosphate and the like can be suitably used.

  As minerals, silicate minerals, carbonate minerals, oxide minerals and the like can be mentioned. Silicate minerals are classified into nesosilicate minerals, sorosilicate minerals, cyclosilicate minerals, inosilicate minerals, layered (phylo) silicate minerals, and tectosilicate minerals based on crystal structure. . In addition, some are classified into fibrous silicate minerals called asbestos based on a classification standard different from the crystal structure.

A nesosilicate mineral is an island-like tetrahedral silicate mineral consisting of independent Si-O tetrahedra ([SiO ₄ ] ^4- ). Nesosilicate minerals include those corresponding to olivines and meteorites. The Nesokei minerals, more specifically, magnesium silicate (forsterite (bitter olivine (continuous solid solution of Mg ₂ SiO ₄ (forsterite) and Fe ₂ SiO ₄ (fayalite)) Earth olivine), Mg ₂ SiO ₄ ), aluminum silicate (Al ₂ SiO ₅ , sillimanite, anorthite, kyanite), zinc silicate (zinc 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 ), etc. may be mentioned.

Sorokei minerals is, Si-O tetrahedral double bond group ^{_{([Si 2 O 7] 6-}} , [Si 5 O 16] 12-) a group derived type silicate mineral consisting of. As a solo silicate mineral, a thing applicable to vesuvite, aragonite etc. is mentioned.

The cyclosilicate mineral is a finite (3-6) bonded cyclic ring of Si-O tetrahedron ([Si ₃ O ₉ ] ^6- , [Si ₄ O ₁₂ ] ^8- , [Si ₆ O ₁₈ ] ^{12 -} ) It is a cyclic silicate mineral consisting of As cyclosilicate minerals, an orbolite, tourmaline, etc. are mentioned.

The inosilicate mineral has chain-like ([Si ₂ O ₆ ] ^4- ) and band-like ([Si ₃ O ₉ ] ^6- , [Si ₄ O ₁₁ ] ⁶ ) in which Si-O tetrahedra linkages extend infinitely. ^- , [Si ₅ O ₁₅ ] ^10- , and [Si ₇ O ₂₁ ] ^14- ) are fibrous silicate minerals. Examples of inosilicate minerals include those corresponding to amphibole, such as those corresponding to pyroxenes such as calcium silicate (wollastonite, CaSiO ₃ ) and the like.

Layered silicate minerals are layered silicate minerals that form a network of Si-O tetrahedra ([SiO ₄ ] ^4- ). In addition, the specific example of a layered silicate mineral is mentioned later.

The tectosilicate mineral is a three-dimensional network type silicate mineral in which Si—O tetrahedra ([SiO ₄ ] ⁴⁻ ) form 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.

  Examples of asbestos include chrysotile, amosite and ansophite.

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.

The oxidizing mineral, spinel (MgAl ₂ O _4), and the like.

Other minerals include strontium titanate (SrTiO ₃ ) and the like. The mineral may be a natural mineral or an artificial mineral.

  Among these minerals, there are those classified as clay minerals. Examples of this clay mineral include crystalline clay minerals and non-crystalline or quasi-crystalline clay minerals. Examples of crystalline clay minerals include layered silicate minerals, those having a structure close to layered silicates, silicate minerals such as other silicate minerals, and layered carbonate minerals.

  The layered silicate mineral comprises a tetrahedral sheet of Si--O and an octahedral sheet of Al--O, Mg--O, etc. in combination with the tetrahedral sheet. Layered silicates are typically classified according to the number of tetrahedral and octahedral sheets, the number of octahedral cations, and the layer charge. The layered silicate mineral may be, for example, one in which all or part of metal ions in the interlayer is substituted with organic ammonium ion or the like.

  Specifically, as layered silicate minerals, there are 1: 1 structure of kaolinite-serpentine group, 2: 1 structure of pyrophyllite-talc group, smectite group, vermiculite group, mica (mica) group And those which fall under the category of brito mica (brittle mica), chlorite (chlorite) and the like.

Examples of the kaolinite-serpentine group include chrysotile, antigorite, lizardite, kaolinite (Al ₂ Si ₂ O ₅ (OH) ₄ ), dickite and the like. The pyrophyllite-talc group includes, for example, talc (Mg ₃ Si ₄ O ₁₀ (OH) ₂ ), willemsite, pyrophyllite (pyrophyllite, Al ₂ Si ₄ O ₁₀ (OH) ₂ Etc.). As a material corresponding to the smectite group, for example, saponite [(Ca / 2, Na) _0.33 (Mg, Fe ²⁺ ) ₃ (Si, Al) ₄ O ₁₀ (OH) ₂ .4 H ₂ O], hectorite, Sauconite, montmorillonite {(Na, Ca) _0.33 (Al, Mg) 2 Si ₄ O ₁₀ (OH) ₂ · n H ₂ O, and clay containing montmorillonite as its main component is referred to as bentonite}, beidellite, nontrite, etc. . As the mica (mica) group, for example, moskovite (white mica, KAl ₂ (AlSi ₃ ) O ₁₀ (OH) ₂ ) sericite (sericite), phlogopite (phlogopite), biotite, lepidolite ( Lithia micas etc. are mentioned. Examples of the group corresponding to the Brithol mica (brittle mica) group include margarite, clintonite, anandite and the like. As a thing applicable to the chlorite (chlorite) family, there are, for example, cushione, sudoite, clinochlor, chamosite, nimite and the like.

As a layered silicate-like structure, a hydrous magnesium silicate having a 2: 1 ribbon structure in which a ribbon-shaped tetrahedral sheet is connected to a next ribbon-shaped tetrahedral sheet while its apex is reversed. Etc. Examples of hydrous magnesium silicates include sepiolite (Naphthalene: 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 aluminosilicates, attapulgite _{[(Mg, Al) 2Si 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 non-crystalline or quasi-crystalline clay minerals include vengerite, imogolite (Al ₂ SiO ₃ (OH)), allophane and the like.

  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 also have high resistance to the 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, crosslinked polymethyl methacrylate (crosslinked PMMA), polyolefin, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamide, polyimide And melamine resins, phenol resins, epoxy resins and the like. These materials may be used alone or in combination of two or more.

  Among these solid particles, particles of boehmite, aluminum hydroxide, magnesium hydroxide and silicate are preferable in terms of obtaining more excellent effects. In these solid particles, the bias of the battery due to -O-H arranged in a sheet shape in the crystal structure strongly attracts the additive selectively, thereby more effectively adding the additive to the depression between the active material particles Can be concentrated.

(Configuration inside the battery)
FIGS. 3A and 3B are enlarged schematic cross-sectional views of a part of the inside of the nonaqueous electrolyte battery according to the first embodiment of the present technology. In addition, illustration of the binder contained in an active material layer, a conductive agent, etc. is abbreviate | omitted.

  As shown in FIG. 3A, in the non-aqueous electrolyte battery according to the first embodiment of the present technology, the solid particles described above are disposed between the separator 55 and the negative electrode active material layer 54B and inside the negative electrode active material layer 54B. A particle 10 has a configuration in which it is disposed in an appropriate area at an appropriate concentration. In this configuration, three regions divided into the depression impregnation region A on the negative electrode side, the upper coating region B on the negative electrode side, and the deep region C on the negative electrode side are formed.

  Similarly, as shown in FIG. 3B, in the non-aqueous 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, which are the solid particles described above, have a configuration in which they are disposed in appropriate regions at appropriate concentrations. In this configuration, three regions divided into the depression impregnation region A on the positive electrode side, the upper coating region B on the positive electrode side, and the deep region C on the positive electrode side are formed.

(Depression impregnation area A, top coat area B, deep area C)
The depression impregnation region A on the negative electrode side and the positive electrode side, the upper coating 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, for example.

(Depression impregnation area A)
(Depression impregnation area on the negative electrode side)
The hollow impregnated region A on the negative electrode side is a region including a hollow 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 which are negative electrode active materials. The hollow impregnation region A includes the particle 10 and at least one of the unsaturated cyclic carbonate represented by the formula (1), and the halogenated carbonate represented by the formula (2) and the formula (3). The electrolyte is impregnated. Thus, the hollow impregnation region A on the negative electrode side is at least one of the unsaturated cyclic carbonate represented by the formula (1) and the halogenated carbonate represented by the formula (2) and the formula (3). Filled with electrolyte containing. Further, the hollow impregnation 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 electrolytic solution.

  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 the negative electrode impregnated impregnation region A including the recesses in which the electrolyte and the particles 10 are disposed. 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 viewing width (typically, the viewing width 50 μm) as shown in FIG. 3A. In this observation field of view, 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 of the cross-sectional image of the negative electrode active material particle 11. The parallel line L2 is a line passing through the deepest portion of the cross-sectional image of the particles 10 included in the depression between the adjacent negative electrode active material particles 11. The deepest portion refers to the position farthest from the separator 55 in the thickness direction of the separator 55. The cross-sectional observation can be performed using, for example, a scanning electron microscope (SEM).

(Depression impregnation area on the positive electrode side)
The depression impregnation area A on the positive electrode side is an area including depressions 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 which are positive electrode active materials. In the hollow impregnation region A, particles 10 which are solid particles and an unsaturated cyclic carbonate represented by the formula (1), and at least at least a halogenated carbonate represented by the formulas (2) and (3) The electrolyte containing 1 type is impregnated. Thus, the depression impregnation region A on the positive electrode side is at least one of the unsaturated cyclic carbonate represented by the formula (1) and the halogenated carbonate represented by the formula (2) and the formula (3). Filled with electrolyte containing. In addition, particles 10 are contained as solid particles contained in the electrolyte in the depression impregnation region A on the positive electrode side. The electrolyte may be a gel electrolyte or a liquid electrolyte composed of a non-aqueous electrolytic solution.

  The region excluding the cross section of the positive electrode active material particle 12 in the region between the two parallel lines L1 and L2 shown in FIG. 3B is a depression impregnated region A on the positive electrode side including the recess in which the electrolyte and the particles 10 are disposed. 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 positive electrode active material layer 53B and the separator 55 and the positive electrode active material layer 53B is observed with a predetermined viewing width (typically, the viewing width 50 μm) as shown in FIG. 3B. In this observation field of view, 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 of the cross-sectional image of the positive electrode active material particle 12. The parallel line L2 is a line passing 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 the position farthest from the separator 55 in the thickness direction of the separator 55.

(Top coat area B)
(Top coat area on the negative electrode side)
The upper-coated area B on the negative electrode side is an area between the hollow impregnated area A on the negative electrode side and the separator 55. The overcoat area B is filled with an electrolyte containing at least one of an unsaturated cyclic carbonate represented by the formula (1) and a halogenated carbonate represented by the formulas (2) and (3). There is. The overcoating region B includes particles 10 which are solid particles contained in the electrolyte. In addition, the particles 10 may not be contained in the top coat region B. 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 a top coated region B on the negative electrode side.

(Top coat area on the positive electrode side)
The upper-coated area B on the positive electrode side is an area between the depression impregnation area A on the positive electrode side and the separator 55. The overcoat area B is filled with an electrolyte containing at least one of an unsaturated cyclic carbonate represented by the formula (1) and a halogenated carbonate represented by the formulas (2) and (3). There is. The overcoating region B includes particles 10 which are solid particles contained in the electrolyte. In addition, the particles 10 may not be contained in the top coat region B. A region between the above-described parallel line L1 and the separator 55 included in the same predetermined observation field of view shown in FIG. 3B is divided as a top coated 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 that is deeper than the depression impregnation region A on the negative electrode side. In the gaps between the negative electrode active material particles 11 in the deep region C, at least the unsaturated carbonate represented by the formula (1), and at least the halogenated carbonate represented by the formulas (2) and (3) An electrolyte containing one type is filled. The deep region C contains the particles 10 contained in the electrolyte. The deep region C may not contain the particle 10.

  Regions of the negative electrode active material layer 54B other than the depression-impregnated region A and the overcoated region B included in the same predetermined observation visual field shown in FIG. 3A are divided as the 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 that is deeper than the depression impregnation region A on the positive electrode side. In the gaps between the positive electrode active material particles 12 in the deep region C on the positive electrode side, unsaturated carbonate ester represented by the formula (1), and halogenated carbonate represented by the formulas (2) and (3) An electrolyte comprising at least one of the esters is filled. The deep region C contains the particles 10 contained in the electrolyte. The deep region C may not contain the particle 10.

  Regions of the positive electrode active material layer 53B other than the depression-impregnated region A and the overcoated region B included in the same predetermined observation visual field shown in FIG. 3B are divided as the 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 field shown in FIG. 3B is divided as a deep region C on the positive electrode side.

(Concentration of solid particles)
The solid particle concentration of the hollow impregnation 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 hollow impregnation region A on the negative electrode side is in the above range, more solid particles are arranged by the depression between adjacent particles in which many cracks appear, and the solid particle is represented by the formula (1) The unsaturated cyclic carbonate (or a compound derived therefrom) and at least one of the halogenated carbonates represented by the formulas (2) and (3) are captured, and the additive is between adjacent active material particles. It becomes easy to stagnate in a hollow. For this reason, the content ratio of the additive in the depression between adjacent particles can be made higher than that in the other portion, whereby an effective film can be formed against the cracks generated in the active material particles. As a result, it is possible to realize a high capacity battery with less cycle degradation of high output discharge. The unsaturated cyclic carbonate represented by the formula (1) in the electrolyte, and at least one of the halogenated carbonates represented by the formulas (2) and (3) are selectively collected in the crack portion. Therefore, the effect of at least one of the unsaturated cyclic carbonate represented by the formula (1) and the halogenated carbonate represented by the formulas (2) and (3) can be minimized. It can be obtained by the addition amount. In addition, by collecting at least one of an unsaturated cyclic carbonate represented by the formula (1) and a halogenated carbonate represented by the formulas (2) and (3) selectively in the crack portion, Since the formation of a film other than the cracked part is suppressed, the unsaturated cyclic carbonate represented by the formula (1) formed by the part other than the cracked part, and the formula (2) and the formula even if the addition amount is increased It is also possible to suppress the increase in resistance and the like by the film derived from at least one of the halogenated carbonates represented by (3).

  Although the function and effect are different from the above, the solid particle concentration of the depression impregnation area A on the positive electrode side is 30% by volume or more and 30% by volume or more and 90% by volume or less from the viewpoint of obtaining more excellent effect. Is preferably 40% by volume to 80% by volume. When the solid particle concentration in the depression impregnation region A on the positive electrode side is in the above range, more solid particles are arranged in the depressions between adjacent particles in which many cracks appear, and Unsaturated cyclic carbonate (or a compound derived therefrom), and at least one of halogenated carbonates represented by Formula (2) and Formula (3) are captured, and the additive is a positive electrode active material layer The depressions between adjacent positive electrode active material particles located on the outermost surface of the For this reason, the unsaturated cyclic carbonate represented by the formula (1), and the formula (2) and the formula (3) in the deep area C on the positive electrode side and the deep area C on the negative electrode side where side reactions occur. Migration of at least one of the represented halogenated carbonates can be further suppressed. In the negative electrode, at least a crack formed in the negative electrode active material particles, the unsaturated cyclic carbonate represented by the formula (1), and the halogenated carbonate represented by the formula (2) and the formula (3) When consumption of one type proceeds, the unsaturated cyclic carbonate represented by the formula (1) stagnated and accumulated in the depression between adjacent active material particles on the positive electrode side, and the formulas (2) and (5) At least one kind of the halogenated carbonate represented by 3) can be supplied to the depression between adjacent active material particles on the negative electrode side.

  The solid particle concentration of the hollow impregnation region A on the negative electrode side is preferably at least 10 times the solid particle concentration of the deep region C on the negative electrode side. The particle concentration of the deep region C on the negative electrode side is preferably 3% by volume or less. If the solid particle concentration in the deep region C on the negative electrode side is too high, there will be too many solid particles between the active material particles, which may cause resistance or cause a side reaction of the trapped additive, resulting in internal resistance It will increase.

  For the same reason, it is preferable that the solid particle concentration of the depression impregnation region A on the positive electrode side is 10 times or more of the solid particle concentration of the deep region C on the positive electrode side. The particle concentration of the deep region C on the positive electrode side is preferably 3% by volume or less. If the solid particle concentration in the deep region C on the positive electrode side is too high, there will be too much between active material particles, which may cause resistance or cause a side reaction of the trapped additive to increase internal resistance. .

(Solid particle concentration)
The solid particle concentration mentioned above is the area percentage of the total area of the particle cross section when the observation field of view of 2 μm × 2 μm is taken ((“total area of particle cross section” ÷ “area of observation field”) × 100) (%) It refers to the volume concentration (volume%) of solid particles defined by In addition, when defining the density | concentration of hollow impregnation area | region A, the said observation visual field is taken, for example in center vicinity of the width direction of the hollow formed between adjacent particle | grains. The observation is performed using, for example, an SEM, and the above-described respective areas can be calculated by processing an image acquired by imaging.

(Thickness of depression impregnation area A, thickness B of overcoat area, thickness C of deep area)
The thickness of the hollow impregnation region A on the negative electrode side is preferably 10% to 40% of the thickness of the negative electrode active material layer 54. When the thickness of the hollow impregnation region A on the negative electrode side is in the above range, the necessary amount of solid particles to be disposed in the hollow can be ensured and the state in which the additive does not excessively enter the deep region C can be maintained. . Furthermore, the thickness of the depression-impregnated region A on the negative electrode side is more preferably in the above range and at least twice the thickness of the top-coated region B on the negative electrode side. This is because the energy density can be further improved by preventing the distance between the electrodes from expanding. Further, for the same reason, the thickness of the depression impregnation region A on the positive electrode side is more preferably twice or more the thickness of the top coating region B on the positive electrode side.

(How to measure the thickness of each area)
When defining the thickness of the depression impregnation region A, the average value of the thickness of the depression impregnation region A in four different observation fields of view is taken as the thickness of the depression impregnation region A. When defining the thickness of the overcoat area B, the average value of the thicknesses of the overcoat area B in four different observation fields of view is taken as the thickness of the overcoat area B. When defining the thickness of the deep region C, an average value of the thicknesses of the deep regions C in four different observation fields of view is taken as the thickness of the deep region C.

(Particle diameter of solid particles)
The particle diameter of the solid particles is preferably such that the particle diameter D50 is equal to or less than 2 / √3-1 of 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. The particle diameter of the solid particles is preferably such that the particle diameter D95 is equal to or greater than "2 // 3-1" times the particle diameter D50 of the active material particles. It is possible to close the gap between the adjacent active material particles at the bottom of the recess with the particle having the larger particle diameter, and to suppress the solid particle from excessively entering the deep region C and adversely affecting the battery characteristics.

(Measurement of particle size)
The particle diameter D50 of the solid particles is, for example, calculated from the particle side of the smaller particle diameter in the particle size distribution of solid particles after removing constituents other than solid particles from the electrolyte containing solid particles and the like by the laser diffraction method. It is the particle diameter of 50% of the accumulated volume. Moreover, the value of the particle diameter D95 of 95% of the volume total can be obtained from the particle size distribution measured above. The particle size D50 of the active material is determined by using a particle size distribution of particles of the active material after removing constituents other than the active material particle from the active material layer containing the active material particles by a laser diffraction method. Particle diameter of 50% of 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 the 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 within the above numerical range, the unsaturated cyclic carbonate represented by the formula (1), and the halogenated carbonate represented by the formula (2) and the formula (3) in which the solid particles are represented by the formula (1) It is preferable because the action of capturing at least one species is enhanced. On the other hand, when the BET specific surface area is too large, even lithium ions are trapped, so the output characteristics tend to be deteriorated. In addition, for example, it can obtain by measuring about solid particles after removing components other than solid particles from electrolyte etc. which contain solid particles like the above.

(A configuration having a depression impregnation area A, a top coat area B, and a deep area C only on the negative electrode side)
Although described later, the electrolyte layer 56 containing solid particles may be formed only on both main surfaces of the negative electrode 54, and the electrolyte layer containing no solid particles on both main surfaces of the positive electrode 54. 56 may be applied and formed. In these cases, only the hollow impregnation region A on the negative electrode side, the upper coating 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. In the present technology, the hollow impregnation region A on the negative electrode side, the upper coating region B on the negative electrode side, and the deep region C on the negative electrode side may be formed only at least on the negative electrode side.

(1-2) Method of Manufacturing an Example of Nonaqueous Electrolyte Battery An example of this nonaqueous electrolyte battery can be manufactured, for example, as follows.

(Method of manufacturing positive electrode)
A positive electrode active material, a conductive agent, and a binder are mixed to prepare a positive electrode mixture, and this positive electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to form a paste-like positive electrode mixture slurry. Make Next, the positive electrode mixture slurry is applied to the positive electrode current collector 53A, the solvent is dried, and compression molding is performed using a roll press machine or the like to form the positive electrode active material layer 53B, thereby producing the positive electrode 53.

(Method of manufacturing negative electrode)
A negative electrode active material and a binder are mixed to prepare a negative electrode mixture, and this negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to prepare a paste-like negative electrode mixture slurry. Next, the 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 using a roll press machine or the like to produce the negative electrode 54.

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

(Solution application)
A coating solution containing a non-aqueous electrolytic solution, a matrix polymer compound, solid particles, and a dilution solvent (such as dimethyl carbonate) was applied in a heated state to both main surfaces of each of the positive electrode 53 and the negative electrode 54 Thereafter, the diluted solvent is evaporated to form the electrolyte layer 56.

  By applying the coating solution in a heated state, the electrolyte containing the solid particles is applied to the depression between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer 54B and the deep region C inside the negative electrode active material layer 54B. It can be soaked. At this time, the solid particles are strained by the depressions between adjacent particles, whereby the particle concentration in the depression impregnation region A on the negative electrode side is increased. Thereby, a difference can be provided between the particle concentration of the depression impregnation region A and the deep region C. Similarly, by applying the coating solution in a heated state, a recess between adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer 53B and an inner portion of the positive electrode active material layer 53B are formed. Region C can be impregnated. At this time, the solid particles are strained by the depressions between adjacent particles, whereby the particle concentration in the depression impregnation region A on the positive electrode side is increased. Thereby, a difference can be provided between the particle concentration of the depression impregnation region A and the deep region C. As solid particles, it is preferable to use those in which the particle diameter D95 of the solid particles is adjusted to a predetermined magnification or more of the particle diameter D50 of the active material particles. For example, as solid particles, solid particles of 2 // 3-1 times or more the particle diameter D50 of active material particles are added to a part of solid particles, and the particle diameter D95 of solid particles is the particle diameter D50 of active material particles It is preferable to use one adjusted to be 2 / 23-1 times or more of. In this way, it is possible to fill the gaps between the particles at the bottom of the recess with some of the solid particles with the larger particle size, making it easier for the solid particles to be shredded.

  In addition, if an excess coating solution is scraped off after apply | coating a coating solution, the distance between electrodes can be prevented from spreading carelessly. In addition, by scraping the surface of the coating solution, more solid particles can be arranged in the depressions between adjacent active material particles, and the ratio of solid particles in the overcoated area A is lowered. Thereby, most of the solid particles are intensively disposed in the hollow impregnation region A, and the unsaturated cyclic carbonate represented by the formula (1), and the halogen represented by the formulas (2) and (3) At least one kind of carbonic acid ester can be gathered more in the vicinity of the crack generated in the active material particles.

  The following may be done. A coating solution (coating solution excluding particles) containing a non-aqueous electrolytic solution, a matrix polymer compound, and a dilution solvent (such as dimethyl carbonate) is coated on both main surfaces of the positive electrode 53 to contain solid particles. An electrolyte layer 56 may be formed. Alternatively, the electrolyte layer 56 may not be formed on one main surface or both main surfaces of the positive electrode 53, and the electrolyte layer 56 containing similar solid particles may be formed only on 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 stacked via the separator 55 to form a laminate, and then the laminate is wound in the longitudinal direction. A protective tape 57 is adhered to the outermost periphery to form a wound electrode body 50.

  Finally, for example, the wound electrode body 50 is sandwiched between the package members 60, and the outer edge portions of the package members 60 are closely attached by heat fusion or the like and sealed. At this time, the adhesive film 61 is inserted between the positive electrode lead 51 and the negative electrode lead 52 and the package member 60. Thereby, the nonaqueous electrolyte battery shown in FIG. 1 and FIG. 2 is completed.

[Modification 1-1]
The non-aqueous electrolyte battery according to the first embodiment may be manufactured as follows. In this production method, in place 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 non-aqueous electrolyte battery, both coating solutions are used as the separator 55. The method is the same as the method of manufacturing an example of the non-aqueous electrolyte battery described above, except that it is formed on at least one of the main surfaces of the main surface, and then the heating and pressurizing steps are further performed.

[Method of Manufacturing Nonaqueous Electrolyte Battery of Modification 1-1]
(Production of positive electrode, negative electrode, separator, preparation of non-aqueous electrolyte)
The production of the positive electrode 53, the negative electrode 54 and the separator 55, and the preparation of the non-aqueous electrolyte are carried out in the same manner as in the method for producing an example of the non-aqueous electrolyte battery.

(Solution application)
A coating solution containing a non-aqueous electrolytic solution, a matrix polymer compound, solid particles, and a dilution solvent (such as dimethyl carbonate) is applied to at least one of the main surfaces of both surfaces of the separator 55, and It is volatilized to form an electrolyte layer 56.

(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, the negative electrode 54, and the separator 55 on which the electrolyte layer 56 is formed are laminated to form a laminated body, and the laminated body is wound in the longitudinal direction to form a protective tape 57 on the outermost periphery. Are bonded to form a wound electrode body 50.

(Heating and pressurizing process)
Next, the wound electrode body 50 is placed in a packaging material such as a tube of latex, sealed, and heated and pressed under hydrostatic pressure. Thereby, the solid particles are moved to the depressions between the adjacent negative electrode active material particles positioned on the outermost surface of the negative electrode active material layer 54B, 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 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 impregnation 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, and the wound electrode body 50 is inserted into the recess, and the unprocessed portion of the exterior member 60 is folded over the recess to form the outer periphery of the recess. Heat weld. At this time, the adhesive film 61 is inserted between the positive electrode lead 51 and the negative electrode lead 52 and the package member 60. Thus, the target nonaqueous electrolyte battery can be obtained.

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

[Method of Manufacturing Nonaqueous Electrolyte Battery of Modification 1-2]
(Preparation of positive electrode, negative electrode, non-aqueous electrolyte)
The production of the positive electrode 53 and the negative electrode 54 and the preparation of the non-aqueous electrolyte are carried out in the same manner as in the method for producing an example of the non-aqueous electrolyte battery.

(Coating formation of solid particle layer)
Next, a paint is applied on at least one of the two main surfaces of the negative electrode 54 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 54B on which the solid particle layer is applied and formed, the solid particles are strained by the depressions between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer 54B. The particle concentration in the impregnation zone A is increased. Similarly, the same paint as described above is applied onto both main surfaces of the positive electrode 53 by a coating method or the like, and then the solvent is removed by drying to form a solid particle layer. At 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 strained by the depressions between adjacent positive electrode active material particles positioned on the outermost surface of the positive electrode active material layer 54B. The particle concentration in the impregnation zone A is increased. As solid particles, for example, it is preferable to use those adjusted so that the particle diameter D95 of the solid particles is equal to or more than a predetermined magnification of the particle diameter D50 of the active material particles. For example, as solid particles, solid particles of 2 // 3-1 times or more the particle diameter D50 of active material particles are added to a part of solid particles, and the particle diameter D95 of solid particles is the particle diameter D50 of active material particles It is preferable to use one adjusted to be 2 / 23-1 times or more of. This allows the particles with the larger particle size to fill the gaps between the particles at the bottom of the recess, making it easier for the solid particles to be crimped.

  In addition, at the time of coating formation of the solid particle layer, if the excess paint is scraped off, the distance between the electrodes can be prevented from inadvertently expanding. Further, by scraping the surface of the paint, more solid particles can be disposed in the depressions between adjacent active material particles, and the ratio of solid particles in the overcoated area A is lowered. As a result, the unsaturated cyclic carbonate ester represented by the formula (1), and the halogenation represented by the formula (2) and the formula (3), in which most of the solid particles are intensively disposed in the hollow impregnation area At least one kind of carbonate ester can be made to gather more in the vicinity of the crack generated in the active material particles.

(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 and the negative electrode 54 are stacked via the separator 55 and wound, and the protective tape 57 is adhered to the outermost peripheral portion to form a wound body which is a precursor of the wound electrode body 50. Next, the wound body is sandwiched by the exterior member 60, and the outer peripheral edge excluding one side is heat-sealed to form a bag, which is housed inside the exterior member 60.

  Next, a non-aqueous electrolyte solution is injected into the inside of the package member 60, and the non-aqueous electrolyte solution is impregnated in the wound body, and then the opening of the package member 60 is heat-sealed in a vacuum atmosphere and sealed. Thus, the target non-electrolyte secondary battery can be obtained.

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

[Method of Manufacturing Nonaqueous Electrolyte Battery of Modification 1-3]
(Production of positive electrode and negative electrode)
The positive electrode 53 and the negative electrode 54 are manufactured in the same manner as the manufacturing method of one example of the non-aqueous electrolyte battery.

(Coating formation of solid particle layer)
Next, in the same manner as in Modification Example 1-2, a solid particle layer is formed on at least one of the 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 a composition for electrolyte)
Next, a composition for electrolyte is prepared, which includes a non-aqueous electrolytic solution, a monomer as a raw material of a polymer compound, a polymerization initiator, and, if necessary, other materials such as a polymerization inhibitor.

(Assembly of non-aqueous electrolyte battery)
Next, in the same manner as the modification 1-2, a wound body which is a precursor of the wound electrode body 50 is formed. Next, the wound body is sandwiched by the exterior member 60, and the outer peripheral edge excluding one side is heat-sealed to form a bag, which is housed inside the exterior member 60.

  Next, the composition for electrolyte is injected into the inside of the bag-like exterior member 60, and then 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. As a result, a polymer compound is formed, whereby the electrolyte layer 56 is formed. From the above, the target nonaqueous electrolyte battery can be obtained.

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

[Method of Manufacturing Nonaqueous Electrolyte Battery of Modification 1-4]
(Production of positive electrode, negative electrode, preparation of non-aqueous electrolyte)
First, manufacturing of the positive electrode 53 and the negative electrode 54 and preparation of a non-aqueous electrolyte are performed in the same manner as in the example of the method for manufacturing the non-aqueous electrolyte battery.

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

(Coating formation of matrix resin layer)
Next, a coating solution containing a non-aqueous electrolytic solution, a matrix polymer compound, and a dispersion solvent such as N-methyl-2-pyrrolidone is applied to at least one of the two main surfaces of the separator 55. After drying, the matrix resin layer is formed by drying or the like.

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

  Next, a recess is formed by deep drawing the exterior member 60 made of a laminate film, and the wound electrode body 50 is inserted into the recess, and the unprocessed portion of the exterior member 60 is folded over the recess, and the outer periphery of the recess Heat welding is performed except for a part (for example, one side) of At this time, the adhesive film 61 is inserted between the positive electrode lead 51 and the negative electrode lead 52 and the package member 60.

  Subsequently, the non-aqueous electrolytic solution is injected into the inside from the unwelded portion of the exterior member 60, and the unwelded portion of the exterior member 60 is sealed by heat fusion or the like. At this time, the non-aqueous electrolytic solution is impregnated into the matrix resin layer by vacuum sealing, and the matrix polymer compound is swelled to form the electrolyte layer 56. Thereby, the target non-aqueous electrolyte battery is obtained.

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

[Method of Manufacturing Nonaqueous Electrolytic Battery of Modification 1-5]
(Production of positive electrode, negative electrode, preparation of non-aqueous electrolyte)
First, manufacturing of the positive electrode 53 and the negative electrode 54 and preparation of the non-aqueous electrolyte are performed in the same manner as in the example of the method of manufacturing the non-aqueous electrolyte battery.

(Formation of solid particle layer)
Next, a paint is applied on at least one of the main surfaces of the separator 55 by a coating method or the like, and 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 (resin) and a solvent can be used.

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

(Heating and pressurizing process)
Next, before injecting the electrolytic solution into the exterior member 60, the wound body is put in a packaging material such as a tube of latex and sealed, and the heating press is performed under hydrostatic pressure. Thereby, the solid particles are moved to the depressions between the adjacent negative electrode active material particles positioned on the outermost surface of the negative electrode active material layer 54B, 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 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 impregnation region A on the positive electrode side is increased.

  Next, the wound body is sandwiched by the exterior member 60, and the outer peripheral edge excluding one side is heat-sealed to form a bag, which is housed inside the exterior member 60. Next, a non-aqueous electrolyte is prepared, injected into the inside of the exterior member 60, impregnated with the non-aqueous electrolyte into the wound body, and thermally fused the opening of the exterior member 60 in a vacuum atmosphere. Seal it. Thus, the target nonaqueous electrolyte battery can be obtained.

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

[Method of Manufacturing Nonaqueous Electrolyte Battery of Modification 1-6]
(Production of positive electrode and negative electrode)
First, the positive electrode 53 and the negative electrode 54 are manufactured in the same manner as in the example of the method of manufacturing the non-aqueous electrolyte battery.

(Preparation of a composition for electrolyte)
Next, a composition for electrolyte is prepared, which includes a non-aqueous electrolytic solution, a monomer as a raw material of a polymer compound, a polymerization initiator, and, if necessary, other materials such as a polymerization inhibitor.

(Formation of solid particle layer)
Next, in the same manner as in the modification 1-5, a solid particle layer is formed on at least one of the two main surfaces of the separator 55.

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

(Heating and pressurizing process)
Next, before injecting the non-aqueous electrolytic solution into the inside of the exterior member 60, the wound body is put in a packaging material such as a tube of latex and sealed, and hot pressing is performed under hydrostatic pressure. Thereby, the solid particles are moved to the depressions between the adjacent negative electrode active material particles positioned on the outermost surface of the negative electrode active material layer 54B, 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 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 impregnation region A on the positive electrode side is increased.

  Next, the wound body is sandwiched by the exterior member 60, and the outer peripheral edge excluding one side is heat-sealed to form a bag, which is housed inside the exterior member 60.

  Next, the composition for electrolyte is injected into the inside of the bag-like exterior member 60, and then 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. As a result, a polymer compound is formed, whereby the electrolyte layer 56 is formed. From the above, the target nonaqueous electrolyte battery can be obtained.

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

[Method of Manufacturing Nonaqueous Electrolyte Battery of Modification 1-7]
(Production of positive electrode and negative electrode)
First, the positive electrode 53 and the negative electrode 54 are manufactured in the same manner as the method of manufacturing an example of the non-aqueous electrolyte battery. Next, the solid particles and the matrix polymer compound are applied to at least one of the two main surfaces of the separator 55 and then dried to form a matrix resin layer.

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

(Heating and pressurizing process)
Next, the wound electrode body 50 is placed in a packaging material such as a tube of latex, sealed, and heated and pressed under hydrostatic pressure. Thereby, the solid particles are moved to the depressions between the adjacent negative electrode active material particles positioned on the outermost surface of the negative electrode active material layer 54B, 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 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 impregnation region A on the positive electrode side is increased.

  Next, a recess is formed by deep drawing the exterior member 60 made of a laminate film, and the wound electrode body 50 is inserted into the recess, and the unprocessed portion of the exterior member 60 is folded over the recess, and the outer periphery of the recess Heat welding is performed except for a part (for example, one side) of At this time, the adhesive film 61 is inserted between the positive electrode lead 51 and the negative electrode lead 52 and the package member 60.

  Subsequently, the non-aqueous electrolytic solution is injected into the inside from the unwelded portion of the exterior member 60, and the unwelded portion of the exterior member 60 is sealed by heat fusion or the like. At this time, the non-aqueous electrolytic solution is impregnated into the matrix resin layer by vacuum sealing, and the matrix polymer compound is swelled to form the electrolyte layer 56. Thereby, the target non-aqueous electrolyte battery is obtained.

[Modification 1-8]
Although the non-aqueous electrolyte battery in which the wound electrode body 50 is packaged by the exterior member 60 has been described in the example of the first embodiment described above and the modified examples 1-1 to 1-7, FIG. 4A to FIG. 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 non-aqueous electrolyte battery in which the stacked electrode assembly 70 is accommodated. FIG. 4B is an exploded perspective view showing how the laminated electrode body 70 is accommodated in the exterior member 60. As shown in FIG. FIG. 4C is an external view showing an appearance from the bottom side of the nonaqueous electrolyte battery shown in FIG. 4A.

  The stacked electrode body 70 uses the stacked electrode body 70 in which the rectangular positive electrode 73 and the rectangular negative electrode 74 are stacked via the rectangular separator 75 and fixed by the 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 similar to the electrolyte layer 56 described above. The positive electrode lead 71 connected to the positive electrode 73 and the 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 and the negative electrode lead 72 adhere closely to the package member 60. A film 61 is provided.

  In the manufacturing method of the non-aqueous electrolyte battery, the wound electrode body 70 is replaced with a laminated electrode body, and the wound body is replaced with a laminated body (a structure in which the electrolyte layer is omitted from the laminated electrode body 70) The manufacturing method of the non-aqueous electrolyte battery of the first embodiment and the modified example 1-1 to the modified example 1-7 is the same as the manufacturing method of the first embodiment described above except that

2. Second Embodiment In a second embodiment of the present technology, a cylindrical non-aqueous electrolyte battery (battery) will be described. The non-aqueous electrolyte battery is, for example, a non-aqueous electrolyte secondary battery capable of charging and discharging, and is, for example, a lithium ion secondary battery.

(2-1) Configuration of Example of Nonaqueous Electrolyte Battery FIG. 5 is a cross-sectional view showing an example of the nonaqueous electrolyte battery according to the second embodiment. The non-aqueous electrolyte battery is, for example, a non-aqueous electrolyte secondary battery capable of charging and discharging. This non-aqueous electrolyte battery is a so-called cylindrical type, and is formed in a strip shape with a liquid non-aqueous electrolyte (hereinafter suitably referred to as a non-aqueous electrolyte) (not shown) inside a substantially hollow cylindrical battery can 81. A wound electrode body 90 in which the positive electrode 91 and the negative electrode 92 are wound via a separator 93 is provided.

  The battery can 81 is made of, for example, iron plated with nickel, and one end thereof is closed and the other end is opened. Inside the battery can 81, a pair of insulating plates 82a and 82b are disposed perpendicularly to the winding circumferential surface so as to sandwich the winding electrode body 90.

  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 the electrochemical non-aqueous electrolyte associated with charging and discharging of the non-aqueous electrolyte battery. At the open end of the battery can 81, a battery cover 83 which is a positive electrode lead plate, a safety valve mechanism and a positive temperature coefficient element (PTC element: Positive Temperature Coefficient) 87 provided inside the battery cover 83 are sealed with an insulating seal. Is attached by being crimped through a gasket 88.

  The battery lid 83 is made of, for example, the same material as the battery can 81, and is provided with an opening for discharging the gas generated inside the battery. In the safety valve mechanism, a safety valve 84, a disk holder 85 and a blocking disk 86 are sequentially stacked. The projecting portion 84 a of the safety valve 84 is connected to the positive electrode lead 95 drawn from the wound electrode body 90 through a sub disc 89 disposed so as to cover the hole 86 a provided at the center of the blocking disc 86. . By connecting the safety valve 84 and the positive electrode lead 95 via the sub disc 89, it is possible to prevent the positive electrode lead 95 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 cover 83 via the thermal resistance element 87.

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

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

  Further, for example, a plurality of degassing holes (not shown) are provided around the hole 86a of the blocking disc 86, and when gas is generated from the wound electrode body 90, the gas is effectively covered by the battery cover It can be discharged to the 83 side.

  When the temperature rises, the resistance value of the heat sensitive resistance element 87 increases, and the electric connection between the battery cover 83 and the spirally wound electrode body 90 is cut off to cut off the current, and abnormal heat generation due to excessive current is caused. To prevent. The gasket 88 is made of, for example, an insulating material, and the surface is coated with asphalt.

  The wound electrode body 90 housed in the non-aqueous electrolyte battery is wound around the center pin 94. The wound electrode body 90 is formed by sequentially laminating the positive electrode 91 and the negative electrode 92 via the separator 93 and winding in the longitudinal direction. The positive electrode lead 95 is connected to the positive electrode 91, and the 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 the battery can 81 and electrically connected.

  FIG. 6 is an enlarged view of a 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]
The positive electrode 91 is obtained by forming a positive electrode active material layer 91B containing a positive electrode active material 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 91B is configured to include, as a positive electrode active material, any one or two or more of positive electrode materials capable of inserting and extracting lithium, and as necessary, a binder. Other materials such as a conductive agent may be included. The positive electrode active material, the conductive agent, and the binder may 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 desirably in the form of metal foil or mesh, but it is electrochemically and chemically stable, and it is not a metal as long as it can be conducted without problems. 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 sides of a negative electrode current collector 92A having a pair of facing surfaces. Although not shown, the negative electrode active material layer 92B may be provided only on one side 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 is configured to include any one or two or more negative electrode materials capable of inserting and extracting lithium as a negative electrode active material, and as necessary, the positive electrode active material layer 91B. And other materials such as a binder and a conductive agent may be included. The negative electrode active material, the conductive agent, and the binder may be the same as those in the first embodiment.

[Separator]
The separator 93 is similar to 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 not shown, the inside of this non-aqueous electrolyte battery has a configuration similar to the configuration shown in FIGS. 3A and 3B described in the first embodiment, with the electrolyte layer 56 omitted. That is, the impregnation region A on the negative electrode side, the upper coating region B on the negative electrode side, and the deep region C on the negative electrode side are formed. An impregnation region A on the positive electrode side, an upper coating region B on the positive electrode side, and a deep region C on the positive electrode side are formed. The impregnation region A may be formed only on the negative electrode side, the upper coating region B on the negative electrode side, and the deep region C on the negative electrode side.

(2-2) Method of Manufacturing Nonaqueous Electrolyte Battery (Method of Manufacturing Positive Electrode, Method of Manufacturing Negative Electrode)
The positive electrode 91 and the negative electrode 92 are manufactured in the same manner as in the first embodiment.

(Formation of solid particle layer)
Next, a paint is applied on at least one of the 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 strained by the depressions between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer 92B. The particle concentration in the impregnation zone A is increased. Similarly, a solid particle layer is formed on both main surfaces of the positive electrode 91 by a coating method or the like. At 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 strained by the depressions between adjacent positive electrode active material particles positioned on the outermost surface of the positive electrode active material layer 91B, and the depressions on the positive electrode side The particle concentration in the impregnation zone A is increased. As solid particles, it is preferable to use those in which the particle diameter D95 of the solid particles is adjusted to a predetermined magnification or more of the particle diameter D50 of the active material particles. For example, as solid particles, solid particles of 2 // 3-1 times or more the particle diameter D50 of active material particles are added to a part of solid particles, and the particle diameter D95 of solid particles is the particle diameter D50 of active material particles It is preferable to use one adjusted to be 2 / 23-1 times or more of. In this way, it is possible to fill the gap at the bottom of the recess by the particles with the larger particle diameter and to make the solid particles easier to be strained.

  In addition, at the time of coating formation of the solid particle layer, if the excess paint is scraped off, the distance between the electrodes can be prevented from inadvertently expanding. Further, by scraping the surface of the paint, more particles are fed into the depressions between adjacent active material particles, and the ratio of the overcoated area B is lowered. As a result, the unsaturated cyclic carbonate ester represented by the formula (1), and the halogenation represented by the formula (2) and the formula (3), in which most of the solid particles are intensively disposed in the hollow impregnation area At least one kind of carbonate ester can be made to gather more in the vicinity of the crack generated in the active material particles.

(Method of manufacturing separator)
Next, the separator 93 is prepared.

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

(Assembly of non-aqueous electrolyte battery)
The positive electrode lead 95 is attached to the positive electrode current collector 91A by welding or the like, and the 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 around the separator 93 to form a wound 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 winding surface of the winding electrode body 90 is sandwiched between the pair of insulating plates 82 and 83 and is housed inside the battery can 81. After the wound electrode body 90 is housed inside the battery can 81, the non-aqueous electrolyte is injected into the inside of the battery can 81 and impregnated in the separator 93. After that, a safety valve mechanism including a battery cover 83, a safety valve 84 and the like and a heat sensitive resistance element 87 are fixed to the open end of the battery can 81 by caulking via a gasket 88. Thereby, the non-aqueous 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 91 B and occluded in the negative electrode active material layer 92 B via the non-aqueous electrolytic solution impregnated in the separator 93. In addition, when discharged, for example, lithium ions are released from the negative electrode active material layer 92B and occluded in the positive electrode active material layer 91B via the non-aqueous electrolytic solution impregnated in the separator 93.

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

(Production of positive electrode and negative electrode)
First, the positive electrode 91 and the negative electrode 92 are manufactured in the same manner as in the example of the non-aqueous electrolyte battery.

(Formation of solid particle layer)
Next, a paint is applied on at least one of the main surfaces of the separator 93 by a coating method or the like, and 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.

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

(Heating and pressurizing process)
Before housing the wound electrode body 90 in the inside of the battery can 81, the wound electrode body 90 is put in a packaging material such as a tube of latex and sealed, and hot pressing is performed under hydrostatic pressure. Thereby, the solid particles are moved to the depressions between the 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 impregnation region A on the positive electrode side is increased.

  The subsequent steps can be performed in the same manner as in the example described above to obtain the target non-aqueous electrolytic battery.

3. Third Embodiment In the third embodiment, a rectangular non-aqueous electrolyte battery will be described.

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

  The non-aqueous electrolyte battery includes a rectangular cylindrical outer can 111, a wound electrode body 120 which is a power generation element housed in the outer can 111, a battery lid 112 for closing the opening of the outer can 111, and a battery lid It is comprised by the electrode pin 113 grade | etc., Provided in the approximate center part of 112. FIG.

  The outer can 111 is formed, for example, of a conductive metal such as iron (Fe) as a hollow, bottomed rectangular cylinder. 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. In addition, the outer peripheral surface of the outer can 111 may be covered with an outer label formed of, for example, a plastic sheet, paper, or the like, or may be protected by applying an insulating paint. The battery cover 112 is formed of, for example, a conductive metal such as iron (Fe) as in the case 111.

  The wound electrode body 120 is obtained by laminating a positive electrode and a negative electrode via a separator, and winding in an oval shape in an elongated manner. The positive electrode, the negative electrode, the separator, and the non-aqueous electrolyte are the same as in the first embodiment, and thus the detailed description is omitted.

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

  The electrode pin 113 is made of a conductive shaft member, and is held by the insulator 114 in a state where its head is protruded to the upper end. An electrode pin 113 is fixed to a substantially central portion of the battery cover 112 via the insulator 114. The insulator 114 is formed of a highly insulating material, and is fitted in the 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 of the positive electrode terminal 121 is fixed to the lower end surface thereof.

  A battery lid 112 provided with such an electrode pin 113 or 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. There is. As a result, the opening of the outer can 111 is sealed by the battery lid 112, and is configured airtight and liquid tight. The battery cover 112 is provided with an internal pressure release mechanism 116 for breaking a part of the battery cover 112 when the pressure in the outer can 111 rises to a predetermined value or more and releasing (releasing) the internal pressure to the outside. ing.

  The internal pressure release mechanism 116 includes two first opening grooves 116 a (one first opening groove 116 a is not shown) linearly extended in the longitudinal direction on the inner surface of the battery lid 112. The lid 32 has a second opening groove 116b which extends in the width direction perpendicular to the longitudinal direction on the inner surface of the lid 32 and whose both ends are in communication with the two first opening grooves 116a. The two first opening grooves 116a are provided parallel to each other along the long side outer edge of the battery cover 112 in the vicinity of the inner side of the two long sides facing the width direction of the battery cover 112. ing. Further, the second opening groove 116 b is provided so as to be located 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.

  The first opening groove 116a and the second opening groove 116b both have, for example, a V shape whose cross-sectional shape is open on the lower surface side. 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 electrolytic solution injection port 117 is provided to penetrate the battery lid 112. The electrolytic solution injection port 117 is used to inject the non-aqueous electrolytic solution after caulking the battery cover 112 and the outer can 111, and after the non-aqueous electrolytic solution is injected, it is sealed by the sealing member 118. Ru. For this reason, in the case where the gel electrolyte is formed in advance between the positive electrode and the negative electrode and the separator to produce the wound electrode body, the electrolytic solution injection port 117 and the sealing member 118 may not be provided.

[Separator]
As the separator, the same separator as that of 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 non-aqueous electrolyte battery has the same configuration as the configuration shown in FIGS. 3A and 3B described in the first embodiment, except that the electrolyte layer 56 is omitted. That is, the impregnation region A on the negative electrode side, the upper coating region B on the negative electrode side, and the deep region C on the negative electrode side are formed. An impregnation region A on the positive electrode side, an upper coating region B on the positive electrode side, and a deep region C on the positive electrode side are formed. The impregnation area A, the top coat area B and the deep area C may be formed only on the negative electrode side.

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

[Method of manufacturing positive electrode and negative electrode]
The positive electrode and the negative electrode can be manufactured by the same method as that of the third embodiment.

(Formation of solid particle layer)
Next, a paint is applied on at least one of the two 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 strained by the depressions between adjacent negative electrode active material particles located on the outermost surface of the negative electrode active material layer. 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. In the outermost surface of the positive electrode active material layer on which the solid particle layer is applied and formed, the solid particles are strained by the depressions between adjacent positive electrode active material particles located on the outermost surface of the positive electrode active material layer. The particle concentration of A increases. As solid particles, it is preferable to use those in which the particle diameter D95 of the solid particles is adjusted to a predetermined magnification or more of the particle diameter D50 of the active material. For example, as solid particles, solid particles of 2 // 3-1 times or more the particle diameter D50 of active material particles are added to a part of solid particles, and the particle diameter D95 of solid particles is the particle diameter D50 of active material particles It is preferable to use one adjusted to be 2 / 23-1 times or more of. This allows the solid particles with the larger particle diameter to fill the gap at the bottom of the recess and make the solid particles easier to be strained. In addition, at the time of coating formation of the solid particle layer, if the excess paint is scraped off, the distance between the electrodes can be prevented from inadvertently expanding. 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 solid particles in the overcoated area B is lowered. As a result, the unsaturated cyclic carbonate ester represented by the formula (1), and the halogenation represented by the formula (2) and the formula (3), in which most of the solid particles are intensively disposed in the hollow impregnation area At least one kind of carbonate ester can be made to gather more in the vicinity of the crack generated in the active material particles.

(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 stacked and wound to produce a wound electrode body 120 wound in an oval shape. Subsequently, the wound electrode body 120 is accommodated in the outer can 111.

  Then, the electrode pin 113 provided on the battery cover 112 and the positive electrode terminal 121 drawn out from the wound electrode body 120 are connected. Also, although not shown, the negative electrode terminal derived from the wound electrode body 120 and the battery can are connected. After that, the package can 111 and the battery lid 112 are fitted, and the non-aqueous electrolyte is injected from the electrolyte injection port 117 under reduced pressure, for example, and sealed by the sealing member 118. Thus, a non-aqueous electrolyte battery can be obtained.

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

(Production of positive electrode and negative electrode)
First, a positive electrode and a negative electrode are produced in the same manner as an example of the non-aqueous electrolyte battery.

(Formation of solid particle layer)
Next, a paint is applied on at least one of the two 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.

(Assembly of non-aqueous electrolyte battery)
Next, in the same manner as an example of the non-aqueous electrolyte battery, the wound electrode body 120 is formed. Next, before the wound electrode body 120 is accommodated in the outer can 111, the wound electrode body 120 is put in a packaging material such as a tube of latex and sealed, and warm pressing is performed under hydrostatic pressure. As a result, the solid particles are moved (pushed into) a recess 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 recess impregnation 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, and the solid particle concentration in the depression impregnation region A on the positive electrode side is increased.

  Thereafter, in the same manner as in the above-described example, it is possible to obtain the target non-aqueous electrolytic battery.

4. Fourth Embodiment FIG. 8 shows a perspective view of a battery pack using single cells, 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, for example, in an electronic device represented by a smartphone. For example, as shown in FIG. 9, the battery pack includes a power supply 211 which is a laminated film secondary battery and a circuit board 216 connected to the power supply 211.

  A pair of adhesive tapes 218 and 219 is attached to both sides of the power supply 211. In the circuit board 216, a protection circuit (PCM: Protection Circuit) Module is formed. The circuit board 216 is connected to the positive electrode lead 212 and the negative electrode lead 213 of the power supply 211 via a pair of tabs 214 and 215 and is connected to a lead wire with connector 217 for external connection. When 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.

  The battery pack further includes, for example, a power supply 211 and a circuit board 216, as shown in FIG. The circuit board 216 includes, for example, a control unit 221, a switch unit 222, a PTC 223, and a temperature detection unit 224. The power supply 211 can be connected to the outside through the positive electrode terminal 225 and the negative electrode terminal 227, so the power supply 211 is charged and discharged through the positive electrode terminal 225 and the negative electrode terminal 227. The temperature detection unit 224 can detect a 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 use state of the power supply 211), and includes, for example, a central processing unit (CPU), a memory, and the like.

  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 in the current path of the power supply 211. Further, for example, when a large current flows during charging, the control unit 221 disconnects the switch unit 222 to cut off the charging current.

  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 in the current path of the power supply 211. Further, for example, when a large current flows at the time of discharge, the control unit 221 cuts off the discharge current by disconnecting 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 ± 0.1 V.

  The switch unit 222 switches the use state of the power supply 211 (whether or not the power supply 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, for example, semiconductor switches such as a field effect transistor (MOSFET) using a metal oxide semiconductor. The charge / discharge current is detected based on, for example, the ON resistance of the switch unit 222.

  The temperature detection unit 224 measures the temperature of the power supply 211 and outputs the measurement result to the control unit 221, and includes, for example, a temperature detection element such as a thermistor. The measurement result by the temperature detection unit 224 is used, for example, 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 have 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 showing a circuit configuration example when a battery according to the first to third embodiments of the present technology (hereinafter appropriately referred to as a secondary battery) is 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.

  Further, the battery pack includes the positive electrode terminal 321 and the negative electrode lead 322, and during charging, 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 charger, respectively, to perform charging. In addition, 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 battery assembly 301 is formed by connecting a plurality of secondary batteries 301 a in series and / or in parallel. The secondary battery 301a is a secondary battery of the present technology. Although FIG. 10 shows an example in which six secondary batteries 301a are connected in two parallel three series (2P3S), it may be 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 302 b has a reverse direction to the charging current flowing from the positive electrode terminal 321 in the direction of the battery assembly 301, and has a forward direction to the discharging current flowing from the negative electrode lead 322 to the battery assembly 301. The diode 303 b has a forward direction with respect to the charging current and a reverse direction with respect to the discharging current. In addition, although the switch part 304 is provided in + side in the example, you may provide in-side.

  The charge control switch 302 a is turned off when the battery voltage becomes the overcharge detection voltage, and is controlled by the charge / discharge control unit so that the charge current does not flow in the current path of the assembled battery 301. After the charge control switch 302a is turned off, only discharge can be performed via the diode 302b. The controller 310 is controlled by the control unit 310 to be turned off when a large current flows during charging, and to interrupt the charging current flowing through the current path of the assembled battery 301.

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

  The temperature detection element 308 is, for example, a thermistor, and is provided in the vicinity of the battery pack 301, measures the temperature of the battery pack 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 of the secondary batteries 301 a configuring the same, A / D converts the measured voltage, and supplies the converted voltage to the control unit 310. The current measurement unit 313 measures the current using the current detection resistor 307, and supplies the measured current to the control unit 310.

  The switch control unit 314 controls the charge control switch 302 a and the discharge control switch 303 a of the switch unit 304 based on the voltage and the current input from the voltage detection unit 311 and the current measurement unit 313. When any voltage of the secondary battery 301a becomes equal to or lower than the overcharge detection voltage or the overdischarge detection voltage, the switch control unit 314 sends a control signal to the switch unit 304 when a large current rapidly flows. By sending, overcharge and overdischarge, over current charge and discharge are prevented.

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

  For example, a semiconductor switch such as a MOSFET can be used as the charge / discharge switch. In this case, parasitic diodes of the MOSFETs function as the diodes 302 b and 303 b. 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 the gate potential which is lower than the source potential by a predetermined value or more. That is, in the normal charge and discharge operation, the control signals CO and DO are set to the low level, and the charge control switch 302a and the discharge control switch 303a are turned on.

  Then, for example, in the case of overcharge or overdischarge, the control signals CO and DO are set to the 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) which is a non-volatile memory. In the memory 317, the numerical value calculated by the control unit 310, the internal resistance value of the secondary battery 301a in the initial state measured at the stage of the manufacturing process, etc. are stored in advance, and rewriting is also possible. . (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 at the time of abnormal heat generation, or performs correction in calculation of the remaining capacity.

<6. Sixth embodiment>
The battery according to the first to third embodiments of the present technology and the battery pack according to the fourth to fifth embodiments of the present technology are devices such as electronic devices, electric vehicles, and storage devices, for example. Can be used to load or supply power.

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

  Further, examples of the electric vehicle include a rail car, a golf cart, an electric cart, an electric car (including a hybrid car), and the like, which are used as a driving power source or an auxiliary power source for these.

  Examples of the power storage device include a power storage power source for a building such as a house or for a power generation facility.

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

  The storage system may have, for example, the following configuration. The first power storage system is a power storage system in which the 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 electronic devices connected to the power storage device. The third power storage system is an electronic device that receives supply of power from the power storage device. These storage systems are implemented as a system that cooperates with an external power supply network to efficiently supply power.

  Furthermore, the fourth power storage system is an electric vehicle having a conversion device that receives supply of electric power from the power storage device and converts it into driving force of the vehicle, and a control device that performs information processing related to vehicle control based on information regarding the power storage device. It is. The fifth power storage system includes a power information transmitting / receiving unit that transmits / receives a signal to / from another device via a network, and is a power system that performs charging / discharging control of the above-described power storage device based on information received by the transmitting / receiving unit. . The sixth power storage system is a power system that receives supply of power from the power storage device described above, or supplies power from the power generation device or the power grid to the power storage device. Hereinafter, the storage system will be described.

(6-1) Storage System in a House as an Application Example An example in which a storage device using a battery of the present technology is applied to a storage system for a house will be described with reference to FIG. For example, in the storage system 400 for the house 401, electric power is stored via the centralized power grid 402 such as the thermal power generation 402a, the nuclear power generation 402b, and the hydraulic power generation 402c to the power network 409, the information network 412, the smart meter 407, the power hub 408, and the like. It is 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 a power generation device 404 in the home. The power supplied to power storage device 403 is stored. The power storage device 403 is used to supply power used in the house 401. The same storage system can be used not only for the house 401 but also for the building.

  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 for controlling the respective devices, a smart meter 407, and a sensor 411 for acquiring various information. The respective devices are 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 electric power is supplied to the power consumption device 405 and / or the power storage device 403. The power consumption device 405 is a refrigerator 405 a, an air conditioner 405 b, a television receiver 405 c, a bath 405 d, and the like. Furthermore, the power consumption device 405 includes an electric vehicle 406. The electric vehicle 406 is an electric car 406a, a hybrid car 406b, and an electric bike 406c.

  The battery of the present technology is applied to 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 of commercial power and transmitting the measured usage to the power company. The power network 409 may be combined with any one or more of direct current feed, alternating current feed, and non-contact feed.

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

  The power hub 408 performs processing such as branching of power lines and DC / AC conversion. As a communication method of the information network 412 connected to the control device 410, a method using a communication interface such as UART (Universal Asynchronous Receiver-Transceiver: transmission / reception circuit for asynchronous serial communication), wireless communication such as Bluetooth, ZigBee, Wi-Fi, etc. There is a method of using a sensor network according to the standard. The Bluetooth system 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 a name of a short distance wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.

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

  The control device 410 that controls each unit is configured by a central processing unit (CPU), a random access memory (RAM), a read only memory (ROM), 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 power generation device 404 in the home, the power consumption device 405, various sensors 411, the server 413, and the information network 412, and adjusts, for example, the usage amount of commercial power and the power generation amount. Have a function to In addition, it may be provided with the function etc. which trade in the electric power market.

  As described above, electric power is stored not only in 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 generated power of the power generation device 404 (solar power generation and wind power generation) in the home Can be stored. Therefore, even if the power generated by the power generation device 404 in the home fluctuates, control can be performed such that the amount of power to be transmitted to the outside can be made constant or discharge as necessary. For example, the power obtained by solar power generation is stored in power storage device 403, and late-night power with low charge is stored in power storage device 403 at night, and the power stored by power storage device 403 is discharged in the time zone where the charge for daytime is high. Can also be used.

  In this example, control unit 410 is described as being stored in power storage device 403, but may be stored in smart meter 407 or may be configured alone. Furthermore, power storage system 400 may be used for a plurality of homes in a collective housing, or may be used for a plurality of detached houses.

(6-2) Storage System in Vehicle as Application Example An example in which the present technology is applied to a storage system for a vehicle will be described with reference to FIG. FIG. 12 schematically illustrates an example of a configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied. The series hybrid system is a car that travels by a power drive conversion device using power generated by a generator driven by an engine or power stored in a battery.

  The hybrid vehicle 500 includes an engine 501, a generator 502, an electric power driving force converter 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 mounted. The battery of the present technology described above is applied to the battery 508.

  Hybrid vehicle 500 travels using electric power / drive power conversion device 503 as a power source. An example of the electric power driving force converter 503 is a motor. The electric power driving force converter 503 is operated by the 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 direct current-AC (DC-AC) or reverse conversion (AC-DC conversion) in necessary places, 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 via the vehicle control device 509, and control the opening degree (throttle opening degree) of a throttle valve (not shown). The 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 rotational force can store the power generated by the generator 502 in the battery 508.

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

  The battery 508 can be connected to a power supply external to the hybrid vehicle 500 to receive power from the external power supply 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, there is, for example, an information processing apparatus that displays a battery remaining amount based on information on a battery remaining amount.

  In the above, the series hybrid vehicle traveling by the motor using the power generated by the generator driven by the engine or the power temporarily stored in the battery has been described as an example. However, this technology is also effective for parallel hybrid vehicles that use the engine and motor outputs as drive sources, and run using only the engine, running only with the motor, and engine and motor running, as appropriate. It is applicable. Furthermore, the present technology can be effectively applied to a so-called electric vehicle that travels by driving only by a drive motor without using an engine.

  Hereinafter, the present technology will be described in detail by way of examples. Note that the present technology is not limited to the configurations of the following embodiments.

Example 1-1
[Production of positive electrode]
91% by mass of lithium cobaltate (LiCoO ₂ ) particles (particle diameter D 50: 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 the positive electrode mixture is dispersed in N-methyl-2-pyrrolidone (NMP) as a dispersion medium to obtain a positive electrode mixture slurry.

The positive electrode mixture slurry was applied to both surfaces of a positive electrode current collector made of a strip-like aluminum foil with 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 molding was performed using a roll press to form a positive electrode active material layer. Finally, the positive electrode terminal was attached to the positive electrode current collector exposed portion to form a positive electrode. The area density of the positive electrode active material layer was adjusted to be 30 mg / cm ² .

[Fabrication of negative electrode]
96% by mass of granular graphite particles (particle diameter D50: 20 μm) which is a negative electrode active material, 1.5% by mass of an acrylic acid modified product of a styrene-butadiene copolymer as a binder, carboxymethyl cellulose as a thickener The negative electrode mixture slurry was prepared by mixing 5% by mass to obtain a negative electrode mixture, and further adding an appropriate amount of water and stirring.

The negative electrode mixture slurry was applied to both surfaces of a negative electrode current collector made of a 15 μm-thick strip-shaped copper foil so that a part of the negative electrode current collector was exposed. Thereafter, the dispersion medium of the applied negative electrode mixture slurry was evaporated and dried, and compression molding was performed using a roll press to form a negative electrode active material layer. Finally, the negative electrode terminal was attached to the positive electrode current collector exposed portion 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 5 μm thick polyethylene (PE) microporous film (polyethylene separator) was prepared.

[Formation of electrolyte layer]
Lithium hexafluorophosphate (LiPF ₆ ) is dissolved as an electrolyte salt in a non-aqueous solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed, and the unsaturated cyclic carbonate is The compound represented by 1) was added to prepare a non-aqueous electrolyte. The composition of the non-aqueous electrolyte was adjusted to a compound represented by EC / DEC / formula (1-1) / LiPF ₆ = 20/69/1/10 by mass ratio. Content of the compound represented by Formula (1-1) of this non-aqueous electrolyte is 1 mass% in the mass percentage with respect to the total amount of non-aqueous electrolyte.

  Subsequently, polyvinylidene fluoride (PVdF) is used as a matrix polymer compound (resin) for holding the non-aqueous electrolyte, and the non-aqueous electrolyte, polyvinylidene fluoride, and dimethyl carbonate (DMC: dimethyl carbonate) as a dilution solvent are used. And, as solid particles, boehmite particles (particle diameter D50: 1 μm) were mixed to prepare a sol-like 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 electrolytic solution, and 50% by mass of dilution solvent in mass percentage relative to the total amount of the application solution.

Subsequently, the coating solution is applied in a heated state to both the positive electrode and the negative electrode and dried to remove the dilution solvent (DMC), and the surface density of the positive electrode and the negative electrode is 3 mg / cm ² per one surface. A gel electrolyte layer was formed. Applying the coating solution in a heated state causes the electrolyte containing boehmite particles, which are solid particles, to be impregnated into the depression between adjacent active material particles positioned on the outermost surface of the negative electrode active material layer and the inside of the active material layer. it can. At this time, the solid particles are strained by the depressions between adjacent particles, whereby the particle concentration in the depression impregnation region A on the negative electrode side is increased. Thereby, a difference can be provided between the particle concentration of the depression impregnation region A and the deep region C. By adjusting the thickness of the depression impregnation area A and the top coat area B to those shown in Table 1 by scraping a part of the coating solution, more solid particles are fed into the depression impregnation area A, and solid particles Were to remain in the depression impregnation area A. As solid particles, solid particles having a particle diameter D50 at least 2 / 23-1 times the particle diameter D50 of the negative electrode active material are added to part of the solid particles, and the particle diameter D95 of the solid particles is the particle diameter of the negative electrode active material particles What was prepared so that it might become 2 / (root) 3-1 times or more (3.5 micrometers) of D50 was used. In this way, it is possible to fill the gaps between the particles at the bottom of the recess with some of the solid particles with the larger particle size, making it easier for the solid particles to be shredded.

[Assembly of laminated film type battery]
A positive electrode, a negative electrode having an electrolyte layer formed on both sides, and a separator were laminated in the order of a positive electrode, a separator, a negative electrode and a separator, and then wound in a flat shape many times in the longitudinal direction. Thereafter, the wound end portion was fixed with an adhesive tape to form a wound electrode body.

  Next, the wound electrode body is covered with a laminate film having a soft aluminum layer, and the lead sides 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 laminate 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 the coating solution to be applied to the negative electrode, the content of the solid particles was reduced to 7% by mass, and the amount of the reduced amount DMC of the solid particles was increased. In the same manner as in No. 1, a laminate film type battery was produced.

Example 1-59
In Example 1-59, when preparing the coating solution to be applied to the negative electrode, the content of the solid particles was increased to 18% by mass, and the amount of the increase in solid particles DMC was reduced. In the same manner as in No. 1, a laminate film type battery was produced.

Example 1-60
In Example 1-59, when preparing the coating solution to be applied to the negative electrode, the content of the solid particles was increased to 20% by mass, and the amount of the increase in solid particles DMC was reduced. In the same manner as in No. 1, a laminate film type battery was produced.

Example 1-61
In Example 1-61, when forming the gel electrolyte layer on the negative electrode, a laminate film type battery was produced in the same manner as in Example 1-1 except that the scraping of the coating solution was weakened.

Example 1-62
In Example 1-62, as a solid particle, a solid particle of 2 / √3-1 of the particle diameter D50 of the negative electrode active material is added to part of the solid particle, and the particle diameter D95 of the solid particle is that of the negative electrode active material particle. What was prepared so that it might become 2 / √3-1 times (3.1 micrometers) of particle diameter D50 was used. A laminated film type battery was produced in the same manner as in Example 1-1 except for the above.

<Example 1-63-Example 1-124>
In Examples 1-63 to 1-124, when the electrolyte layer was formed, the compounds shown in Table 1 below were added as halogenated carbonates instead of unsaturated cyclic carbonates, except that A laminated film type battery was produced in the same manner as in each of Example 1-1 to Example 1-62.

Comparative Example 1-1
A laminated film type battery was produced in the same manner as Example 1-1 except that the compound represented by the formula (1-1) was not added to the non-aqueous electrolyte.

Comparative Example 1-2
A laminated film type battery was produced in the same manner as in Example 1-1 except that vinyl ethylene carbonate (VEC) was added instead of the compound represented by the formula (1-1) to the non-aqueous electrolytic solution. .

Comparative Example 1-3
A laminated film type battery was produced in the same manner as in Example 1-1 except that no boehmite particles were added to the coating solution.

Comparative Example 1-4
A laminated film type battery was produced in the same manner as in Example 1-1 except that gel electrolyte layers were formed on both main surfaces of the separator instead of forming gel electrolyte layers on the electrodes. did. In this example, most of the solid particles contained in the electrolyte layer formed on the surface of the separator do not enter the depressions between adjacent active material particles located on the outermost surface of the active material layer. 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 (1-1) was not added to the non-aqueous electrolyte. A laminated film type battery was produced in the same manner as in Example 1-1 except for the above.

Comparative Example 1-6
In Comparative Example 1-6, solid particles having a particle diameter D50 of 2 / √3-1 or more of the particle diameter D50 of the negative electrode active material were not added to part of the solid particles as the solid particles, and the particle diameter D95 of the solid particles was negative electrode active material What was prepared so that it might be set to 2 /? 3-1 or less (2.0 micrometers) of particle diameter D50 of particles was used. A laminated film type battery was produced in the same manner as in Example 1-1 except for the above.

Comparative Example 1-7
In Comparative Example 1-7, when forming the gel electrolyte layer on the negative electrode, the operation of scraping off the coating solution was not performed. In this case, since the distance between the electrodes increases, the length of the electrodes is shortened and wound, and the outer diameter size is adjusted so as not to change. A laminated film type battery was produced in the same manner as in Example 1-1 except for the above.

<Comparative Example 1-8 to Comparative Example 1-11>
In Comparative Example 1-8 to Comparative Example 1-12, the compound represented by the formula (2-1) was added as a halogenated carbonate in place of the unsaturated cyclic carbonate in the formation of the electrolyte layer. Laminated film type batteries were produced in the same manner as in Comparative Examples 1-3 to 1-4 and Comparative Examples 1-6 to 1-7, respectively, except for the above.

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

(Measurement of particle size)
In the particle size distribution of solid particles obtained by removing the electrolyte component and the like from the electrolyte layer, the particle diameter of 50% of the total volume of particles calculated from the particle side of the smaller particle diameter is taken as the particle diameter D50 of the particles. . In addition, the value of the particle diameter D95 of 95% of the volume total was also obtained from the measured particle size distribution as needed. Similarly, the active material particles were similarly measured for particles in which components other than the active material were removed from the active material layer.

(Measurement of BET specific surface area)
The BET specific surface area of the solid particles after removing the electrolyte component and the like from the electrolyte layer was determined using a BET specific surface area measuring device.

(Measurement of solid particle concentration and depression impregnation area A, overcoat area B, deep area C)
Using a SEM, observation was made at four places in a 50 μm wide viewing field. In each observation field of view, each thickness of the impregnated area A, the overcoated area B, and the deep area C and the particle concentration of each area were measured. The particle concentration was obtained by determining the area percentage of the total area of the particle cross section ((“total area of particle cross section” “area of observation field”) × 100%) for the observation field of 2 μm × 2 μm in each region .

(Battery evaluation: high power cycle test, measurement of battery capacity)
The following high power cycle test was performed on each of the produced batteries. After performing constant current constant voltage charging at a charge voltage of 4.2 V and a current of 1 A at 23 ° C until the total charging time reaches 5 hours, constant current discharge up to 3.0 V with a constant current of 0.5 A went. The discharge capacity at this time was taken as the initial capacity of the battery. Moreover, this was made into battery capacity.

  After performing constant current and constant voltage charging at a charge voltage of 4.2 V and a current of 1 A at 23 ° C., 500 cycles of charge and discharge for performing constant current discharge up to 3.0 V with a constant current of 10 A are performed. The discharge capacity of the Then, [capacity after 500 cycles / initial discharge capacity] × 100 (%) was determined as a capacity retention rate.

It was determined as follows according to the size of the capacity retention rate.
Fail: Less than 60% Acceptable: 60% or more and less than 70% Good: 70% or more and less than 80% Excellent: 80% or more and 100% or less

  Table 1 shows the evaluation results.

  As shown in Table 1, in Example 1-1 to Example 1-124, solid particles were disposed at an appropriate concentration in an appropriate region inside the battery, and therefore, the cycle characteristics of high-power discharge were excellent. . Also, the battery capacity was sufficient.

Example 2-1
In the same manner as in Example 1-1, a laminate film type battery was produced.

Example 2-2 to Example 2-56
In Example 2-2 to Example 2-56, at the time of formation of the electrolyte layer, as the unsaturated cyclic carbonate, instead of the compound represented by Formula (1-1), the unsaturated cyclic carbonate is used. A laminated film type battery was produced in the same manner as in Example 2-1 except that the compounds shown in Table 2 shown above were added.

Example 2-57
A laminated film type battery was produced in the same manner as in Example 1-63.

<Example 2-58 to Example 2-77>
In Example 2-58 to Example 2-77, when forming the electrolyte layer, instead of the compound represented by Formula (2-1), the compounds shown in Table 2 below are used as halogenated carbonates. A laminated film type battery was produced in the same manner as in Example 2-57 except for the addition.

(Battery evaluation: high power cycle test, measurement of battery capacity)
About the produced laminated film type battery of each Example, it carried out similarly to Example 1-1, and measured the high output cycle test and battery capacity.

  Table 2 shows the evaluation results.

  As shown in Table 2, in Example 2-1 to Example 2-77, since solid particles were disposed at an appropriate concentration in an appropriate region inside the battery, the cycle characteristics of high-power discharge were excellent. . Also, the battery capacity was sufficient.

Example 3-1 to Example 3-9
In Example 3-1 to Example 3-9, as shown in Table 3 below, the same as Example 1-1 except that the addition amount of the compound represented by Formula (1-1) was changed Then, a laminated film type battery was produced.

Example 3-10 to Example 3-18
Examples 3-1 to 3-18 are the same as Example 1-63, except that the amount of the compound represented by Formula (2-1) is changed as shown in Table 3 below. Then, a laminated film type battery was produced.

(Battery evaluation: high power cycle test, measurement of battery capacity)
About the produced laminated film type battery of each Example, it carried out similarly to Example 1-1, and measured the high output cycle test and battery capacity.

  Table 3 shows the evaluation results.

  As shown in Table 3, in Examples 3-1 to 3-18, the solid particles were disposed at an appropriate concentration in an appropriate region inside the battery, and therefore, the cycle characteristics of high-power discharge were excellent. .

Example 4-1 to Example 4-11
In Example 4-1 to Example 4-11, it is the same as Example 1-1 except that the particle diameter and the specific surface area of solid boehmite particles are changed as shown in Table 4 below. , A laminated film type battery was produced.

Example 4-12 to Example 4-22
Example 4-12 to Example 4-22 are the same as Example 1-63, except that the particle diameter and specific surface area of solid boehmite particles are changed as shown in Table 4 below. , A laminated film type battery was produced.

(Battery evaluation: high power cycle test, measurement of battery capacity)
About the produced laminated film type battery of each Example, it carried out similarly to Example 1-1, and measured the high output cycle test and battery capacity.

  Table 4 shows the evaluation results.

  As shown in Table 4, in Examples 4-1 to 4-22, the solid particles were disposed at an appropriate concentration in an appropriate region inside the battery, and therefore, the cycle characteristics of high-power discharge were excellent. . Also, the battery capacity was sufficient.

Example 5-1
In the same manner as in Example 1-1, a laminate film type battery was produced.

Example 5-2
First, in the same manner as in Example 5-1, the positive electrode and the negative electrode were produced, and a separator was prepared.

  Next, in the same manner as in Example 1-1, the same coating solution as in Example 1-1 is applied to both sides of the separator, dried to remove the dilution solvent (DMC), and gelled on the surface of the separator. An electrolyte layer was formed.

  Thereafter, the positive electrode, the negative electrode, and the separator having a gel electrolyte layer formed on both sides thereof are laminated in the order of the positive electrode, the separator, the negative electrode, and the separator, and wound in a flat shape many times in the longitudinal direction. Thereafter, the wound end portion was fixed with an adhesive tape to form a wound electrode body.

  Next, the wound electrode body was bagged and subjected to hydrostatic pressing. As a result, the solid particles are pushed into the depression between the adjacent positive electrode active material particles on the outermost surface of the positive electrode active material layer and the depression 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 sides 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 to seal Stopped and sealed. Thus, a laminate 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 5-3
First, in the same manner as in Example 5-1, the positive electrode and the negative electrode were produced, and a separator was prepared.

(Formation of solid particle layer)
Next, a paint 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 coated on both sides of the separator, and then the solvent was removed by drying. As a result, a solid particle layer was formed so that the solid content per side was 0.5 mg / cm ² .

  Next, the positive electrode, the negative electrode, and the separator having the solid particle layer formed on both sides 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. Thereafter, the wound end portion was fixed with an adhesive tape to form a wound body.

  Next, the wound collector put in a bag of heated oil was placed and subjected to hydrostatic pressing. 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 by a laminate film having a soft aluminum layer, and the outer peripheral edge excluding one side was heat-sealed to form a bag, which was housed inside the laminate film. Next, a non-aqueous electrolytic solution was injected into the inside of the package member, and the non-aqueous electrolytic solution was impregnated into the wound body, and then the opening of the laminate film was heat-sealed in a vacuum atmosphere and sealed. Thus, a laminate 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 5-4
Similarly to Example 5-1, a positive electrode and a negative electrode were produced, and a separator was prepared.

  After applying the coating solution to both sides of the separator as follows, it was dried to form a matrix resin layer.

  First, a coating solution was prepared by dispersing boehmite particles and polyvinylidene fluoride (PVdF), which is a matrix polymer compound, in N-methyl-2-pyrrolidone (NMP). 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 It was 80% by mass.

  Next, the 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 having the matrix resin layer formed on both sides are laminated in the order of the positive electrode, the separator, the negative electrode, and the separator, and wound in flat shape many times in the longitudinal direction. The wound electrode body was formed by fixing with an adhesive tape.

  Next, the wound electrode body bagged in heated oil was placed and subjected to hydrostatic pressing. As a result, the solid particles were pushed into the depressions on the outermost surface of the positive electrode active material layer and the depressions on the outermost surface of the negative electrode active material layer.

  Next, the wound electrode body was sandwiched between the package members, and the three sides were heat-fused. In addition, the lamination film which has a soft aluminum layer was used for the exterior member.

  After that, an electrolyte 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). In addition, the thing similar to Example 1-1 was used as electrolyte solution. From the above, a laminate 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 5-5
First, in the same manner as in Example 5-1, the positive electrode and the negative electrode were prepared, and a separator was prepared.

(Formation of solid particle layer)
A paint 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 introduced into the hollow impregnated regions A on the positive electrode side and the negative electrode side, and the thickness of the hollow impregnated region A was made to be twice or more the thickness of the overcoated region B. Thereafter, NMP was removed by drying to form a solid particle layer so that the solid content was 0.5 mg / cm ^{2 on} one side.

  Next, a positive electrode, a negative electrode having a solid particle layer formed on both sides, and a separator were laminated in the order of a positive electrode, a separator, a negative electrode, and a separator, and wound in a flat shape many times in the longitudinal direction. Thereafter, the wound end portion was fixed with an adhesive tape to form a wound body.

  Next, this wound body was sandwiched by a laminate film having a soft aluminum layer, and the outer peripheral edge excluding one side was heat-sealed to form a bag, which was housed inside the laminate film. Next, a non-aqueous electrolytic solution was injected into the inside of the package member, and the non-aqueous electrolytic solution was impregnated into the wound body, and then the opening of the laminate film was heat-sealed in a vacuum atmosphere and sealed. Thus, a laminate 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 5-6
A laminated film type battery was produced in the same manner as in Example 5-1 except that the gel electrolyte layer was formed only on both sides of the negative electrode.

<Examples 5-7 to 5-8, Examples 5-10, Examples 5-12, and Examples 5-14 to 5-15>
In Examples 5-7, 5-10, 5-10, 5-12, and 5-14, when forming the electrolyte layer, Formula (1-1) A laminated film type battery was produced in the same manner as in Example 5-1 to Example 5-6 except that the compound represented by the formula (2-1) was added instead of the compound represented by .

<Example 5-9, Example 5-11, Example 5-13>
In Examples 5-9, 5-11, and 5-13, except for using a non-woven fabric in place of the separator (polyethylene separator), Examples 5-7, Examples 5-8, Examples Laminated film type batteries were produced in the same manner as 5-10, Example 5-12, and Example 5-14 to Example 5-15.

<Comparative Example 5-1>
A laminated film type battery was produced in the same manner as in Example 5-1 except that the gel electrolyte layer was formed only on both sides of the positive electrode.

Comparative Example 5-2
A laminated film type battery was produced in the same manner as in Example 5-7 except that the gel electrolyte layer was formed only on both sides of the positive electrode.

(Battery evaluation: high power cycle test, measurement of battery capacity)
About the produced laminated film type battery of each Example, it carried out similarly to Example 1-1, and measured the high output cycle test and battery capacity.

  Table 5 shows the evaluation results.

  As shown in Table 5, in Examples 5-1 to 5-16, the solid particles were disposed at an appropriate concentration in an appropriate region inside the battery, and thus the cycle characteristics of high-power discharge were excellent. . Also, the battery capacity was sufficient.

Example 6-1
Next, a rectangular positive electrode and a rectangular negative electrode having the same configuration as in Example 1-1 except that the rectangular shape was used, and a rectangular separator were produced.

(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 5-3.

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

  Next, the laminated electrode body bagged in heated oil was placed and subjected to hydrostatic pressing. 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, 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 injected into this, and the remaining one side was heat-fused and sealed under reduced pressure. As a result, laminated film type batteries shown in FIGS. 4A to 4C, each having a battery shape of 4.5 mm in thickness, 30 mm in width, and 50 mm in height, were produced.

Example 6-2
A laminated electrode body was formed in the same manner as in Example 6-1, and the laminated electrode body bagged in heated oil was placed and subjected to hydrostatic pressing. Thus, the depressions on the outermost surface of the positive electrode active material layer and the depressions on the outermost surface of the negative electrode active material were pushed.

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

  Subsequently, the non-aqueous electrolyte was poured from above the insulating plate into the inside of the cylindrical battery can. Finally, the battery lid was sealed at the open portion of the battery can by caulking via an insulating sealing gasket. Thus, a cylindrical battery having a diameter of 18 mm and a height of 65 mm (ICR 18650 size) was produced.

Example 6-3
A laminated electrode body was formed in the same manner as in Example 6-1, and the laminated electrode body bagged in heated oil was placed and subjected to hydrostatic pressing. Thus, the depressions on the outermost surface of the positive electrode active material layer and the depressions on the outermost surface of the negative electrode active material were pushed.

[Assembly of square battery]
Next, the laminated electrode body was housed 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 injection port. It sealed by the sealing member and sealed. Thus, a square battery having a battery shape of 4.5 mm in thickness, 30 mm in width, and 50 mm in height (453050 size) was produced.

Example 6-4
In Example 6-4, a simplified battery pack (soft pack) shown in FIG. 8 and FIG. 9 was produced using the same laminate film type battery as that of Example 1-1.

<Example 6-5 to Example 6-8>
In Examples 6-5 to 6-8, in forming the electrolyte layer, the compound represented by Formula (2-1) was added instead of the compound represented by Formula (1-1) Laminated film type batteries were produced in the same manner as in Example 6-1 to Example 6-4 except for the above.

(Battery evaluation: high power cycle test)
A high power cycle test was conducted on the laminated film type batteries of each of the produced examples in the same manner as in Example 1-1.

  Table 6 shows the evaluation results.

  As shown in Table 6, in Examples 6-1 to 6-8, the solid particles were disposed at an appropriate concentration in an appropriate region inside the battery, and therefore, the cycle characteristics of high-power discharge were excellent. . Also, the battery capacity was sufficient.

  In the above-described Examples and Comparative Examples (Tables 1 to 6), the same applies even if a halogenated chain carbonate such as fluoromethyl methyl carbonate, bis (fluoromethyl) carbonate or difluoromethyl methyl carbonate is used as an additive component Tend to be obtained.

7. Other Embodiments Although the present technology has been described above by the respective embodiments and examples, the present technology is not limited to these, and various modifications are possible within the scope of the present technology.

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

  In addition, 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 spirit of the present technology. For example, the non-aqueous electrolyte battery may be a primary battery.

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

（式（１）中、Ｘは、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−Ｃ（＝Ｒ３）−、−Ｃ（＝Ｒ１）−Ｃ（Ｒ４）（Ｒ５）−、−Ｃ（＝Ｒ１）−Ｃ（Ｒ４）（Ｒ５）−Ｃ（Ｒ６）（Ｒ７）−、−Ｃ（Ｒ４）（Ｒ５）−Ｃ（＝Ｒ１）−Ｃ（Ｒ６）（Ｒ７）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−Ｃ（Ｒ４）（Ｒ５）−、−Ｃ（＝Ｒ１）−Ｃ（Ｒ４）（Ｒ５）−Ｃ（＝Ｒ２）−、−Ｃ（＝Ｒ１）−Ｏ−Ｃ（Ｒ４）（Ｒ５）−、−Ｃ（＝Ｒ１）−Ｏ−Ｃ（＝Ｒ２）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ８）−、−Ｃ（＝Ｒ１）−Ｃ（＝Ｒ２）−Ｃ（＝Ｒ８）−からなる群から選ばれた何れか一の２価の基である。Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、炭素数１の２価の炭化水素基または炭素数１の２価のハロゲン化炭化水素基である。Ｒ４、Ｒ５、Ｒ６およびＲ７は、それぞれ独立して、１価の水素基（−Ｈ）、炭素数１以上８以下の１価の炭化水素基、炭素数１以上８以下の１価のハロゲン化炭化水素基または炭素数１以上６以下の１価の酸素含有炭化水素基である。Ｒ８は、炭素数２以上５以下のアルキレン基または炭素数２以上５以下のハロゲン化アルキレン基である。）

（式（２）中、Ｒ２１〜Ｒ２４は、それぞれ独立して、水素基、ハロゲン基、アルキル基またはハロゲン化アルキル基であり、Ｒ２１〜Ｒ２４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。）

（式（３）中、Ｒ２５〜Ｒ３０は、それぞれ独立して、水素基、ハロゲン基、アルキル基またはハロゲン化アルキル基であり、Ｒ２５〜Ｒ３０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。）
［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のみを有する［１］又は［２］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］の何れか一に記載の電池。
［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］の何れか一に記載の電池。
［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］の何れか一に記載の電池。
［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］の何れか一に記載の電池。
［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］の何れか一に記載の電池。
［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］の何れか一に記載の電池。
［１０］
前記式（１）で表される不飽和環状炭酸エステルの含有量は、０．０１質量％以上１０質量％以下である［１］〜［９］の何れか一に記載の電池。
［１１］
前記式（２）および式（３）で表されるハロゲン化炭酸エステルの含有量は、０．０１質量％以上５０質量％以下である［１］〜［１０］の何れか一に記載の電池。
［１２］
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］〜［１１］の何れか一に記載の電池。
［１３］
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［１２］に記載の電池。
［１４］
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［１３］に記載の電池。
［１５］
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］〜［１４］の何れか一に記載の電池
［１６］
前記電解質は、ゲル状の電解質である［１］〜［１５］のいずれか一に記載の電池。
［１７］
［１］〜［１６］の何れか一に記載の電池と、
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。
［１８］
［１］〜［１６］の何れか一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。
［１９］
［１］〜［１６］の何れか一に記載の電池と、
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。
［２０］
［１］〜［１６］の何れか一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。
［２１］
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［２０］に記載の蓄電装置。
［２２］
［１］〜［１６］の何れか一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。 The present technology can also have the following configurations.
[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 electrolyte and solid particles,
Negative electrode side recessed impregnation region and negative electrode side deep region,
Or
A hollow impregnation region on the negative electrode side, a deep region on the negative electrode side, and a hollow impregnation region on the positive electrode side and a deep region on the positive electrode side,
The hollow impregnated region on the negative electrode side is a region including a hollow between adjacent negative electrode active material particles positioned on the outermost surface of the negative electrode active material layer, in which the electrolyte and the solid particles are disposed,
The deep region on the negative electrode side is a region inside the negative electrode active material layer that is deeper than the hollow impregnated region on the negative electrode side, in which the electrolyte or the electrolyte and the solid particles are disposed,
The depression impregnation region on the positive electrode side is a region including depressions between adjacent positive electrode active material particles positioned on the outermost surface of the positive electrode active material layer, in which the electrolyte and the solid particles are disposed,
The deep region on the positive electrode side is a region inside the positive electrode active material layer which is deeper than the hollow impregnated region on the positive electrode side, in which the electrolyte or the electrolyte and the solid particles are disposed,
The concentration of the solid particles in the hollow impregnation region on the negative electrode side is 30% by volume or more,
The concentration of the solid particles in the depression impregnation region on the positive electrode side is 30% by volume or more,
A battery, wherein the electrolytic solution contains at least one of an unsaturated cyclic carbonate represented by the following formula (1) and a halogenated carbonate represented by the formulas (2) and (3).

(In formula (1), X is -C (= R1) -C (= R2)-, -C (= R1) -C (= R2) -C (= R3)-, -C (= R1) -C (R4) (R5)-, -C (= R1) -C (R4) (R5) -C (R6) (R7)-, -C (R4) (R5) -C (= R1) -C (R6) (R7)-, -C (= R1) -C (= R2) -C (R4) (R5)-, -C (= R1) -C (R4) (R5) -C (= R2) -, -C (= R1) -O-C (R4) (R5)-, -C (= R1) -O-C (= R2)-, -C (= R1) -C (= R8)-, It is any one divalent group selected from the group consisting of -C (= R1) -C (= R2) -C (= R8)-R1, R2 and R3 are each independently carbon Number 1 divalent hydrocarbon group or carbon number 1 divalent halogenated hydrocarbon R4, R5, R6 and R7 are each independently a monovalent hydrogen group (-H), a monovalent hydrocarbon group having 1 to 8 carbon atoms, a monovalent having 1 to 8 carbon atoms Or a monovalent oxygen-containing hydrocarbon group having 1 to 6 carbon atoms, R 8 is an alkylene group having 2 to 5 carbon atoms or a halogenated alkylene group having 2 to 5 carbon atoms. is there.)

(In formula (2), R 21 to R 24 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of R 21 to R 24 is a halogen group or a halogenated alkyl group Is)

(In formula (3), R 25 to R 30 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of R 25 to R 30 is a halogen group or a halogenated alkyl group Is)
[2]
The battery according to [1] , which has the hollow impregnation region on the negative electrode side and the deep region on the negative electrode side, and the hollow impregnation region on the positive electrode side and the deep region on the positive electrode side.
[3]
The battery according to [1] or [2] , having only the hollow impregnated region on the negative electrode side and the deep region on the negative 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]
The solid particle concentration of the at least one hollow impregnation region is at least 10 times the solid particle concentration of the deep region on the same electrode side as the at least one hollow impregnation region, according to any one of [1] to [4] Battery described.
[6]
The battery according to any one of [1] to [5], wherein the thickness of the hollow 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.
[7]
The particle diameter D95 of the solid particles contained in the at least one hollow impregnation region is at least 2 / 倍 3-1 times 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 impregnated region is 2 / √3-1 times or less of the particle diameter D50 of the active material particles described in any one of [1] to [7] Battery.
[9]
The battery according to any one of [1] to [8], wherein a BET specific surface area of the solid particle is 1 m ² / g or more and 60 m ² / g or less.
[10]
Content of the unsaturated cyclic carbonate represented by said Formula (1) is a battery as described in any one of [1]-[9] which is 0.01 mass% or more and 10 mass% or less.
[11]
Content of the halogenated carbonate represented by said Formula (2) and Formula (3) is a battery as described in any one of [1]-[10] which is 0.01 mass% or more and 50 mass% or less .
[12]
The battery according to any one of [1] to [11], wherein the solid particles are at least one of inorganic particles and organic particles.
[13]
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 may be melamine, melamine cyanurate, melamine polyphosphate, crosslinked poly (methyl methacrylate), polyolefin, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamide, polyimide, melamine resin, phenol resin, epoxy The battery according to [12], which is at least any particle selected from the group consisting of a resin.
[14]
The silicate mineral includes talc, calcium silicate, zinc silicate, zirconium silicate, aluminum silicate, magnesium silicate, kaolinite, sepiolite, imogolite, sericite, pyrophyllite, mica, zeolite, mullite, saponite And 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 [13], wherein the oxide mineral is spinel.
[15]
The battery according to any one of [1] to [14], wherein the electrolyte further includes a polymer compound holding the electrolytic solution.
The battery according to any one of [1] to [15], wherein the electrolyte is a gel electrolyte.
[17]
The battery according to any one of [1] to [ 16 ],
A control unit that controls the battery;
A battery pack having an outer package containing the battery.
[18]
The electronic device which has a battery as described in any one of [1]-[ 16 ], and receives supply of electric power from the said battery.
[19]
The battery according to any one of [1] to [ 16 ],
A converter that receives supply of electric power from the battery and converts it into a driving force of a vehicle;
A control device that performs information processing related to vehicle control based on the information related to the battery.
[20]
An electricity storage device comprising the battery according to any one of [1] to [16] and supplying power to an electronic device connected to the battery.
[21]
It has a power information control device that sends and receives signals to and from other devices via a network,
The power storage device according to [ 20 ], which performs charge / discharge control of the battery based on the information received by the power information control device.
[ 22 ]
The electric power system which receives supply of electric power from the battery as described in any one of [1]-[16], or electric power is supplied to the said battery from a power generation device or an electric power grid.

  Reference Signs List 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, 54 A · · · Negative electrode current collector, 54 B · · · Negative electrode active material layer, 55 · · · · · · · · · · · · · · · · · · · · · · · · · · protective tape, 60 · · · exterior member, 61 · · Adhesive film, 70 · · · stacked electrode body, 71 · · · positive electrode lead, 72 · · · negative electrode lead, 73 · · · · · · · · · · · · · · · · · · · · · · · · · · · fixed Members 81: battery can 82a, 82b: insulating plate 83: battery cover 84: safety valve 84a: convex portion 85: disc holder 86: shut off Disc, 86a: hole, 87: thermal resistance element, 88: gasket, 89 Subdisk 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 package 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 , 117: electrolyte solution inlet, 118: sealing member, 120: wound electrode body, 101: battery cell, 101a: terrace portion, 102a, 102b: lead, 103a To 103 c: 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 substrate, 217: connector Attached 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 · · · · · · · · battery pack, 301a · · · secondary battery, 302a · · · charge control switch, 302b · · · · · · · 30a · · · discharge control switch, 303b · · · · · · Diode, 304 · · · switch unit, 307 · · · current detection resistor, 308 · · · temperature detection element, 310 · · · control unit, 311 · · · voltage detection unit, 313 · · · current measurement Fixed part, 314 ... switch control part, 317 ... memory, 318 ... temperature detection part, 321 ... positive electrode terminal, 322 ... negative electrode terminal, 400 ... 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 car 406b: 406b Hybrid car, 406c: electric bike, 407: smart meter, 408: power hub, 409: power grid, 410: control device, 411: sensor, 412 Information network 413 server 500 hybrid vehicle 501 engine 502 generator 503 power driving force converter 504a driving wheel 504b Drive wheel 505a: wheel 505b: wheel 508: battery 509: vehicle control device 510: sensor 511: charging port

Claims (14)

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 electrolyte and solid particles,
A hollow impregnation region on the negative electrode side, a deep region on the negative electrode side, and a hollow impregnation region on the positive electrode side and a deep region on the positive electrode side,
The hollow impregnated region on the negative electrode side is a region including a hollow between adjacent negative electrode active material particles positioned on the outermost surface of the negative electrode active material layer, in which the electrolyte and the solid particles are disposed,
The deep region on the negative electrode side is a region inside the negative electrode active material layer that is deeper than the hollow impregnated region on the negative electrode side, in which the electrolyte or the electrolyte and the solid particles are disposed,
The depression impregnation region on the positive electrode side is a region including depressions between adjacent positive electrode active material particles positioned on the outermost surface of the positive electrode active material layer, in which the electrolyte and the solid particles are disposed,
The deep region on the positive electrode side is a region inside the positive electrode active material layer which is deeper than the hollow impregnated region on the positive electrode side, in which the electrolyte or the electrolyte and the solid particles are disposed,
The concentration of the solid particles in the hollow impregnation region on the negative electrode side is 30% by volume or more,
The concentration of the solid particles in the depression impregnation region on the positive electrode side is 30% by volume or more,
The solid particle concentration in the deep region on the negative electrode side is 3% by volume or less,
The solid particle concentration in the deep region on the positive electrode side is 3% by volume or less,
The solid particles include boehmite, talc, zinc oxide, tin oxide, silicon oxide, magnesium oxide, antimony oxide, aluminum oxide, magnesium sulfate, calcium sulfate, barium sulfate, strontium sulfate, magnesium carbonate, calcium carbonate, barium carbonate, carbonate Lithium, magnesium hydroxide, aluminum hydroxide, zinc hydroxide, boron carbide, silicon carbide, silicon nitride, boron nitride, aluminum nitride, titanium nitride, lithium fluoride, aluminum fluoride, aluminum fluoride, calcium fluoride, barium fluoride, fluoride Magnesium, diamond, trilithium phosphate, magnesium phosphate, magnesium hydrogen phosphate, calcium silicate, zinc silicate, zirconium silicate, aluminum silicate, magnesium silicate, spinel, hydrotalcite At least one member selected from the group consisting of dolomite, kaolinite, sepiolite, imogolite, serisite, pyrophyllite, mica, zeolite, mullite, saponite, attapulgite, montmorillonite, ammonium polyphosphate, melamine cyanurate, melamine polyphosphate and polyolefins A species,
The said electrolyte solution is a lithium ion secondary battery containing unsaturated cyclic carbonate represented by following formula (1), and at least 1 sort (s) of the halogenated carbonate represented by Formula (2) and Formula (3) .

(In formula (1), X is -C (= R1) -C (= R2)-, -C (= R1) -C (= R2) -C (= R3)-, -C (= R1) -C (R4) (R5)-, -C (= R1) -C (R4) (R5) -C (R6) (R7)-, -C (R4) (R5) -C (= R1) -C (R6) (R7)-, -C (= R1) -C (= R2) -C (R4) (R5)-, -C (= R1) -C (R4) (R5) -C (= R2) -, -C (= R1) -O-C (R4) (R5)-, -C (= R1) -O-C (= R2)-, -C (= R1) -C (= R8)-, It is any one divalent group selected from the group consisting of -C (= R1) -C (= R2) -C (= R8)-R1, R2 and R3 are each independently carbon Number 1 divalent hydrocarbon group or carbon number 1 divalent halogenated hydrocarbon group R4, R5, R6 and R7 are each independently a monovalent hydrogen group (-H), a monovalent hydrocarbon group having 1 to 8 carbon atoms, a monovalent having 1 to 8 carbon atoms Or a monovalent oxygen-containing hydrocarbon group having 1 to 6 carbon atoms, R 8 is an alkylene group having 2 to 5 carbon atoms or a halogenated alkylene group having 2 to 5 carbon atoms. is there.)

(In formula (2), R 21 to R 24 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of R 21 to R 24 is a halogen group or a halogenated alkyl group Is)

(In formula (3), R 25 to R 30 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of R 25 to R 30 is a halogen group or a halogenated alkyl group Is) The thickness of the negative electrode side of the recess impregnation zone, the negative active 10% to 40% of the thickness of less lithium ion secondary battery according to claim 1, wherein the material layer. Particle diameter D95 of the solid particles contained in the recess impregnation zone of the negative electrode side is state, and are 2 / √3-1 times the particle diameter D50 of the negative electrode active material particles,
The particle diameter D95 of the solid particles contained in the recess impregnation zone of the positive electrode side, the positive active material Ru der 2 / √3-1 times the particle diameter D50 of particles according to claim 1 or 2 lithium according to the ion Secondary battery. Particle size of the solid particles contained in the recess impregnation zone of the negative electrode side D50 is Ri 2 / √3-1 times der following particle size D50 of the negative electrode active material particles,
The particle diameter D50 of the solid particles contained in the recess impregnation zone of the positive electrode side, the positive electrode active 2 / √3-1 fold der Ru any of claims 1 3 or less particle diameter D50 of material particles Lithium ion secondary battery as described. The lithium ion secondary battery according to any one of claims 1 to 4 , wherein a BET specific surface area of the solid particles is 1 m ² / g or more and 60 m ² / g or less. The lithium ion secondary battery according to any one of claims 1 to 5 , wherein the content of the unsaturated cyclic carbonate represented by the formula (1) is 0.01% by mass or more and 10% by mass or less. The lithium ion according to any one of claims 1 to 6 , wherein the content of the halogenated carbonate represented by the formula (2) and the formula (3) is 0.01% by mass or more and 50% by mass or less. Next battery. The lithium ion secondary battery according to any one of claims 1 to 7 , wherein the electrolyte further comprises a polymer compound holding the electrolytic solution. The lithium ion secondary battery according to any one of claims 1 to 8 , wherein the electrolyte is a gel electrolyte. A lithium ion secondary battery according to any one of claims 1 to 9 ,
A control unit that controls the lithium ion secondary battery;
A battery pack including an outer package including the lithium ion secondary battery. It has a lithium ion secondary battery according to any of claims 1 9, receives power from the lithium-ion secondary battery electronics. A lithium ion secondary battery according to any one of claims 1 to 9 ,
A converter that receives supply of power from the lithium ion secondary battery and converts it into a driving force of a vehicle;
A control device that performs information processing related to vehicle control based on information related to the lithium ion secondary battery. A storage device comprising the lithium ion secondary battery according to any one of claims 1 to 9 , and supplying power to an electronic device connected to the lithium ion secondary battery. The electric power system which receives supply of electric power from the lithium ion secondary battery as described in any one of Claim 1 to 9 , or electric power is supplied to the said lithium ion secondary battery from an electric power generating apparatus or an electric power grid.

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