JP2017033921A - Secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithium ion battery of such configuration and structure that warpage due to the volumetric change of a negative electrode active material is less likely to occur, without providing (adding) any special member or structure in the lithium ion battery.SOLUTION: A lithium ion battery is constituted by housing a structure 1, winding or laminating a positive electrode, a separator and a negative electrode, in an exterior member 2, and filled with an electrolyte. The outer surface along the XZ plane of the structure 1 is the first surface 1A and second surface 1B of the structure 1, the inner surface of the exterior member 2 facing the first surface 1A of the structure 1 is the first surface 2A of the exterior member 2, and the inner surface of the exterior member 2 facing the second surface 1B of the structure 1 is the second surface 2B of the exterior member 2. Assuming that the dynamic friction coefficient of the first surface 2A of the exterior member 2 is μ, and the dynamic friction coefficient of the second surface 2B of the exterior member 2 is μ, following relation is satisfied; μ>μ.SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to a secondary battery.

  In a secondary battery having features such as thinness, lightness, and flexibility, a structure in which a positive electrode, a separator, and a negative electrode are wound or laminated is housed in an exterior member made of a laminate film, for example. And filled with electrolyte. By the way, for example, in a secondary battery composed of a lithium ion secondary battery, the negative electrode active material expands and contracts due to lithium insertion / extraction reaction (or alloying reaction) during charging / discharging. There is a problem that the stress applied to the member increases or decreases and the secondary battery itself is deformed. Here, “deformation” means expansion in the stacking direction (the stacking direction of the positive electrode, separator, and negative electrode) due to expansion of the negative electrode active material, expansion in the negative electrode surface, and accompanying force applied to each layer. This refers to both warping that the entire secondary battery is bent due to non-uniformity.

  Problems such as deformation of the secondary battery are becoming more apparent because thin and large secondary batteries are required for various electronic devices such as smartphones and tablet terminals in recent years. In general, the exclusive space of the battery in the electronic device is determined at the design stage. Therefore, it is necessary to design the volume of the secondary battery to be small in advance so that it will fit in the exclusive space even if the secondary battery is deformed. From the viewpoint of battery capacity, the deformation of the secondary battery is a major disadvantage. It is.

JP 2006-338993 A JP2009-140904A

  Various means for suppressing the volume change of the negative electrode active material have been proposed. For example, in the technique disclosed in Japanese Patent Application Laid-Open No. 2006-338993, after the negative electrode mixture layer is applied to the negative electrode current collector foil through a mesh, the mesh is removed, thereby increasing the volume of the negative electrode mixture layer during charging. A buffer space is formed to mitigate the effects of However, since there is no negative electrode mixture in the buffer space, the battery capacity is reduced accordingly. In the technique disclosed in Japanese Patent Application Laid-Open No. 2009-140904, the volume density of the electrode mixture layer is increased to increase the rigidity of the electrode, so that even when a laminate film is used as an exterior member, deformation in the thickness direction of the secondary battery is achieved. Can be suppressed. However, even if the rigidity of the electrode is increased to suppress the expansion in the thickness direction of the secondary battery, the difference in the expansion amount due to the asymmetry in the thickness direction in the constituent members inside the secondary battery generates a bending moment. Therefore, the effect of preventing warpage is limited.

  Therefore, an object of the present disclosure is to provide a secondary battery having a configuration and a structure in which warpage due to a volume change of the negative electrode active material hardly occurs without providing (adding) a special member or structure to the secondary battery. It is in.

The secondary battery according to the first to third aspects of the present disclosure for achieving the above object is configured by housing a structure in which a positive electrode, a separator, and a negative electrode are wound or stacked in an exterior member, A secondary battery filled with an electrolyte,
The longitudinal direction of the structure is the X direction, the short direction of the structure is the Z direction, the thickness direction of the structure is the Y direction,
The outer surface along the XZ plane of the structure is the first surface of the structure and the second surface of the structure,
The inner surface of the exterior member that faces the first surface of the structure is the first surface of the exterior member, and the inner surface of the exterior member that faces the second surface of the structure is the second surface of the exterior member.

And in the secondary battery according to the first aspect of the present disclosure, when the dynamic friction coefficient of the first surface of the exterior member is μ ₁ and the dynamic friction coefficient of the second surface of the exterior member is μ ₂ ,
μ ₁ > μ ₂
Satisfied. In the secondary battery according to the second aspect of the present disclosure, the first surface of the exterior member is subjected to a surface treatment different from that of the second surface of the exterior member. Furthermore, in the secondary battery according to the third aspect of the present disclosure, the combination of (material constituting the first surface of the exterior member, material constituting the second surface of the exterior member) is (polypropylene, Nylon), (polypropylene, polyethylene), or (polyethylene, nylon).

The secondary battery according to the fourth aspect of the present disclosure for achieving the above object is configured by accommodating a structure in which a positive electrode, a separator, and a negative electrode are wound or stacked in an exterior member and filled with an electrolyte. A secondary battery,
The exterior member is
A first exterior member, and
A second exterior member in which a recess for housing the structure is formed and an outer edge is fixed to the first exterior member;
Consisting of
The material constituting the first exterior member is different from the material constituting the second exterior member.

In the secondary battery according to the first aspect of the present disclosure, the relationship between the dynamic friction coefficient μ ₁ of the first surface of the exterior member and the dynamic friction coefficient μ ₂ of the second surface is defined. In the secondary battery according to the second aspect, the first surface of the exterior member is subjected to a surface treatment different from the second surface of the exterior member, and the secondary battery according to the third aspect of the present disclosure. In this case, since the combination of (the material constituting the first surface of the exterior member and the material constituting the second surface of the exterior member) is defined, the structure resulting from the volume change of the negative electrode active material during charging Generation | occurrence | production of the curvature of a body can be suppressed by the 1st surface and 2nd surface of an exterior member. In the secondary battery according to the fourth aspect of the present disclosure, the material constituting the first exterior member and the material constituting the second exterior member are different, and therefore, due to the volume change of the negative electrode active material during charging. Generation | occurrence | production of the warped structure can be suppressed by the combination of a 1st exterior member and a 2nd exterior member. Note that the effects described in the present specification are merely examples and are not limited, and may have additional effects.

1A is a conceptual diagram showing a cross section of the secondary battery of Example 1, FIG. 1B is a conceptual diagram showing a cross section of the secondary battery of Example 3, and FIG. 1C is a secondary diagram of Example 6. It is a conceptual diagram which shows the cross section of a battery. 2A and 2B are conceptual diagrams showing a cross-section of the secondary battery of Example 4, and FIG. 2C is a schematic partial cross-sectional view of the first exterior member and the second exterior member. 3 is a schematic exploded perspective view of a laminate film type secondary battery of Example 5. FIG. 4A is a schematic exploded perspective view of a laminated film type secondary battery of Example 5 in a state different from that shown in FIG. 3, and FIG. 4B is a laminated film type secondary battery of Example 5. It is typical sectional drawing along arrow AA of FIG. 3, FIG. 4A of the winding electrode body (structure) in a battery. 5A, FIG. 5B, FIG. 5C, and FIG. 5D are schematic partial cross-sectional views in which a part of the wound electrode body (structure) shown in FIG. Schematic cross-sectional view for explaining an aspect, schematic partial cross-sectional view for explaining a second aspect relating to the arrangement of the insulating material, and a third aspect relating to the arrangement of the insulating material It is a typical partial sectional view. 6 is a schematic exploded perspective view of an application example (battery pack: single cell) of the secondary battery of the present disclosure in Example 7. FIG. 7A is a block diagram illustrating a configuration of an application example (battery pack: single cell) of the secondary battery according to the present disclosure in the seventh embodiment illustrated in FIG. 6, and FIG. 7B illustrates a secondary of the present disclosure according to the seventh embodiment. It is a block diagram showing the structure of the application example (battery pack: assembled battery) of a battery. 8A, FIG. 8B, and FIG. 8C are respectively a block diagram showing a configuration of an application example (electric vehicle) of the secondary battery of the present disclosure in Example 7, and an application example of the secondary battery of the present disclosure in Example 7 ( 8 is a block diagram illustrating a configuration of a power storage system) and a block diagram illustrating a configuration of an application example (electric tool) of the secondary battery of the present disclosure in Example 7. FIG.

Hereinafter, although this indication is explained based on an example with reference to drawings, this indication is not limited to an example and various numerical values and materials in an example are illustrations. The description will be given in the following order.
1. 1. General description of secondary batteries according to first to fourth aspects of the present disclosure Example 1 (secondary battery according to the first aspect of the present disclosure)
3. Example 2 (a modification of Example 1, a secondary battery according to the second aspect of the present disclosure)
4). Example 3 (Modification of Example 1 to Example 2, secondary battery according to the third aspect of the present disclosure)
5). Example 4 (secondary battery according to the fourth aspect of the present disclosure)
6). Example 5 (secondary battery having a structure in which a positive electrode, a separator, and a negative electrode are wound, which is a modification of Example 1 to Example 4)
7). Example 6 (secondary battery having a structure in which a positive electrode, a separator, and a negative electrode are laminated), which is a modification of Example 1 to Example 4.
8). Example 7 (Application Example of Secondary Battery of Present Disclosure)
9. Other

<Secondary Battery According to First to Fourth Aspects of Present Disclosure, General Description>
In the secondary battery according to the first aspect of the present disclosure, the first surface of the exterior member can be made of a material different from the material constituting the second surface of the exterior member. Specifically, (polypropylene, nylon), (polypropylene, polyethylene), or (polyethylene, nylon) as a combination of (material constituting the first surface of the exterior member, material constituting the second surface of the exterior member) ). In the secondary battery according to the first aspect of the present disclosure including such a preferable mode, the first surface of the exterior member is configured to have a surface treatment different from the second surface of the exterior member. Alternatively, the first surface of the exterior member can be configured to be rougher than the roughness of the second surface of the exterior member. In addition, in such a structure, the 1st surface of an exterior member can be made into the structure which consists of the same material as the material which comprises the 2nd surface of an exterior member.

  In the secondary battery according to the second aspect of the present disclosure, the first surface of the exterior member is subjected to surface treatment, and the second surface of the exterior member is not subjected to surface treatment. can do. Alternatively, the first surface of the exterior member can be configured to be rougher than the roughness of the second surface of the exterior member. In the secondary battery according to the second aspect of the present disclosure including such a form, the first surface of the exterior member may be made of the same material as the material constituting the second surface of the exterior member. However, the present invention is not limited to this, and the first surface of the exterior member can be made of a material different from the material constituting the second surface of the exterior member. In the latter case, specifically, as a combination of (a material constituting the first surface of the exterior member, a material constituting the second surface of the exterior member), (polypropylene, nylon), (polypropylene, polyethylene), or (Polyethylene, nylon).

  Furthermore, in the secondary battery according to the second aspect of the present disclosure including the various preferable modes described above, or in the various preferable configurations described above of the secondary battery according to the first aspect of the present disclosure. The surface treatment can be a roughening treatment. In this case, the roughening treatment can be a chemical treatment, an ultraviolet treatment, an ozone treatment, or a plasma treatment. In addition, an etching process can be mentioned as a chemical process, and an argon plasma process, an oxygen plasma process, a nitrogen plasma process etc. can be mentioned specifically as a plasma process. Alternatively, the roughening treatment can be an embossing treatment, and specifically includes a treatment for forming irregularities using a press device or a roller. Alternatively, the roughening process may be a blasting process. Specifically, as the blasting treatment, for example, an acute-angled abrasive or a spherical abrasive made of an alumina abrasive, a silicon carbide abrasive, glass beads, or the like is used at high speed using compressed air or centrifugal force. Examples thereof include a sand blasting method and a shot blasting method in which fine irregularities are formed by jetting and impact. That is, unevenness is formed on the first surface of the exterior member, the second surface of the exterior member can be flat, and the second surface of the exterior member can be formed on the first surface of the exterior member. The unevenness formed on the first surface of the exterior member may be larger than the unevenness formed on the second surface of the exterior member. It can be set as the structure by which large unevenness | corrugation is formed on average. The above description can also be applied to a preferable configuration of the secondary battery according to the fourth aspect of the present disclosure.

  Furthermore, in the secondary battery according to the first to third aspects of the present disclosure including the various preferable modes and configurations described above, the structure having the larger expansion amount when the structure is expanded by charging is structured. The first surface of the body, the smaller one can be the second surface of the structure, or the structure can be warped so that the first surface is convex when charged. Can do.

Furthermore, in the secondary battery according to the first to third aspects of the present disclosure including the various preferable modes and configurations described above, the Young's modulus of the exterior member is 5 × 10 ⁸ Pa to 7 × 10 ^9. Pa is preferred.

  Furthermore, in the secondary battery according to the first to third aspects of the present disclosure including the various preferable modes and configurations described above, the exterior member includes the first resin layer (the first plastic material layer, the melt). It is preferable to adopt a form having a laminated structure of an adhesive layer), a metal layer, and a second resin layer (second plastic material layer, surface protective layer), that is, a laminated film. In the case of a laminated film type secondary battery, for example, after the exterior member is folded so that the fusion layers face each other through the structure, the outer peripheral edge portions of the fusion layers are fused. However, the exterior member may be a laminate of two laminated films with an adhesive or the like. The fusion layer is made of an olefin resin film such as polyethylene, polypropylene, modified polyethylene, modified polypropylene, or a polymer thereof. A metal layer consists of aluminum foil, stainless steel foil, nickel foil, etc., for example. The surface protective layer is made of, for example, nylon or polyethylene terephthalate (PET). Among these, the exterior member is preferably an aluminum laminated film in which a polyethylene film, an aluminum foil, and a nylon film are laminated in this order. However, the exterior member may be a laminate film having another laminated structure, a polymer film such as polypropylene, or a metal film.

  Here, the first resin layer (fusion layer) constitutes the first surface and the second surface of the exterior member. Or the sheet-like member which comprises the 1st surface and 2nd surface of an exterior member is distribute | arranged between the 1st resin layer (fusion layer) and the 1st surface and 2nd surface of a structure. . Alternatively, a sheet-like member constituting the first surface of the exterior member is disposed between the first resin layer (fusion layer) and the first surface of the structure, and the first resin layer (fusion layer) ) Constitutes the second surface of the exterior member. Or the sheet-like member which comprises the 2nd surface of an exterior member is distribute | arranged between the 1st resin layer (fusion layer) and the 2nd surface of a structure, The 1st resin layer (fusion layer) ) Constitutes the first surface of the exterior member.

In the secondary battery according to the fourth aspect of the present disclosure, the first exterior member may have a higher Young's modulus than the second exterior member. And in the secondary battery which concerns on the 4th aspect of this indication containing the various desirable forms explained above, the 1st exterior member has the lamination structure of the 1A resin layer, the 1st metal layer, and the 1B resin layer. And the second exterior member may have a laminated structure of the second A resin layer, the second metal layer, and the second B resin layer, and in this case, the first metal layer is made of stainless steel, The second metal layer may be made of aluminum or an aluminum alloy, and the thickness of the first metal layer may be 1 × 10 ⁻⁵ m to 1.8 × 10 ⁻⁴ m, The thickness of the two metal layers may be 5 × 10 ⁻⁵ m to 2 × 10 ⁻⁴ m.

  Furthermore, in the secondary battery according to the fourth aspect of the present disclosure including the various preferable forms and configurations described above, the outer edge of the second exterior member is thermally fused and fixed to the first exterior member. It can be.

In the secondary battery according to the fourth aspect of the present disclosure including the various preferable embodiments described above, the longitudinal direction of the structure is the X direction, the short direction of the structure is the Z direction, and the thickness direction of the structure is The outer surface along the XZ plane of the structure is defined as the first surface of the structure and the second surface of the structure, and the inner surface of the first exterior member facing the first surface of the structure (for example, the first surface described later) The first exterior member constituting the first exterior member is the first surface of the first exterior member, and the inner surface of the second exterior member facing the second surface of the structure (for example, the second exterior member constituting the second exterior member described later). 2B resin layer) is the second surface of the second exterior member. In the secondary battery according to the fourth aspect of the present disclosure, the dynamic friction coefficient of the first surface of the first exterior member is μ ₁ , and the dynamic friction coefficient of the second surface of the second exterior member is μ ₂ . When
μ ₁ > μ ₂
It can be set as the structure which satisfies these.

  Alternatively, in the secondary battery according to the fourth aspect of the present disclosure including the various preferable modes described above, the inner surface of the first exterior member facing the first surface of the structure (for example, the first exterior described later) The first B resin layer constituting the member is the first surface of the first exterior member, and the inner surface of the second exterior member facing the second surface of the structure (for example, the second B resin constituting the second exterior member described later) Layer) is the second surface of the second exterior member, the first surface of the first exterior member may have a different surface treatment from the second surface of the second exterior member. Alternatively, the first surface of the first exterior member can be configured to be rougher than the roughness of the second surface of the second exterior member. In such a configuration, the first surface of the first exterior member can be made of the same material as that constituting the second surface of the second exterior member, but is not limited thereto. The first surface of the first exterior member can be made of a material different from the material constituting the second surface of the second exterior member.

  Alternatively, in the secondary battery according to the fourth aspect of the present disclosure including the various preferable modes described above, the inner surface of the first exterior member facing the first surface of the structure (for example, the first exterior described later) The first B resin layer constituting the member is the first surface of the first exterior member, and the inner surface of the second exterior member facing the second surface of the structure (for example, the second B resin constituting the second exterior member described later) (Layer) is the second surface of the second exterior member, the combination of (material constituting the first surface of the first exterior member, material constituting the second surface of the second exterior member) is (polypropylene, nylon) ), (Polypropylene, polyethylene), or (polyethylene, nylon).

  Here, in the secondary battery according to the fourth aspect of the present disclosure, a larger amount of expansion when the structure is expanded by charging is a first surface of the structure, and a smaller surface is the second surface of the structure. It can be configured. Moreover, when charged, the structure can be configured to warp so that the first surface is convex. The first B resin layer of the first exterior member faces the first surface of the structure, and the second B resin layer of the second exterior member faces the second surface of the structure. Here, as described above, the first B resin layer of the first exterior member corresponds to the inner surface of the first exterior member facing the first surface of the structure, and the second B resin layer of the second exterior member is the structure. This corresponds to the inner surface of the second exterior member facing the second surface. Alternatively, the first B resin layer of the first exterior member corresponds to the first surface of the exterior member in the secondary battery according to the first to third aspects of the present disclosure, and the second B resin of the second exterior member. The layer corresponds to the second surface of the exterior member.

Furthermore, in the secondary battery according to the fourth aspect of the present disclosure including the various preferable modes and configurations described above, the first exterior member and the second exterior member are made of a laminate film. In particular,
The first A resin layer (the first A plastic material layer) and the first B resin layer (the first B plastic material layer, the first surface of the first exterior member) are made of different materials,
The 2A resin layer (2A plastic material layer) and the 2B resin layer (2B plastic material layer, the second surface of the second exterior member) are made of different materials,
The first A resin layer and the second A resin layer are made of the same material, or alternatively, the first A resin layer and the second A resin layer are made of different materials,
The first B resin layer and the second B resin layer are made of the same material, or the first B resin layer and the second B resin layer are made of different materials,
The first metal layer and the second metal layer can be made of different materials.

  Here, the 1A resin layer of the 1st exterior member and the 2A resin layer of the 2nd exterior member function as a surface protection layer, and the 1B resin layer of the 1st exterior member and the 2B resin layer of the 2nd exterior member are Functions as a fusion layer. Then, after the first exterior member and the second exterior member are overlapped so that the fusion layers face each other through the structure, the fusion layer is fused. As described above, the fusion layer is made of an olefin resin film such as polyethylene, polypropylene (PP), modified polyethylene, modified polypropylene, or a polymer thereof. The surface protective layer is made of, for example, nylon, polyethylene terephthalate (PET) or the like, as described above.

  Furthermore, in the secondary battery according to the first to fourth aspects of the present disclosure including the various preferable forms and configurations described above, the electrolyte may be formed of a gel electrolyte. It is not limited to. For gel electrolytes, the vacuum injection process of the electrolyte is not required, and a continuous coating process can be adopted, which is advantageous in terms of productivity when manufacturing large-area secondary batteries. is there.

  The separator separates the positive electrode and the negative electrode, and allows lithium ions to pass through while preventing a short circuit of current due to contact between the positive electrode and the negative electrode. In the secondary battery according to the first to fourth aspects of the present disclosure including the various preferable modes and configurations described above, the material constituting the separator is made of polypropylene resin, polyethylene resin, or polyimide resin. It can be in the form. That is, the separator is, for example, a porous film made of a synthetic resin such as polyolefin resin (polypropylene resin or polyethylene resin), polyimide resin, polytetrafluoroethylene resin, aromatic polyamide; porous film such as ceramic; glass fiber; liquid crystal It is comprised from the nonwoven fabric which consists of a polyester fiber, an aromatic polyamide fiber, and a cellulosic fiber. Or a separator can also be comprised from the laminated film in which two or more types of porous films were laminated | stacked, and can also be set as the separator with which the inorganic substance layer was apply | coated, and an inorganic substance containing separator.

In the secondary battery according to the first aspect of the present disclosure, the relationship between the dynamic friction coefficient μ ₁ of the first surface of the exterior member and the dynamic friction coefficient μ ₂ of the second surface is defined. , JIS P8147: 2010 may be used for the measurement. Specifically, a steel (steel) material is used as a test piece on the table, and a first surface (a member constituting the exterior member) and a second surface (a member constituting the exterior member) are used as the thread test pieces. used to obtain the coefficient of dynamic friction between the first surface of the steel material and the package member as mu _1, obtains the dynamic friction coefficient between the second surface of the steel material and the package member as mu _2, the mu ₁ values and mu ₂ Compare the values. Steel is a kind of standard specimen. When the sample of the first surface (member constituting) and the second surface (member constituting) of the exterior member having the size specified in JIS P8147: 2010 cannot be collected, the first surface of the exterior member, A sample of the same size (a sample as large as possible) may be collected from the second surface of the exterior member and used for the test.

  The first surface of the structure and the second surface of the structure are composed of, for example, a negative electrode active material layer, or are composed of a negative electrode current collector, or are composed of a positive electrode active material layer, or It is comprised from a positive electrode electrical power collector, or is comprised from the protective tape affixed on the outermost periphery part of the structure.

  Examples of the shape and form of the secondary battery include a flat laminate type (laminate film type).

  In the secondary battery of the present disclosure, specifically, for example, in a lithium ion secondary battery, the positive electrode active material may include lithium atoms. In the positive electrode, a positive electrode active material layer is formed on one side or both sides of the positive electrode current collector. As a material constituting the positive electrode current collector, copper (Cu), aluminum (Al), nickel (Ni), magnesium (Mg), titanium (Ti), iron (Fe), cobalt (Co), zinc (Zn), Examples include germanium (Ge), indium (In), gold (Au), platinum (Pt), silver (Ag), palladium (Pd), etc., or alloys containing any of these, and conductive materials such as stainless steel. can do. The positive electrode active material layer includes a positive electrode material capable of inserting and extracting lithium as a positive electrode active material. The positive electrode active material layer may further contain a positive electrode binder, a positive electrode conductive agent, and the like. Examples of the positive electrode material include lithium-containing compounds (compounds containing lithium atoms). From the viewpoint of obtaining a high energy density, it is preferable to use a lithium-containing composite oxide or a lithium-containing phosphate compound. The lithium-containing composite oxide is an oxide containing lithium and one or more elements (hereinafter referred to as “other elements”, excluding lithium) as constituent elements, and has a layered rock salt type crystal structure or It has a spinel crystal structure. Specific examples include lithium-cobalt materials, lithium-nickel materials, spinel manganese materials, and superlattice structure materials. Alternatively, the lithium-containing phosphate compound is a phosphate compound containing lithium and one or more elements (other elements) as constituent elements, and has an olivine type crystal structure.

  In the negative electrode, a negative electrode active material layer is formed on one side or both sides of the negative electrode current collector. As a material constituting the negative electrode current collector, copper (Cu), aluminum (Al), nickel (Ni), magnesium (Mg), titanium (Ti), iron (Fe), cobalt (Co), zinc (Zn), Examples include germanium (Ge), indium (In), gold (Au), platinum (Pt), silver (Ag), palladium (Pd), etc., or alloys containing any of these, and conductive materials such as stainless steel. can do. The negative electrode active material layer includes a negative electrode material capable of inserting and extracting lithium as a negative electrode active material. The negative electrode active material layer may further contain a negative electrode binder, a negative electrode conductive agent, and the like. The negative electrode binder and the negative electrode conductive agent can be the same as the positive electrode binder and the positive electrode conductive agent. The surface of the negative electrode current collector is preferably roughened from the viewpoint of improving the adhesion of the negative electrode active material layer to the negative electrode current collector based on the so-called anchor effect. In this case, at least the surface of the region of the negative electrode current collector on which the negative electrode active material layer is to be formed should be roughened. As a roughening method, for example, a method of forming fine particles using electrolytic treatment can be mentioned. The electrolytic treatment is a method of providing irregularities on the surface of the negative electrode current collector by forming fine particles on the surface of the negative electrode current collector using an electrolysis method in an electrolytic cell. Alternatively, the negative electrode can be composed of a lithium foil, a lithium sheet, or a lithium plate.

  The negative electrode active material layer can be formed based on, for example, a coating method, a gas phase method, a liquid phase method, a thermal spraying method, or a firing method (sintering method). The application method is a method in which a negative electrode active material in the form of particles (powder) is mixed with a negative electrode binder or the like, and then the mixture is dispersed in a solvent such as an organic solvent and applied to the negative electrode current collector. The vapor phase method is a PVD method (physical vapor deposition method) such as a vacuum deposition method, a sputtering method, an ion plating method or a laser ablation method, or various CVD methods (chemical vapor deposition methods) including a plasma CVD method. It is. Examples of the liquid phase method include an electrolytic plating method and an electroless plating method. The thermal spraying method is a method of spraying a molten or semi-molten negative electrode active material onto a negative electrode current collector. The firing method is, for example, a method in which a mixture dispersed in a solvent using a coating method is applied to the negative electrode current collector and then heat-treated at a temperature higher than the melting point of the negative electrode binder, etc. Examples thereof include a reactive firing method and a hot press firing method.

  In order to prevent unintentional deposition of lithium on the negative electrode during charging, the chargeable capacity of the negative electrode material is preferably larger than the discharge capacity of the positive electrode. That is, the electrochemical equivalent of the negative electrode material capable of inserting and extracting lithium is preferably larger than the electrochemical equivalent of the positive electrode. The lithium deposited on the negative electrode is, for example, lithium metal when the electrode reactant is lithium.

When configuring the secondary battery of the present disclosure from the lithium ion secondary battery, as the lithium salt that constitutes the non-aqueous electrolyte suitable for use, for _{example, LiPF 6, LiClO 4, LiBF} 4, LiAsF 6, LiSbF 6, LiTaF ₆ , LiNbF ₆ , LiAlCl ₄ , LiCF ₃ SO ₃ , LiCH ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , LiC ₄ F ₉ SO ₃ , Li (FSO ₂ ) ₂ N Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C, LiBF ₃ (C ₂ F ₅ ), LiB (C ₂ O ₄ ) ₂ , LiB (C ₆ F ₅ ) ₄ , LiPF ₃ (C ₂ F ₅ ) ₃ , 1 / 2Li ₂ B ₁₂ F ₁₂ , Li ₂ SiF ₆ , LiCl, LiBr, and LiI can be mentioned, but are not limited thereto. It is not a thing. Moreover, as an organic solvent, cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC); chain carbonates such as dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) Esters; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), 1,3 dioxolane (DOL), 4-methyl-1,3 dioxolane (4-MeDOL); 1,2 dimethoxyethane (DME) , 1,2-diethoxyethane (DEE) chain ether; γ-butyrolactone (GBL), γ-valerolactone (GVL) cyclic ester; methyl acetate, ethyl acetate, propyl acetate, methyl formate, ethyl formate And chain esters such as propyl formate, methyl butyrate, methyl propionate, ethyl propionate, and propyl propionate. Alternatively, as the organic solvent, tetrahydropyran, 1,3 dioxane, 1,4 dioxane, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), N-methylpyrrolidinone (NMP), N- Methyl oxazolidinone (NMO), N, N′-dimethylimidazolidinone (DMI), dimethyl sulfoxide (DMSO), trimethyl phosphate (TMP), nitromethane (NM), nitroethane (NE), sulfolane (SL), acetonitrile (AN) , Glutaronitrile (GLN), adiponitrile (ADN), methoxyacetonitrile (MAN), 3-methoxypropionitrile (MPN), and diethyl ether. Alternatively, an ionic liquid can be used. A conventionally well-known thing can be used as an ionic liquid, What is necessary is just to select as needed.

Generally, due to the asymmetry of the internal structure of the secondary battery, the amount of expansion in the XZ plane during charging differs between the front (front) surface side and the back surface side of the secondary battery. In Example 1, based on the two-dimensional stress simulation, the expansion of the structure due to the expansion of the negative electrode active material of the secondary battery, and the dynamic friction coefficients of the first surface and the second surface of the exterior member made of the laminate film We examined how μ ₁ and μ ₂ affect the warpage of the secondary battery.

The secondary battery in Example 1 is a secondary battery in which a structure in which a positive electrode, a separator, and a negative electrode are wound or stacked is housed in an exterior member and filled with an electrolyte. And, as shown in FIG. 1A, a schematic cross-sectional view (conceptual diagram) along the XY plane,
(A) The longitudinal direction of the structure 1 is the X direction, the transverse direction of the structure 1 is the Z direction, and the thickness direction of the structure 1 is the Y direction.
(B) The outer surface along the XZ plane of the structure 1 (that is, parallel to or substantially parallel to the XZ plane) is defined as the first surface 1A of the structure 1 and the second surface 1B of the structure 1.
(C) The inner surface of the exterior member 2 that faces the first surface 1A of the structure 1 is the first surface 2A of the exterior member 2, and the inner surface of the exterior member 2 that faces the second surface 1B of the structure 1 is the exterior member 2. The second surface 2B.

Here, for simplification, in the secondary battery as a model, the first portion (the portion on the first surface 1A side) 1a and the second portion (the portion on the second surface 1B side) of the structure 1 ) Assume that it is integrated with 1b. The thickness of the first portion 1a of the structure 1 (the thickness in the Y direction) is 1.0 mm, and the thickness of the second portion 1b of the structure 1 (the thickness in the Y direction) is 1.0 mm. To do. Further, it is assumed that the first part 1a and the second part 1b are symmetric with respect to the boundary 1c. Furthermore, the length in the longitudinal direction (X direction) of the structure 1 is set to 40.0 mm. Further, the thickness of the exterior member 2 made of a laminate film is 0.1 mm, and the length of the exterior member 2 in the longitudinal direction (X direction) is 42.0 mm. Further, the expansion rates in the X direction and Y direction of the first portion 1a during charging are 1.1% and 6.0%, and the expansion rates in the X direction and Y direction of the second portion 1b are 1.0%. %, 6.0%. In other words, the larger amount of expansion when the structure 1 is expanded by charging is the first surface 1A of the structure 1, and the smaller one is the second surface 1B of the structure 1. Alternatively, when charged, the structure 1 warps so that the first surface 1A is convex. The same applies to the following embodiments. Further, the Young's modulus of the first part 1a and the second part 1b is 4 × 10 ⁹ Pa, the Poisson's ratio is 0.3, the Young's modulus of the exterior member 2 made of a laminate film is 4 × 10 ⁹ Pa, and the Poisson's ratio is 0.3. The same applies to Examples 2 to 3 below.

The above conditions of the original, the dynamic friction coefficient mu ₁ value of the first surface 2A of the outer member 2, the dynamic friction coefficient mu ₂ value of the second surface 2B of the exterior member 2, the warpage amount of the secondary cell (unit: The simulation was performed in six cases shown in Table 1 below to see how the mm) changes. The results are shown in Table 1. In order to make the dynamic friction coefficient μ ₁ of the first surface 2A of the exterior member 2 different from the dynamic friction coefficient μ ₂ of the second surface 2B of the exterior member 2, the first surface of the exterior member 2 is the same as in the second embodiment. 2A may be made of a material different from the material constituting the second surface 2B of the exterior member 2, or alternatively, a surface different from the second surface 2B of the exterior member 2 on the first surface 2A of the exterior member 2 What is necessary is just to process.

<Table 1>
Case 1 2 3 4 5 6
μ ₁ 0 0 0.4 0.4 0.5 0.6
μ ₂ 0 0.4 0.4 0 0.1 0.2
Warpage amount 0.17 0.22 0.17 0.12 0.12 0.12

From the simulation results in Table 1, Case 4, Case 5, and Case 6 are used to suppress the warpage of the entire secondary battery by the binding force of the exterior member 2 (specifically, a laminate film) against the secondary battery. It turned out to be preferable. That is,
μ ₁ > μ ₂
Is satisfied, the occurrence of warpage of the structure 1 due to the volume change of the negative electrode active material and the occurrence of warpage of the entire secondary battery during charging are suppressed by the binding force of the exterior member 2 against the secondary battery. I found out that That is, when the movement of the first surface 1A of the structure 1 relative to the first surface 2A of the exterior member 2 and the movement of the second surface 1B of the structure 1 relative to the second surface 2B of the exterior member 2 are compared, Due to the difference in the dynamic friction coefficients μ ₁ and μ ₂ between the first surface 2A and the second surface 2B, the first surface 1A of the structure 1 is difficult to move, and the second surface 1B of the structure 1 is easy to move. Therefore, when charged, the structure 1 tends to warp so that the first surface 1A is convex, but due to the difference in motion between the first surface 1A and the second surface 1B of the structure 1, the structure 1 The amount of warping that the first surface 1A of the body 1 is convex can be reduced. In case 2, μ ₁ <μ ₂ is satisfied. Therefore, the first surface 1A of the structure 1 is easy to move, and the second surface 1B of the structure 1 is difficult to move. Therefore, when charged, due to the difference in motion between the first surface 1A and the second surface 1B of the structure 1, the amount of warping that the first surface 1A of the structure 1 becomes convex increases, It was the highest value in Case 6. In case 1 and case 3, μ ₁ = μ ₂ . Therefore, the first surface 1 </ b> A of the structure 1 is easier to move than the cases 4 to 6. Therefore, when charged, due to the difference in motion between the first surface 1A and the second surface 1B of the structure 1, the amount of warping that the first surface 1A of the structure 1 becomes convex increases, and the case 4˜ The value was higher than in Case 6.

  Example 2 is a modification of Example 1 and relates to a secondary battery according to the second aspect of the present disclosure. In the secondary battery of Example 2, the first surface 2A of the exterior member 2 is subjected to a surface treatment different from that of the second surface 2B of the exterior member 2. Alternatively, the first surface 2A of the exterior member 2 is rougher than the roughness of the second surface 2B of the exterior member 2. The first surface 2A of the exterior member 2 may be composed of the same material as the material constituting the second surface 2B of the exterior member 2, or may be composed of a different material. The same material, specifically, the exterior member 2 includes a first resin layer (first plastic material layer, a fusion layer, specifically made of polyethylene film), a metal layer (specifically, aluminum And a laminated structure of a second resin layer (a second plastic material layer, which is a surface protective layer, specifically, a nylon film). The first resin layer constitutes the first surface 2A and the second surface 2B of the exterior member 2. The same applies to the first embodiment. The electrolyte is made of a gel electrolyte, and the material constituting the separator is made of polypropylene resin, polyethylene resin, or polyimide resin. The same applies to the first embodiment.

  In Example 2, the first surface 2A of the exterior member 2 was subjected to surface treatment, and the second surface 2B of the exterior member 2 was not subjected to surface treatment. Further, as described above, the first surface 2A of the exterior member 2 is made of the same material as that constituting the second surface 2B of the exterior member 2. In Example 2, the surface treatment was a roughening treatment. That is, the first surface 2A of the exterior member 2 is uneven, and the second surface 2B of the exterior member 2 is flat. Alternatively, the first surface 2A of the exterior member 2 is More irregularities are formed per unit area than the irregularities formed on the second surface 2B, or alternatively, the first surface 2A of the exterior member 2 is formed on the second surface 2B of the exterior member 2. On the average, unevenness larger than the unevenness is formed. In other words, the first surface 2A of the exterior member 2 is roughened, and the second surface 2B of the exterior member 2 is not roughened. For example, the first surface of the exterior member 2 that has been roughened by subjecting the first resin layer constituting the roll-shaped exterior member 2 to a roughening treatment based on the roll-to-roll method. After obtaining the exterior member 2 in which 2A and the second surface 2B of the exterior member 2 that is not roughened are alternately arranged, the first surface 1A of the structure 1 and the first surface 2A of the exterior member 2 are The secondary battery may be assembled so that the second surface 1B of the structure 1 and the second surface 2B of the exterior member 2 face each other.

  Specifically, the roughening process was a chemical process (more specifically, an etching process). That is, the first resin layer constituting the roll-shaped exterior member 2 is printed, exposed, and developed with a photosensitive etching resist ink based on the roll-to-roll method, whereby the first resin layer of the exterior member 2 is formed. After the etching resist with the exposed surface 2A is formed, the first resin layer is etched to remove the etching resist. Thus, it is possible to obtain the exterior member 2 in which the first surface 2A of the exterior member 2 roughened by etching and the second surface 2B of the exterior member 2 not roughened are alternately arranged. The second surface 1A of the structure 1 and the first surface 2A of the exterior member 2 are opposed to each other, and the second surface 1B of the structure 1 and the second surface 2B of the exterior member 2 are opposed to each other. A battery can be assembled.

  Alternatively, the surface treatment is specifically ultraviolet treatment, ozone treatment or plasma treatment. That is, the first resin layer constituting the roll-shaped exterior member 2 is irradiated with ultraviolet rays, ozone is sprayed, or plasma particles are collided based on the roll-to-roll method. Thus, it is possible to obtain the exterior member 2 in which the first surface 2A of the exterior member 2 that is roughened and the second surface 2B of the exterior member 2 that is not roughened are alternately arranged. The second surface 1A of the structure 1 and the first surface 2A of the exterior member 2 are opposed to each other, and the second surface 1B of the structure 1 and the second surface 2B of the exterior member 2 are opposed to each other. A battery can be assembled.

  Alternatively, the surface treatment is specifically an embossing treatment. That is, the exterior member 2 roughened by applying unevenness to the first resin layer constituting the roll-shaped exterior member 2 using a press device or a roller based on the roll-to-roll method. Thus, the exterior member 2 in which the first surface 2A and the second surface 2B of the exterior member 2 that is not roughened are alternately arranged can be obtained. The second surface 1A of the structure 1 and the first surface 2A of the exterior member 2 are opposed to each other, and the second surface 1B of the structure 1 and the second surface 2B of the exterior member 2 are opposed to each other. A battery can be assembled.

  Alternatively, the surface treatment is specifically a blasting treatment. That is, for the first resin layer constituting the roll-shaped exterior member 2, based on the roll-to-roll method, an acute-angled abrasive made of an alumina abrasive, a silicon carbide abrasive, glass beads, etc. The first surface 2A of the exterior member 2 roughened by applying fine irregularities based on a sandblasting method or a shotblasting method in which a spherical abrasive is sprayed at high speed using compressed air or centrifugal force, and The exterior member 2 in which the second surfaces 2B of the exterior member 2 that are not roughened are alternately arranged can be obtained. The second surface 1A of the structure 1 and the first surface 2A of the exterior member 2 are opposed to each other, and the second surface 1B of the structure 1 and the second surface 2B of the exterior member 2 are opposed to each other. A battery can be assembled.

  In the secondary battery of Example 2, the first surface of the exterior member was subjected to a surface treatment different from that of the second surface of the exterior member, which was caused by the volume change of the negative electrode active material during charging. Generation | occurrence | production of the curvature of a structure and generation | occurrence | production of the curvature of the whole secondary battery can be suppressed with the binding force of the exterior member with respect to a secondary battery. That is, when the sliding state of the first surface of the structure relative to the first surface of the exterior member is compared with the sliding state of the second surface of the structure relative to the second surface of the exterior member, the first surface of the structure is When the battery is charged, the structure tends to warp so that the first surface is convex, but due to the difference in the sliding state between the first surface and the second surface of the structure, the structure It is possible to reduce the amount of warping that the first surface of the projection becomes convex.

  Example 3 is a modification of Example 1 to Example 2 and relates to a secondary battery according to the third aspect of the present disclosure. That is, in the secondary battery of Example 3, the combination of (material constituting the first surface of the exterior member, material constituting the second surface of the exterior member) is (polypropylene, nylon), (polypropylene, Polyethylene) or (polyethylene, nylon). Alternatively, the first surface 2A of the exterior member 2 is made of a material different from the material constituting the second surface 2B of the exterior member 2.

  As shown in FIG. 1B, a schematic cross-sectional view (conceptual diagram) along the XY plane, the second surface 2B of the exterior member 2 is composed of a sheet-like member 2C. The sheet-like member 2 </ b> C is disposed between the material extending portion 2 </ b> A ′ constituting the first surface 2 </ b> A of the exterior member 2 and the second surface 1 </ b> B of the structure 1. Specifically, the sheet-like member 2C is bonded to the portion of the extending portion 2A ′ facing the second surface 1B of the structure 1.

More specifically, the exterior member 2 is composed of a first resin layer (a first plastic material layer, a fusion layer, specifically made of a polypropylene film), a metal layer (specifically, an aluminum foil). ) And a second resin layer (a second plastic material layer, a surface protective layer, specifically made of a nylon film). The first resin layer constitutes the first surface 2A and the extending portion 2A ′ of the exterior member 2. Moreover, the 2nd surface 2B of the exterior member 2 is comprised by the sheet-like member 2C which consists of a nylon film piece. Here, μ ₁ > μ ₂ is satisfied.

Alternatively, more specifically, the exterior member 2 includes a first resin layer (a first plastic material layer, a fusion layer, specifically made of a polypropylene film), a metal layer (specifically, aluminum). And a laminated structure of a second resin layer (a second plastic material layer, which is a surface protective layer, specifically, a nylon film). The first resin layer constitutes the first surface 2A and the extending portion 2A ′ of the exterior member 2. Moreover, the 2nd surface 2B of the exterior member 2 is comprised by the sheet-like member 2C which consists of a polyethylene film piece. Here, μ ₁ > μ ₂ is satisfied.

Alternatively, more specifically, the exterior member 2 includes a first resin layer (a first plastic material layer, a fusion layer, specifically made of a polyethylene film), a metal layer (specifically, an aluminum film). And a laminated structure of a second resin layer (a second plastic material layer, which is a surface protective layer, specifically, a nylon film). The first resin layer constitutes the first surface 2A and the extending portion 2A ′ of the exterior member 2. Moreover, the 2nd surface 2B of the exterior member 2 is comprised by the sheet-like member 2C which consists of a nylon film piece. Here, μ ₁ > μ ₂ is satisfied.

  In the secondary battery of Example 3, since the combination of (the material constituting the first surface of the exterior member and the material constituting the second surface of the exterior member) is defined, the negative electrode active material during charging It is possible to suppress the occurrence of warpage of the structure due to the volume change of the secondary battery and the warpage of the entire secondary battery by the restraining force of the exterior member with respect to the secondary battery.

  Example 4 relates to the secondary battery according to the fourth aspect of the present disclosure. 2A and 2B are conceptual diagrams showing a cross section of the secondary battery of Example 4. FIG. 2A shows a state after the first exterior member and the second exterior member are thermally fused, and FIG. These show the state before heat-seal | fusing a 1st exterior member and a 2nd exterior member (however, it shows except the structure 1), and the typical partial cross section of a 1st exterior member and a 2nd exterior member The diagram is shown in FIG. 2C.

  In Example 4, based on a two-dimensional stress simulation, expansion of the structure due to expansion of the negative electrode active material of the secondary battery, and materials constituting the first exterior member and the second exterior member (in particular, the material) The Young's modulus of the secondary battery has an effect on the warpage of the secondary battery.

The secondary battery of Example 4 is also a secondary battery in which a structure 1 in which a positive electrode, a separator, and a negative electrode are wound or stacked is housed in an exterior member and filled with an electrolyte. The exterior member includes a first exterior member 7 and a second exterior member 8 in which a recess 9 for housing the structure 1 is formed and an outer edge 8 a is fixed to the first exterior member 7. Here, the material constituting the first exterior member 7 is different from the material constituting the second exterior member 8. The first exterior member 7 has a higher Young's modulus than the second exterior member 8. Specifically, the first exterior member 7 has a laminated structure of a first A resin layer 7A, a first metal layer 7C, and a first B resin layer 7B, and the second exterior member 8 includes the second A resin layer 8A, the first It has a laminated structure of two metal layers 8C and a second B resin layer 8B. The first metal layer 7C is made of stainless steel, and the second metal layer 8C is made of aluminum. The thickness of the first metal layer 7C is 1 × 10 ⁻⁵ m to 1.8 × 10 ⁻⁴ m, and the thickness of the second metal layer 8C is 5 × 10 ⁻⁵ m to 2 × 10 ^−4. m. More specifically, the specifications of the first exterior member 7 and the second exterior member 8 are shown in Table 2 below.

As in the first embodiment, for simplification, in the secondary battery as a model, the first portion (the portion on the first surface 1A side) 1a and the second portion (first portion) of the structure 1 are used. It is assumed that the portion 1b on the second surface 1B side is integrated. The thickness (the thickness in the Y direction) of the first portion 1a of the structure 1 is 1.0 mm, and the thickness (the thickness in the Y direction) of the second portion 1b of the structure 1 is 1.0 mm. Further, it is assumed that the first part 1a and the second part 1b are symmetric with respect to the boundary 1c. Furthermore, the length in the longitudinal direction (X direction) of the structure 1 is set to 40.0 mm. The thicknesses of the first exterior member 7 and the second exterior member 8 are as shown in Table 2, and the length of the second exterior member 8 in the longitudinal direction (X direction) is 42.0 mm. Further, the expansion rates in the X direction and Y direction of the first portion 1a during charging are 1.1% and 6.0%, and the expansion rates in the X direction and Y direction of the second portion 1b are 1.0%. %, 6.0%. In other words, the larger amount of expansion when the structure 1 is expanded by charging is the first surface 1A of the structure 1, and the smaller one is the second surface 1B of the structure 1. Alternatively, when charged, the structure 1 warps so that the first surface 1A is convex. The Young's modulus of the first part 1a and the second part 1b is 4 × 10 ⁹ Pa and the Poisson's ratio is 0.3.

<Table 2>
Young's modulus thickness (μm)
1A resin layer 7A PET resin 25
First metal layer 7C stainless steel 20 × 10 ⁹ Pa 50
1B resin layer 7B PP resin 25
2A resin layer 8A PET resin 25
Second metal layer 8C Aluminum 4 × 10 ⁹ Pa 50
2B resin layer 8B PP resin 25

  In Reference Example 4, the first metal layer 7C was made of the same material (aluminum) as the second metal layer 8C. Except for this point, the configuration and structure of the secondary battery of Reference Example 4 are the same as the configuration and structure of the secondary battery of Example 4. That is, when a laminate film using a highly rigid stainless steel foil is adopted for the flat portion 9A (see FIG. 2A) of the laminate film (Example 4), and when a laminate film using a normal aluminum foil is used ( In Reference Example 4), the warpage during charging was compared by structural calculation. That is, simulation was performed to see how the amount of warpage (unit: mm) during charging of the secondary batteries of Example 4 and Reference Example 4 changed. As a result, the amount of warpage of the secondary battery of Example 4 was 0.13 mm. On the other hand, the amount of warpage of the secondary battery of Reference Example 4 was 0.16 mm. That is, the amount of warpage of the secondary battery of Example 4 was improved by 19% {= (1−0.13 / 0.16) × 100%} compared to the secondary battery of Reference Example 4. I found out.

  When the internal structure of the secondary battery is asymmetric between the front surface side and the back surface side, it is unavoidable that a bending moment is generated due to the difference in the expansion amount of the structure in the height (thickness) direction. Due to this bending moment, the entire secondary battery may be deformed, and the reliability of the secondary battery characteristics may be impaired. In Example 4, deformation of the secondary battery during charging can be suppressed by using a laminate film of high-stiffness stainless steel foil for the flat portion. As for the stainless steel foil, the rigidity is further increased by increasing the thickness. However, if the laminate film using the thick stainless steel foil is pressed to seal the structure of the secondary battery, the workability is poor. . Therefore, the exterior member is divided into a first exterior member (corresponding to the flat portion of the laminate film) and a second exterior member (other portions, which are provided with a recess, a depression, or an emboss), The flat surface portion is made of stainless steel foil to increase the rigidity, and the aluminum foil is used in the recess (emboss) to avoid the problem of formability.

  In addition, the combination of the first exterior member and the second exterior member of Example 4 is classified into an exterior member in the secondary battery in Example 1, an exterior member in the secondary battery in Example 2, and an exterior in the secondary battery in Example 3. It can be applied to members.

  The fifth embodiment is a modification of the first to fourth embodiments. In the following description, the secondary battery described in Example 1 to Example 3 will be mainly described as an example, but the description can be applied to the secondary battery described in Example 4. Needless to say. The same applies to Example 6 described later.

  The secondary battery of Example 5 is a flat laminate film type secondary battery in which a positive electrode, a separator, and a negative electrode are wound. A schematic exploded perspective view of the secondary battery of Example 5 is shown in FIGS. 3 and 4A, and a schematic enlargement along the arrow AA of the wound electrode body (structure) shown in FIGS. 3 and 4A. A cross-sectional view (a schematic enlarged cross-sectional view along the YZ plane) is shown in FIG. 4B. Furthermore, FIG. 5A shows a schematic partial cross-sectional view (schematic partial cross-sectional view along the XY plane) in which a part of the wound electrode body (structure) shown in FIG. 4B is enlarged.

  In the secondary battery of Example 5, the wound electrode body (structure) 20 is housed inside the exterior member 10 (or the first exterior member and the second exterior member) made of a laminate film. In the following description, the exterior member 10, the first exterior member, and the second exterior member may be collectively referred to as “exterior member 10 or the like”. The wound electrode body 20 can be produced by laminating the positive electrode 23 and the negative electrode 24 via the separator 25 and the electrolyte layer 26 and then winding the laminate. A positive electrode lead 21 is attached to the positive electrode 23, and a negative electrode lead 22 is attached to the negative electrode 24. The outermost periphery of the wound electrode body 20 is protected by a protective tape 27. Therefore, the protective tape 27 corresponds to the first surface of the structure and the second surface of the structure.

  In such a wound electrode body (structure) 20, the laminate is wound around the winding center. In FIG. 4B, the XZ plane passing through the winding center is indicated by CC, and the XZ plane passing through the winding center corresponds to the boundary 1c between the first portion 1a and the second portion 1b in the first embodiment. To do. And in FIG. 4B, the winding part (equivalent to the 1st part 1a in Example 1) located above the XZ plane shown by CC, and the saddle located below the XZ plane shown by CC The turn portion (corresponding to the second portion 1b in the first embodiment) is different in the number of turns (the number of turns), and the attachment positions of the positive electrode lead 21 and the negative electrode lead 22 are different. That is, it was caused by the thickness direction (Y direction) asymmetry (winding number asymmetry, lead mounting position asymmetry) in the wound electrode body (structure) 20 which is a component inside the secondary battery. The difference in expansion causes a bending moment. However, even in Example 5, by providing the various regulations described in Examples 1 to 4, a secondary battery is provided that is less likely to be warped due to volume change of the negative electrode active material during charging. can do.

  The positive electrode lead 21 and the negative electrode lead 22 protrude in the same direction from the inside of the exterior member 10 and the like toward the outside. The positive electrode lead 21 is formed from a conductive material such as aluminum. The negative electrode lead 22 is formed from a conductive material such as copper, nickel, and stainless steel. These conductive materials have, for example, a thin plate shape or a mesh shape.

  The exterior member 10 is a single film that can be folded in the direction of the arrow R shown in FIG. 3, and a recess (recess or emboss) for housing the wound electrode body 20 is formed in a part of the exterior member 10. Is provided. Specifically, the exterior member 10 has, for example, a moisture resistance in which a nylon film (thickness 30 μm), an aluminum foil (thickness 40 μm), and an unstretched polypropylene film (thickness 30 μm) are laminated in this order from the outside. An aluminum laminate film (total thickness 100 μm). Alternatively, the exterior member has the configuration and structure described in the fourth embodiment.

  In order to prevent intrusion of outside air, the adhesive film 11 is inserted between the exterior member 10 and the like and the positive electrode lead 21, and between the exterior member 10 and the like and the negative electrode lead 22. The adhesion film 11 is made of a material having adhesion to the positive electrode lead 21 and the negative electrode lead 22, for example, a polyolefin resin, and more specifically, a polyolefin resin such as polyethylene, polypropylene, modified polyethylene, and modified polypropylene.

  As shown in FIGS. 4B and 5A, the positive electrode 23 has a positive electrode active material layer 23B on one or both surfaces of the positive electrode current collector 23A. The negative electrode 24 has a negative electrode active material layer 24B on one or both surfaces of the negative electrode current collector 24A.

When producing the positive electrode 23, first, 91 parts by mass of a positive electrode active material <LiCoO ₂ >, 3 parts by mass of a positive electrode binder (polyvinylidene fluoride), and 6 parts by mass of a positive electrode conductive agent (graphite, graphite) are mixed. Thus, a positive electrode mixture is obtained. Then, the positive electrode mixture is mixed with an organic solvent (N-methyl-2-pyrrolidone) to obtain a paste-like positive electrode mixture slurry. Next, after applying the positive electrode mixture slurry on both surfaces of the strip-shaped positive electrode current collector 23A (a 12 μm thick aluminum foil) using a coating apparatus, the positive electrode mixture slurry is dried to form the positive electrode active material layer 23B. To do. And the positive electrode active material layer 23B is compression-molded using a roll press machine.

When Li _1.15 (Mn _0.65 Ni _0.22 Co _0.13 ) _0.85 O ₂ is used as the positive electrode active material, first, nickel sulfate <NiSO ₄ >, cobalt sulfate <CoSO ₄ >, and manganese sulfate <MnSO ₄ > are mixed. Then, the mixture is dispersed in water to prepare an aqueous solution. Next, while sufficiently stirring the aqueous solution, sodium hydroxide <NaOH> is added to the aqueous solution to obtain a coprecipitate (manganese / nickel / cobalt composite coprecipitate hydroxide). Thereafter, the coprecipitate is washed with water and dried, and then lithium hydroxide monohydrate is added to the coprecipitate to obtain a precursor. And said positive electrode active material can be obtained by baking a precursor (800 degreeC x 10 hours) in air | atmosphere.

When LiNi _0.5 Mn _1.50 O ₄ is used as the positive electrode active material, first, lithium carbonate <Li ₂ CO ₃ >, manganese oxide <MnO ₂ >, and nickel oxide <NiO> are weighed and a ball mill is used. Mix the weighed material. In this case, the mixing ratio (molar ratio) of the main elements is Ni: Mn = 25: 75. Next, the mixture is fired in the atmosphere (800 ° C. × 10 hours) and then cooled. Next, after remixing the fired product using a ball mill, the fired product is refired in the atmosphere (700 ° C. × 10 hours), whereby the positive electrode active material can be obtained.

  Alternatively, a compound represented by the following formula (A) or a LiNiMnO-based material can be used as the positive electrode active material.

Li _{1 + a} (Mn _b Co _c Ni _1-bc ) _1-a M ⁰ _d O _2-e (A)
Here, “M ⁰ ” is at least one element belonging to Group 2 to Group 15 (excluding manganese, cobalt and nickel) in the long-period periodic table, and 0 <a <0.25, 0 3 ≦ b <0.7, 0 ≦ c <1-b, 0 ≦ d ≦ 1, 0 ≦ e ≦ 1 are satisfied. Specifically, Li _1.15 (Mn _0.65 Ni _0.22 Co _0.13 ) _0.85 O ₂ can be exemplified. Further, as the LiNiMnO-based material, specifically, LiNi _0.5 Mn _1.50 O ₄ can be exemplified.

When producing the negative electrode 24, first, 97 parts by mass of a negative electrode active material (graphite, graphite) and 3 parts by mass of a negative electrode binder (polyvinylidene fluoride) are mixed to obtain a negative electrode mixture. The average particle diameter d ₅₀ of graphite is 20 μm. Next, the negative electrode mixture is mixed with an organic solvent (N-methyl-2-pyrrolidone) to obtain a paste-like negative electrode mixture slurry. And after apply | coating a negative mix slurry on both surfaces of strip | belt-shaped negative electrode collector 24A (15-micrometer-thick copper foil) using a coating apparatus, a negative mix slurry is dried and negative electrode active material layer 24B is formed. To do. And the negative electrode active material layer 24B is compression-molded using a roll press machine.

Alternatively, a negative electrode active material (silicon) and a negative electrode binder precursor (polyamic acid) may be mixed to form a negative electrode mixture. In this case, the mixing ratio is silicon: polyamic acid = 80: 20 in terms of dry mass ratio. The average particle diameter d ₅₀ of silicon is 1 μm. N-methyl-2-pyrrolidone and N, N-dimethylacetamide are used as a solvent for the polyamic acid. Further, after the compression molding, the negative electrode mixture slurry is heated in a vacuum atmosphere under conditions of 400 ° C. × 12 hours. Thereby, polyimide which is a negative electrode binder is formed.

  The separator 25 is made of a microporous polyethylene film having a thickness of 20 μm. The wound electrode body 20 is impregnated with a non-aqueous electrolyte solution that is a gel electrolyte.

  The electrolyte layer 26 includes a non-aqueous electrolyte solution and a holding polymer compound, and the non-aqueous electrolyte solution is held by the holding polymer compound. The electrolyte layer 26 is a gel electrolyte, and high ionic conductivity (for example, 1 mS / cm or more at room temperature) is obtained, and leakage of the non-aqueous electrolyte is prevented. The electrolyte layer 26 may further contain other materials such as additives.

  The following Table 3 and Table 4 can be illustrated as a composition of a non-aqueous electrolyte solution.

<Table 3>
Organic solvent: EC / PC 1/1 by mass ratio
Lithium salt constituting non-aqueous electrolyte: LiPF ₆ 1.0 mol / organic solvent 1 kg
Other additives: Vinylene carbonate (VC) 1% by mass

<Table 4>
Organic solvent: EC / DMC / FEC
2.7 / 6.3 / 1.0 by mass ratio
Lithium salt constituting non-aqueous electrolyte: LiPF ₆ 1.0 mol / organic solvent 1 kg

Specific examples of the holding polymer compound include polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, polysiloxane, polyvinyl fluoride (PVF), poly Chlorotrifluoroethylene (PCTFE), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoro Ethylene copolymer (ECTFE), polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene It can be exemplified polycarbonate, polyethylene oxide, polyvinyl chloride. These may be used alone or in combination. The holding polymer compound may be a copolymer. Specific examples of the copolymer include a copolymer of vinylidene fluoride and hexafluoropyrene. Among them, polyvinylidene fluoride is used as a homopolymer from the viewpoint of electrochemical stability. And a copolymer of vinylidene fluoride and hexafluoropyrene is preferred as the copolymer. Further, the filler may contain a compound having high heat resistance such as Al ₂ O ₃ , SiO ₂ , TiO ₂ , BN (boron nitride).

When preparing a non-aqueous electrolyte solution, although mentioned later for details, a 1st compound, a 2nd compound, a 3rd compound, and another material are mixed and stirred. As the first compound, bisfluorosulfonylimide lithium <LiFSI> or bistrifluoromethylsulfonylimide lithium <LiTFSI> is used. As the second compound, acetonitrile (AN), propionitrile (PN) or butyronitrile (BN), which is a non-oxygen-containing mononitrile compound, or methoxyacetonitrile (MAN), which is an oxygen-containing mononitrile compound, is used. Further, as the third compound, vinylene carbonate (VC), vinyl ethylene carbonate (VEC) or methylene ethylene carbonate (MEC), which is an unsaturated cyclic carbonate, or 4-fluoro-1,3 which is a halogenated carbonate, is used. -Dioxolan-2-one (FEC) or bis (fluoromethyl) carbonate (DFDMC) or succinonitrile (SN) which is a polynitrile compound is used. Furthermore, as other materials, ethylene carbonate (EC) which is a cyclic carbonate, dimethyl carbonate (DMC) which is a chain carbonate, lithium hexafluorophosphate <LiPF ₆ > which is an electrolyte salt, boron tetrafluoride Lithium acid <LiBF ₄ > is used.

  In the electrolyte layer 26 which is a gel electrolyte, the solvent of the non-aqueous electrolyte solution is a wide concept including not only a liquid material but also a material having ion conductivity capable of dissociating an electrolyte salt. . Therefore, when using a polymer compound having ion conductivity, the polymer compound is also included in the solvent. Instead of the gel electrolyte layer 26, a non-aqueous electrolyte solution may be used as it is. In this case, the wound electrode body 20 is impregnated with a non-aqueous electrolyte solution.

  Specifically, when forming the electrolyte layer 26, first, a non-aqueous electrolyte solution is prepared. Then, a non-aqueous electrolyte solution, a holding polymer compound, and an organic solvent (dimethyl carbonate) are mixed to prepare a sol precursor solution. As a holding polymer compound, a copolymer of hexafluoropropylene and vinylidene fluoride (the copolymerization amount of hexafluoropropylene = 6.9% by mass) is used. Next, after applying the precursor solution to the positive electrode 23 and the negative electrode 24, the precursor solution is dried to form the gel electrolyte layer 26.

  An insulating material may be provided in any of the regions (interactive material regions) between the positive electrode active material included in the positive electrode 23 and the negative electrode active material included in the negative electrode 24. The place where an insulating material is arrange | positioned will not be specifically limited if it is either in the area | region between active materials. That is, the insulating material may be present in the positive electrode 23 (positive electrode active material layer 23B), may be present in the negative electrode 24 (negative electrode active material layer 24B), or the positive electrode 23 and the negative electrode 24. May exist between the two. As an example, as to the place where the insulating material is disposed, for example, there are three modes as described below.

  In the first aspect, as shown in FIG. 5B, the positive electrode active material layer 23 </ b> B includes a particulate positive electrode active material 211. A layer containing an insulating material (an active material insulating layer 212 which is a first insulating layer) is formed on the surface of the positive electrode active material 211. The active material insulating layer 212 may cover only a part of the surface of the positive electrode active material 211 or may cover the entire surface. When the active material insulating layer 212 covers a part of the surface of the positive electrode active material 211, a plurality of active material insulating layers 212 that are separated from each other may exist. The active material insulating layer 212 may be a single layer or a multilayer.

The active material insulating layer 212 is made of an inorganic insulating material such as insulating ceramics, or is made of an organic insulating material such as an insulating polymer compound, or is made of an inorganic insulating material and an organic insulating material. . Specific examples of the insulating ceramic include aluminum oxide <Al ₂ O ₃ >, silicon oxide <SiO ₂ >, magnesium oxide <MgO>, titanium oxide <TiO ₂ >, and zirconium oxide <ZrO ₂ >. LiNbO ₃ , LIPON <Li _{3 + y} PO _4−x N _x , where 0.5 ≦ x ≦ 1, −0.3 <y <0.3>, LISICON (Lithium-Super-Ion-CONductor ), Thio-LISICON (for example, Li _3.25 Ge _0.25 P _0.75 S ₄ ), Li ₂ S, Li ₂ S—P ₂ S ₅ , Li ₂ S—SiS ₂ , Li ₂ S—GeS ₂ , Li _{2 S-B 2 S 5, Li} 2 S-Al 2 S 5 and _{Li 2 O-Al 2 O 3} -TiO 2 -P 2 O 5 (LATP) may be exemplified. The insulating polymer compound can be the same as the material constituting the binder, and among them, a homopolymer of vinylidene fluoride (for example, polyvinylidene fluoride) or a copolymer (for example, vinylidene fluoride and A copolymer with hexafluoropropylene) is preferred. This is because it has excellent physical strength and is electrochemically stable. The monomer copolymerized with vinylidene fluoride may be a monomer other than hexafluoropropylene.

  The procedure for forming the active material insulating layer 212 on the surface of the positive electrode active material 211 is, for example, as follows. Note that the case where the active material insulating layer 212 includes insulating ceramics will be described as an example. When the active material insulating layer 212 is formed, the positive electrode active material 211 particles and the insulating ceramic particles are mixed. Then, the mixture is pulverized and mixed using a ball mill, a jet mill, a pulverizer, a fine powder pulverizer, or the like. In this case, a dispersion medium such as water or a solvent may be added to the mixture. As a result, the insulating ceramic is deposited on the surface of the positive electrode active material 211, so that the active material insulating layer 212 is formed. In addition, insulating ceramics may be deposited using mechanochemical treatment such as mechanofusion. Insulating ceramics may be deposited on the surface of the positive electrode active material 211 based on a PVD method such as a sputtering method or a CVD method. Alternatively, a sol-gel method may be used. In this case, after the positive electrode active material 211 is immersed in an alkoxide solution containing aluminum, silicon, etc., the precursor layer is deposited on the surface of the positive electrode active material 211. The precursor layer may be fired.

  In the second mode, as shown in FIG. 5C, a layer containing an insulating material (a negative electrode insulating layer 213 as a second insulating layer) is provided on the surface of the negative electrode 24 (negative electrode active material layer 24B). Details regarding the covering state, the layer structure, the constituent materials, and the like of the negative electrode insulating layer 213 are the same as those of the active material insulating layer 212 described above. In this case, in particular, when the negative electrode insulating layer 213 includes an insulating polymer compound, the adhesion of the separator 25 to the negative electrode 24 is improved, so that the wound electrode body 20 is hardly distorted. As a result, the decomposition reaction of the non-aqueous electrolyte solution is suppressed, and leakage of the non-aqueous electrolyte solution impregnated in the separator 25 is also suppressed. Therefore, even if charging / discharging is repeated, the resistance is difficult to increase and the secondary battery is difficult to expand.

  The procedure for forming the negative electrode insulating layer 213 on the surface of the negative electrode active material layer 24B is, for example, as follows. The case where the negative electrode insulating layer 213 includes insulating ceramics and an insulating polymer compound will be described as an example. When forming the negative electrode insulating layer 213, the insulating ceramic particles, the insulating polymer compound, and a solvent such as N-methyl-2-pyrrolidone are mixed to disperse the insulating ceramic particles in the solvent. At the same time, the insulating polymer compound is dissolved in a solvent. Then, after the negative electrode 24 is immersed in the mixed solution, the negative electrode 24 is taken out from the mixed solution and dried. As a result, the solvent in the mixed solution volatilizes and the insulating polymer compound forms a film, so that the negative electrode insulating layer 213 is formed on the surface of the negative electrode active material layer 24B. In this case, the thickness of the negative electrode insulating layer 213 may be adjusted by pressurizing the negative electrode 24 before drying. Instead of immersing the negative electrode 24 in the mixed solution, the mixed solution may be applied to the surface of the negative electrode active material layer 24B.

Alternatively, when forming the negative electrode insulating layer 213, first, 80 parts by mass of powdery insulating ceramics and 20 parts by mass of an insulating polymer compound (polyvinylidene fluoride) are mixed, and then the mixture is dispersed in an organic solvent. To prepare a treatment solution. Aluminum oxide <Al ₂ O ₃ > and silicon oxide <SiO ₂ > are used as the powdery insulating ceramic. The average particle diameter d ₅₀ of the insulating ceramic is 0.5 μm. And after immersing the negative electrode 24 in a processing solution, the thickness of the processing solution supplied to the surface of the negative electrode 24 is adjusted using a gravure roller. Then, the treatment solution is dried at 120 ° C. using a dryer, and the organic solvent in the treatment solution is volatilized. In this manner, the negative electrode insulating layer 213 can be formed on the surface of the negative electrode active material layer 24B. The thickness of the negative electrode insulating layer 213 is set to 5 μm, for example.

  In the third mode, as shown in FIG. 5D, a layer containing an insulating material (a separator insulating layer 214 as a third insulating layer) is provided on the surface of the separator 25. The separator insulating layer 214 may be provided on the surface facing the positive electrode 23 of the separator 25, may be provided on the surface facing the negative electrode 24, or may be provided on both surfaces. Details regarding the covering state, the layer structure, the constituent materials, and the like of the separator insulating layer 214 are the same as those of the active material insulating layer 212 described above. In this case, in particular, when the separator insulating layer 214 includes an insulating polymer compound, the adhesion of the separator 25 to the positive electrode 23 and the negative electrode 24 is improved, so that the negative electrode insulating layer 213 includes a polymer compound. Advantages similar to those of the inclusion are obtained.

  When forming the separator insulating layer 214, first, a treatment solution is prepared based on the same procedure as that for preparing the negative electrode insulating layer 213. Next, the separator 25 is immersed in the treatment solution. Then, after pulling up the separator 25 from the processing solution, the separator 25 is washed with water. Then, the treatment solution supplied to the surface of the separator 25 is dried with hot air at 80 ° C. to volatilize the organic solvent in the treatment solution. In this way, the separator insulating layer 214 can be formed on both surfaces of the separator 25. The thickness (total thickness) of the separator insulating layer 214 formed on both surfaces of the separator 25 is, for example, 4.5 μm.

  The procedure for forming the separator insulating layer 214 on the surface of the separator 25 is the same as the procedure for forming the negative electrode insulating layer 213 described above. When the separator insulating layer 214 includes only the insulating polymer compound, the same procedure as that when the separator insulating layer 214 includes the insulating ceramic and the insulating polymer compound is used except that the insulating ceramic particles are not used. May be used.

  By disposing an insulating material in any of the areas between the active materials, both battery characteristics and safety can be achieved. That is, when an insulating material is disposed in the region between the active materials, safety such as thermal runaway is less likely to occur inside the secondary battery, and thus safety is improved. In addition, when the non-aqueous electrolyte contains the first compound (described later), the surface condition of the insulating material is optimized due to the reaction with the first compound, so that the insulating material region has insulating properties. Even if the material is present, the lithium ions easily move smoothly, so that the battery characteristics are ensured. Therefore, safety is improved while ensuring battery characteristics.

The mechanism by which the surface state of the insulating material is optimized is considered to be as follows, for example. That is, when the insulating material includes an insulating ceramic such as aluminum oxide, lithium ions tend to hardly move due to the hydroxyl group <—OH> present on the particle surface of the insulating material. However, when the first compound (described later) is contained in the non-aqueous electrolyte solution, the first compound and the insulating material react with each other, so that the coating that hardly inhibits the movement of lithium ions on the surface of the insulating material. Is formed. In this case, for example, the first compound contains a SO ₂ -F bond, SO ₂ -F bond and because the hydroxyl group and is _{reacted, F-SO 2 -N-SO} 2 on the surface of the particles of the ceramic -O- A good film with bonds is formed. And with this film, the surface state of the ceramic is modified so that it is difficult to inhibit the movement of lithium ions.

  The secondary battery provided with the gel electrolyte layer 26 can be manufactured based on, for example, the following three types of procedures. In the following description, the procedure for forming the insulating layers 212, 213, and 214 is omitted.

  In the first procedure, first, the positive electrode active material layer 23B is formed on both surfaces of the positive electrode current collector 23A, and the negative electrode active material layer 24B is formed on both surfaces of the negative electrode current collector 24A. On the other hand, a non-aqueous electrolyte solution, a holding polymer compound, and an organic solvent are mixed to prepare a sol precursor solution. And after apply | coating a precursor solution to the positive electrode 23 and the negative electrode 24, a precursor solution is dried and the gel-like electrolyte layer 26 is formed. Thereafter, using a welding method or the like, the positive electrode lead 21 is attached to the positive electrode current collector 23A, and the negative electrode lead 22 is attached to the negative electrode current collector 24A. Next, the positive electrode 23 and the negative electrode 24 are laminated through a separator 25 made of a microporous polypropylene film having a thickness of 25 μm and wound to produce a wound electrode body 20, and then a protective tape is provided on the outermost peripheral portion. 27 is pasted. Then, after folding the exterior member 10 so as to sandwich the wound electrode body 20, the outer peripheral edges of the exterior member 10 are bonded to each other using a heat fusion method or the like, and the wound electrode body is placed inside the exterior member 10. 20 is enclosed. Alternatively, after that, the wound electrode body 20 is housed in the concave portion of the second exterior member, and the first exterior member and the second exterior member are bonded using a heat fusion method or the like, and the first exterior member and the first exterior member are bonded. 2 Enclose the wound electrode body inside the exterior member. An adhesive film (acid-modified propylene film having a thickness of 50 μm) 11 is inserted between the positive electrode lead 21 and the negative electrode lead 22 and the exterior member 10 or the like.

  Alternatively, in the second procedure, first, the positive electrode 23 and the negative electrode 24 are prepared. Then, the positive electrode lead 21 is attached to the positive electrode 23, and the negative electrode lead 22 is attached to the negative electrode 24. Thereafter, the positive electrode 23 and the negative electrode 24 are laminated via the separator 25 and wound to produce a wound body that is a precursor of the wound electrode body 20, and then the protective tape 27 is provided on the outermost peripheral portion of the wound body. Paste. Next, after folding the exterior member 10 so as to sandwich the wound body, the remaining outer peripheral edge portion excluding the outer peripheral edge portion on one side of the exterior member 10 is bonded using a heat sealing method or the like to form a bag The wound body is housed inside the exterior member 10. Alternatively, after that, the wound body is accommodated in the concave portion of the second exterior member, and the first exterior member and the second exterior member are bonded using a heat fusion method or the like, so that the first exterior member and the second exterior member are bonded. A wound electrode body is sealed inside the member. On the other hand, a non-aqueous electrolyte solution, a monomer that is a raw material for the polymer compound, a polymerization initiator, and other materials such as a polymerization inhibitor as necessary are mixed to prepare an electrolyte composition. And after inject | pouring the composition for electrolytes into the exterior member 10 grade | etc., The exterior member 10 grade | etc., Is sealed using the heat sealing | fusion method etc. FIG. Thereafter, the monomer is thermally polymerized to form a polymer compound. As a result, the gel electrolyte layer 26 is formed.

  Alternatively, in the third procedure, a wound body is produced in the same manner as in the second procedure, except that the separator 25 coated with the polymer compound on both sides is used. Store inside. The polymer compound applied to the separator 25 is, for example, a polymer (homopolymer, copolymer or multi-component copolymer) containing vinylidene fluoride as a component. Specifically, polyvinylidene fluoride, a binary copolymer containing vinylidene fluoride and hexafluoropropylene as components, and a ternary copolymer containing vinylidene fluoride, hexafluoropropylene and chlorotrifluoroethylene as components. Such as coalescence. One or two or more other polymer compounds may be used together with the polymer containing vinylidene fluoride as a component. Thereafter, a non-aqueous electrolyte solution is prepared and injected into the exterior member 10 or the like, and then the opening of the exterior member 10 or the like is sealed using a thermal fusion method or the like. Next, heating is performed while applying a load to the exterior member 10 and the like, and the separator 25 is brought into close contact with the positive electrode 23 and the negative electrode 24 through the polymer compound. As a result, the non-aqueous electrolytic solution is impregnated into the polymer compound, and the polymer compound is gelled to form the electrolyte layer 26.

  In the third procedure, the swelling of the secondary battery is suppressed more than in the first procedure. Further, in the third procedure, compared with the second procedure, the solvent and the monomer that is a raw material of the polymer compound hardly remain in the electrolyte layer 26, so that the formation process of the polymer compound is well controlled. The Therefore, the positive electrode 23, the negative electrode 24, the separator 25, and the electrolyte layer 26 are sufficiently adhered.

  The secondary battery of Example 5 operates as follows, for example. That is, when lithium ions are released from the positive electrode 23 during charging, the lithium ions are occluded in the negative electrode 24 through the nonaqueous electrolytic solution. On the other hand, when lithium ions are released from the negative electrode 24 during discharge, the lithium ions are occluded in the positive electrode 23 through the nonaqueous electrolytic solution. The secondary battery, for example, has an open circuit voltage (battery voltage) at the time of full charge of 4.2 to 6.0 volts, preferably 4.25 to 6.0 volts, more preferably 4.3 to 4 volts. Desirably designed to be .55 volts. In this case, compared to the case where the open circuit voltage at the time of full charge is designed to be 4.2 volts, the amount of lithium released per unit mass is large even when the same type of positive electrode active material is used. Become. In this way, the amount of the positive electrode active material and the amount of the negative electrode active material are adjusted, and the secondary battery is designed so that the open circuit voltage (battery voltage) at the time of full charge becomes a predetermined voltage (upper limit voltage). Thus, a high energy density can be obtained.

  The sixth embodiment is also a modification of the first to fourth embodiments. The secondary battery of Example 6 is a flat laminate film type secondary battery in which a positive electrode, a separator, and a negative electrode are laminated. FIG. 1C shows a schematic cross-sectional view (schematic partial cross-sectional view along the XY plane) of the secondary battery of Example 6.

  Even in the secondary battery of Example 6, the structure (laminated electrode body) 3 is accommodated in the exterior member 2 ″ made of a laminate film. The structure 3 includes the separator 6 and the electrolyte layer (not shown). The positive electrode 4 is composed of a positive electrode current collector 4A and a positive electrode active material layer 4B, and the positive electrode active material layer 4B is a positive electrode. The negative electrode 5 is composed of a negative electrode current collector 5A and a negative electrode active material layer 5B, and the negative electrode active material layer 5B is formed on both surfaces of the negative electrode current collector 5A. In the illustrated example, the negative electrode current collector 5A / the negative electrode active material layer 5B / the separator 6 / the positive electrode active material layer 4B / the positive electrode current collector 4A / the positive electrode active material layer from the top to the bottom of the drawing. 4B / Separator 6 / Negative electrode active material layer 5B / Negative electrode current collector 5A / Negative electrode It is laminated in the order of material layer 5B / separator 6 / positive electrode active material layer 4B / positive electrode current collector 4A / positive electrode active material layer 4B / separator 6. In the illustrated example, positive electrode 4 / separator 6 is laminated. / Six pairs of negative electrodes 5 are stacked, each of the positive electrodes 4 is attached with a positive electrode lead (not shown), and the negative electrode 5 is attached with a negative electrode lead (not shown). The plurality of positive leads are grouped into one positive output terminal (not shown), and the plurality of negative leads are grouped into one negative output terminal (not shown). The electric body 5A corresponds to the first surface and the second surface of the structure, and the inner surface of the exterior member 2 ″ facing the negative electrode current collector 5A occupying the outermost side of the structure 3 is the first surface of the exterior member and Corresponds to the second side.

  In such a structure 3, in FIG. 1C, the XZ plane passing through the center in the thickness direction of the structure 3 is indicated by AA. This corresponds to the boundary 1c between the first portion 1a and the second portion 1b. And in FIG. 1C, the laminated part located above the XZ plane indicated by AA (corresponding to the first part 1a in Example 1) and the laminated part located below the XZ plane indicated by AA (Corresponding to the second portion 1b in the first embodiment), the attachment positions of the positive electrode lead and the negative electrode lead are different. That is, the difference in the expansion amount due to the asymmetry in the thickness direction (asymmetry of the mounting position of the lead) in the structure (laminated electrode body) 3 which is a constituent member inside the secondary battery generates a bending moment. However, even in Example 6, by providing the various regulations described in Examples 1 to 4, a secondary battery is provided that is less likely to warp due to volume change of the negative electrode active material during charging. can do.

  Since the secondary battery of Example 6 has substantially the same configuration and structure as the secondary battery of Example 5 except for the difference between winding and stacking, detailed description is omitted. To do. Moreover, since the secondary battery of Example 6 can be manufactured by the substantially same method as the secondary battery of Example 5, detailed description is abbreviate | omitted.

  In Example 7, an application example of the secondary battery of the present disclosure will be described.

  Applications of the secondary battery of the present disclosure include machines, devices, instruments, devices, systems (a plurality of devices, etc.) that can use the secondary battery of the present disclosure as a power source for driving / operation or a power storage source for power storage. If it is an aggregate | assembly of this, it will not specifically limit. The secondary battery used as a power source may be a main power source (a power source used preferentially) or an auxiliary power source (a power source used in place of or switched from the main power source). There may be. When a secondary battery is used as an auxiliary power source, the main power source is not limited to the secondary battery.

  Specific uses of the secondary battery of the present disclosure include video cameras, camcorders, digital still cameras, mobile phones, personal computers, television receivers, various display devices, cordless phones, headphone stereos, music players, and portable devices. Various electronic devices such as radio, electronic books and electronic newspapers, portable information terminals including PDAs (Personal Digital Assistants), electrical devices (including portable electronic devices); toys; portable living devices such as electric shavers Lighting devices such as room lights; medical electronic devices such as pacemakers and hearing aids; storage devices such as memory cards; battery packs used in personal computers as removable power supplies; electric tools such as electric drills and electric saws; A power storage system such as a home battery system that stores power for emergencies. System and home energy server (household power storage device); power storage unit and backup power source; electric vehicles such as electric automobiles, electric motorcycles, electric bicycles, Segway (registered trademark); Can exemplify driving of a power motor, for example, but is not limited to these applications.

  Especially, it is effective that the secondary battery of this indication is applied to a battery pack, an electric vehicle, an electric power storage system, an electric tool, electronic equipment, electric equipment, etc. Since excellent battery characteristics are required, the performance can be effectively improved by using the secondary battery of the present disclosure. The battery pack is a power source using a secondary battery, and is a so-called assembled battery or the like. The electric vehicle is a vehicle that operates (runs) using a secondary battery as a driving power source, and may be an automobile (such as a hybrid automobile) that is provided with a driving source other than the secondary battery. The power storage system is a system that uses a secondary battery as a power storage source. For example, in a household power storage system, power is stored in a secondary battery that is a power storage source, so that household electrical products and the like can be used using the power. An electric power tool is a tool in which a movable part (for example, a drill etc.) moves, using a secondary battery as a driving power source. Electronic devices and electric devices are devices that exhibit various functions using a secondary battery as a power source (power supply source) for operation.

  Hereinafter, some application examples of the secondary battery will be specifically described. Note that the configuration of each application example described below is merely an example, and the configuration can be changed as appropriate.

  FIG. 6 shows a schematic perspective view of a disassembled battery pack using unit cells, and FIG. 7A shows a block diagram showing the configuration of the battery pack (unit cell). The battery pack is a simple battery pack (so-called soft pack) using one secondary battery, and is mounted, for example, on an electronic device typified by a smartphone. The battery pack includes a power source 31 composed of a secondary battery of Examples 1 to 6 of a laminate film type, and a circuit board 35 connected to the power source 31. A positive electrode lead 32 and a negative electrode lead 33 are attached to the power supply 31.

  A pair of adhesive tapes 37 are attached to both side surfaces of the power supply 31. The circuit board 35 is provided with a protection circuit (PCM: Protection Circuit Module). The circuit board 35 is connected to the positive electrode lead 32 through the tab 34A, and is connected to the negative electrode lead 33 through the tab 34B. Further, a lead wire 36 with a connector for external connection is connected to the circuit board 35. In a state where the circuit board 35 is connected to the power supply 31, the circuit board 35 is protected from above and below by a label 38 and an insulating sheet 39. By affixing the label 38, the circuit board 35 and the insulating sheet 39 are fixed. The circuit board 35 includes a control unit 41, a switch unit 42, a PTC element 43, a temperature detection unit 44, and a temperature detection element 44A. The power source 31 can be connected to the outside via the positive terminal 45A and the negative terminal 45B, and is charged and discharged. The power source 31 is charged and discharged via the positive terminal 45A and the negative terminal 45B. The temperature detection unit 44 can detect the temperature via the temperature detection element 44A.

  The control unit 41 that controls the operation of the entire battery pack (including the usage state of the power supply 31) includes a central processing unit (CPU), a memory, and the like. When the battery voltage reaches the overcharge detection voltage, the control unit 41 disconnects the switch unit 42 so that no charging current flows in the current path of the power supply 31. In addition, when a large current flows during charging, the control unit 41 disconnects the switch unit 42 and cuts off the charging current. In addition, when the battery voltage reaches the overdischarge detection voltage, the control unit 41 disconnects the switch unit 42 so that no discharge current flows in the current path of the power supply 31. Further, when a large current flows during discharge, the control unit 41 cuts off the switch unit 42 and cuts off the discharge current.

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

  The switch unit 42 switches the usage state of the power source 31 (whether the power source 31 can be connected to an external device) in accordance with an instruction from the control unit 41. The switch unit 42 includes a charge control switch, a discharge control switch, and the like. The charge control switch and the discharge control switch are composed of a semiconductor switch such as a field effect transistor (MOSFET) using a metal oxide semiconductor, for example. The charge / discharge current is detected based on the on-resistance of the switch unit 42, for example. The temperature detection unit 44 including a temperature detection element 44 </ b> A such as a thermistor measures the temperature of the power supply 31 and outputs the measurement result to the control unit 41. The measurement result of the temperature detection unit 44 is used for charge / discharge control by the control unit 41 at the time of abnormal heat generation, correction processing at the time of remaining capacity calculation by the control unit 41, and the like. The circuit board 35 may not be provided with the PTC element 43. In this case, the PTC element may be separately provided on the circuit board 35.

  Next, a block diagram showing a configuration of a battery pack (assembled battery) different from that shown in FIG. 7A is shown in FIG. 7B. This battery pack includes, for example, a control unit 51, a memory 52, a voltage detection unit 53, a current measurement unit 54, a current detection resistor 54A, a temperature detection unit 55, a temperature inside a housing 50 made of a plastic material or the like. A detection element 55A, a switch control unit 56, a switch unit 57, a power source 58, a positive terminal 59A, and a negative terminal 59B are provided.

  The control unit 51 controls the operation of the entire battery pack (including the usage state of the power supply 58), and includes, for example, a CPU. The power source 58 is, for example, an assembled battery including two or more secondary batteries (not shown) described in the first to sixth embodiments, and the connection form of the secondary batteries may be in series or in parallel. However, both types may be used. For example, the power source 58 includes six secondary batteries connected in two parallel three series.

  The switch unit 57 switches the usage state of the power source 58 (whether the power source 58 can be connected to an external device) in accordance with an instruction from the control unit 51. The switch unit 57 includes, for example, a charge control switch, a discharge control switch, a charging diode, and a discharging diode (all not shown). The charge control switch and the discharge control switch are composed of semiconductor switches such as MOSFETs, for example.

  The current measurement unit 54 measures current using the current detection resistor 54 </ b> A and outputs the measurement result to the control unit 51. The temperature detection unit 55 measures the temperature using the temperature detection element 55 </ b> A and outputs the measurement result to the control unit 51. The temperature measurement result is used, for example, for charge / discharge control by the control unit 51 at the time of abnormal heat generation, correction processing at the time of remaining capacity calculation by the control unit 51, and the like. The voltage detection unit 53 measures the voltage of the secondary battery in the power source 58, converts the measured voltage from analog to digital, and supplies the converted voltage to the control unit 51.

  The switch control unit 56 controls the operation of the switch unit 57 in accordance with signals input from the current measurement unit 54 and the voltage detection unit 53. For example, when the battery voltage reaches the overcharge detection voltage, the switch control unit 56 disconnects the switch unit 57 (charge control switch) and controls the charging current not to flow through the current path of the power source 58. As a result, the power source 58 can only discharge through the discharging diode. The switch control unit 56 cuts off the charging current when a large current flows during charging, for example. Furthermore, for example, when the battery voltage reaches the overdischarge detection voltage, the switch control unit 56 disconnects the switch unit 57 (discharge control switch) so that the discharge current does not flow through the current path of the power source 58. To do. As a result, the power source 58 can only be charged via the charging diode. The switch control unit 56 cuts off the discharge current when a large current flows during discharge, for example.

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

  The memory 52 is composed of, for example, an EEPROM which is a nonvolatile memory. The memory 52 stores, for example, numerical values calculated by the control unit 51, secondary battery information (for example, internal resistance in an initial state) measured in the manufacturing process stage, and the like. If the full charge capacity of the secondary battery is stored in the memory 52, the control unit 51 can grasp information such as the remaining capacity. The temperature detection element 55 </ b> A composed of a thermistor or the like measures the temperature of the power source 58 and outputs the measurement result to the control unit 51. The positive terminal 59A and the negative terminal 59B are terminals connected to an external device (for example, a personal computer) that is operated by the battery pack, an external device (for example, a charger) that is used to charge the battery pack. . Charging / discharging of the power supply 58 is performed via the positive terminal 59A and the negative terminal 59B.

  Next, FIG. 8A shows a block diagram illustrating a configuration of an electric vehicle such as a hybrid vehicle which is an example of the electric vehicle. The electric vehicle includes, for example, a control unit 61, various sensors 62, a power source 63, an engine 71, a generator 72, inverters 73 and 74, a driving motor 75, a differential device 76, a metal housing 60, and the like. A transmission 77 and a clutch 78 are provided. In addition, the electric vehicle includes, for example, a differential device 76, a front wheel drive shaft 81, a front wheel 82, a rear wheel drive shaft 83, and a rear wheel 84 connected to a transmission 77.

  For example, the electric vehicle can travel using either the engine 71 or the motor 75 as a drive source. The engine 71 is a main power source, such as a gasoline engine. When the engine 71 is used as a power source, the driving force (rotational force) of the engine 71 is transmitted to the front wheels 82 or the rear wheels 84 via, for example, a differential device 76 that is a driving unit, a transmission 77, and a clutch 78. The rotational force of the engine 71 is also transmitted to the generator 72, and the generator 72 generates AC power using the rotational force. The AC power is converted into DC power via the inverter 74 and stored in the power source 63. . On the other hand, when the motor 75 which is a conversion unit is used as a power source, the power (DC power) supplied from the power source 63 is converted into AC power via the inverter 73, and the motor 75 is driven using AC power. The driving force (rotational force) converted from electric power by the motor 75 is transmitted to the front wheels 82 or the rear wheels 84 via, for example, a differential device 76, a transmission 77, and a clutch 78, which are driving units.

  When the electric vehicle decelerates via a braking mechanism (not shown), the resistance force at the time of deceleration may be transmitted as a rotational force to the motor 75, and the motor 75 may generate AC power using the rotational force. The AC power is converted into DC power via the inverter 73, and the DC regenerative power is stored in the power source 63.

  The control unit 61 controls the operation of the entire electric vehicle, and includes, for example, a CPU. The power source 63 includes one or more secondary batteries (not shown) described in the first to sixth embodiments. The power supply 63 may be configured to be connected to an external power supply and to store power by receiving power supply from the external power supply. The various sensors 62 are used, for example, to control the rotational speed of the engine 71 and to control the opening of a throttle valve (not shown) (throttle opening). The various sensors 62 include, for example, a speed sensor, an acceleration sensor, an engine speed sensor, and the like.

  Although the case where the electric vehicle is a hybrid vehicle has been described, the electric vehicle may be a vehicle (electric vehicle) that operates using only the power source 63 and the motor 75 without using the engine 71.

  Next, FIG. 8B shows a block diagram showing the configuration of the power storage system. The power storage system includes, for example, a control unit 91, a power source 92, a smart meter 93, and a power hub 94 in a house 90 such as a general house and a commercial building.

  The power source 92 is connected to, for example, an electric device (electronic device) 95 installed inside the house 90 and can be connected to an electric vehicle 97 stopped outside the house 90. The power source 92 is connected to, for example, a private generator 96 installed in the house 90 via a power hub 94 and can be connected to an external centralized power system 98 via the smart meter 93 and the power hub 94. is there. The electric device (electronic device) 95 includes, for example, one or more home appliances. Examples of the home appliance include a refrigerator, an air conditioner, a television receiver, and a water heater. The private power generator 96 is composed of, for example, a solar power generator or a wind power generator. Examples of the electric vehicle 97 include an electric vehicle, a hybrid vehicle, an electric motorcycle, an electric bicycle, and Segway (registered trademark). Examples of the centralized power system 98 include a commercial power source, a power generation device, a power transmission network, and a smart grid (next generation power transmission network), and examples thereof include a thermal power plant, a nuclear power plant, a hydroelectric power plant, and a wind power plant. Examples of the power generation device provided in the centralized power system 98 can include various solar cells, fuel cells, wind power generation devices, micro hydropower generation devices, geothermal power generation devices, etc. It is not limited to these.

  The control unit 91 controls the operation of the entire power storage system (including the usage state of the power supply 92), and includes, for example, a CPU. The power source 92 includes one or more secondary batteries (not shown) described in the first to sixth embodiments. The smart meter 93 is, for example, a network-compatible power meter installed in a house 90 on the power demand side, and can communicate with the power supply side. For example, the smart meter 93 can efficiently and stably supply energy by controlling the balance between supply and demand in the house 90 while communicating with the outside.

  In this power storage system, for example, power is accumulated in the power source 92 from the centralized power system 98 that is an external power source via the smart meter 93 and the power hub 94, and from the private generator 96 that is an independent power source via the power hub 94. Thus, power is stored in the power source 92. Since the electric power stored in the power source 92 is supplied to the electric device (electronic device) 95 and the electric vehicle 97 in accordance with an instruction from the control unit 91, the electric device (electronic device) 95 can be operated and the electric device The vehicle 97 can be charged. In other words, the power storage system is a system that makes it possible to store and supply power in the house 90 using the power source 92.

  The power stored in the power source 92 can be used arbitrarily. Therefore, for example, power can be stored in the power source 92 from the centralized power system 98 at midnight when the electricity rate is low, and the power stored in the power source 92 can be used during the day when the electricity rate is high.

  The power storage system described above may be installed for each house (one household), or may be installed for each of a plurality of houses (multiple households).

  Next, FIG. 8C shows a block diagram showing the configuration of the power tool. The electric tool is, for example, an electric drill, and includes a control unit 101 and a power source 102 inside a tool main body 100 made of a plastic material or the like. For example, a drill portion 103 which is a movable portion is rotatably attached to the tool body 100. The control unit 101 controls the operation of the entire power tool (including the usage state of the power source 102), and includes, for example, a CPU. The power source 102 includes one or more secondary batteries (not shown) described in the first to sixth embodiments. The control unit 101 supplies power from the power source 102 to the drill unit 103 in response to an operation switch (not shown).

  Although the present disclosure has been described based on the preferred embodiments, the present disclosure is not limited to these embodiments, and various modifications can be made. The configuration and structure of the secondary battery described in the examples are merely examples, and can be changed as appropriate.

  Hereinafter, the positive electrode, the negative electrode, the non-aqueous electrolyte, and the like constituting the secondary battery will be described in detail.

  Details of the lithium-containing composite oxide and the lithium-containing phosphate compound, which are preferable materials constituting the positive electrode material, are as follows. In addition, although it does not specifically limit as another element which comprises a lithium containing complex oxide and a lithium containing phosphoric acid compound, Any 1 type or 2 types or more of the elements which belong to 2nd group-15th group in a long period type periodic table are mentioned. From the viewpoint that a high voltage can be obtained, nickel <Ni>, cobalt <Co>, manganese <Mn>, and iron <Fe> are preferably used.

  Specific examples of the lithium-containing composite oxide having a layered rock salt type crystal structure include compounds represented by formula (B), formula (C), and formula (D).

_{Li a Mn 1-bc Ni b} M 11 c O 2-d F e (B)

Here, M ¹¹ is cobalt <Co>, magnesium <Mg>, aluminum <Al>, boron <B>, titanium <Ti>, vanadium <V>, chromium <Cr>, iron <Fe>, copper <Cu >, Zinc <Zn>, zirconium <Zr>, molybdenum <Mo>, tin <Sn>, calcium <Ca>, strontium <Sr> and tungsten <W>. , A, b, c, d, e are
0.8 ≦ a ≦ 1.2
0 <b <0.5
0 ≦ c ≦ 0.5
b + c <1
−0.1 ≦ d ≦ 0.2
0 ≦ e ≦ 0.1
Satisfied. However, the composition differs depending on the charge / discharge state, and a is the value of the complete discharge state.

Li _a Ni _1-b M ¹² _b O _2-c F _d (C)

Here, M ¹² is cobalt <Co>, manganese <Mn>, magnesium <Mg>, aluminum <Al>, boron <B>, titanium <Ti>, vanadium <V>, chromium <Cr>, iron <Fe >, Copper <Cu>, zinc <Zn>, molybdenum <Mo>, tin <Sn>, calcium <Ca>, strontium <Sr> and tungsten <W>. , A, b, c, d are
0.8 ≦ a ≦ 1.2
0.005 ≦ b ≦ 0.5
−0.1 ≦ c ≦ 0.2
0 ≦ d ≦ 0.1
Satisfied. However, the composition differs depending on the charge / discharge state, and a is the value of the complete discharge state.

Li _a Co _1-b M ¹³ _b O _2-c F _d (D)

Here, M < ¹³ > is nickel <Ni>, manganese <Mn>, magnesium <Mg>, aluminum <Al>, boron <B>, titanium <Ti>, vanadium <V>, chromium <Cr>, iron <Fe >, Copper <Cu>, zinc <Zn>, molybdenum <Mo>, tin <Sn>, calcium <Ca>, strontium <Sr> and tungsten <W>. , A, b, c, d are
0.8 ≦ a ≦ 1.2
0 ≦ b <0.5
−0.1 ≦ c ≦ 0.2
0 ≦ d ≦ 0.1
Satisfied. However, the composition differs depending on the charge / discharge state, and a is the value of the complete discharge state.

As the lithium-containing composite oxide having a layered rock salt type crystal structure, specifically, LiNiO ₂ , LiCoO ₂ , LiCo _0.98 Al _0.01 Mg _0.01 O ₂ , LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , LiNi _0.8 Co _0.15 Al _0.05 Examples include O ₂ , LiNi _0.33 Co _0.33 Mn _0.33 O ₂ , Li _1.2 Mn _0.52 Co _0.175 Ni _0.1 O ₂ , and Li _1.15 (Mn _0.65 Ni _0.22 Co _0.13 ) O ₂ .

Moreover, the compound represented by Formula (E) can be illustrated as lithium containing complex oxide which has a spinel type crystal structure.
Li _a Mn _2-b M ¹⁴ _b O _c F _d (E)

Here, M ¹⁴ is cobalt <Co>, nickel <Ni>, magnesium <Mg>, aluminum <Al>, boron <B>, titanium <Ti>, vanadium <V>, chromium <Cr>, iron <Fe >, Copper <Cu>, zinc <Zn>, molybdenum <Mo>, tin <Sn>, calcium <Ca>, strontium <Sr> and tungsten <W>. , A, b, c, d are
0.9 ≦ a ≦ 1.1
0 ≦ b ≦ 0.6
3.7 ≦ c ≦ 4.1
0 ≦ d ≦ 0.1
Satisfied. However, the composition differs depending on the charge / discharge state, and a is the value of the complete discharge state. Specifically, LiMn ₂ O ₄ can be exemplified as the lithium-containing composite oxide having a spinel crystal structure.

Furthermore, the compound represented by Formula (F) can be illustrated as a lithium containing phosphate compound which has an olivine type crystal structure.
Li _a M ¹⁵ PO ₄ (F)

Here, M ¹⁵ is cobalt <Co>, manganese <Mn>, iron <Fe>, nickel <Ni>, magnesium <Mg>, aluminum <Al>, boron <B>, titanium <Ti>, vanadium <V >, Niobium <Nb>, copper <Cu>, zinc <Zn>, molybdenum <Mo>, calcium <Ca>, strontium <Sr>, tungsten <W>, and zirconium <Zr>. It is a kind of element, and the value of a is
0.9 ≦ a ≦ 1.1
Satisfied. However, the composition differs depending on the charge / discharge state, and a is the value of the complete discharge state. Specific examples of the lithium-containing phosphate compound having an olivine type crystal structure include LiFePO ₄ , LiMnPO ₄ , LiFe _0.5 Mn _0.5 PO ₄ , and LiFe _0.3 Mn _0.7 PO ₄ .

Alternatively, as the lithium-containing composite oxide, a compound represented by the formula (G) can be exemplified.
(Li ₂ MnO ₃ ) _x (LiMnO ₂ ) _1-x (G)
Here, the value of x is
0 ≦ x ≦ 1
Satisfied. However, the composition differs depending on the charge / discharge state, and x is the value of the complete discharge state.

  Other positive electrodes include, for example, oxides such as titanium oxide, vanadium oxide, and manganese dioxide; disulfides such as titanium disulfide and molybdenum sulfide; chalcogenides such as niobium selenide; and conductive polymers such as sulfur, polyaniline, and polythiophene. It may be.

  Specific examples of the binder include synthetic rubbers such as styrene butadiene rubber, fluorine rubber, and ethylene propylene diene; and polymer materials such as polyvinylidene fluoride and polyimide. Examples of the conductive agent include carbon materials such as graphite, carbon black, acetylene black, and ketjen black. If the material has conductivity, a metal material, a conductive polymer, or the like may be used. You can also.

  Details of the material constituting the negative electrode are as follows.

  Examples of the material constituting the negative electrode include a carbon material. Since the carbon material has very little change in crystal structure during insertion and extraction of lithium, a high energy density can be stably obtained. Further, since the carbon material also functions as a negative electrode conductive agent, the conductivity of the negative electrode active material layer is improved. Examples of the carbon material include graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), and graphite (graphite). However, the (002) plane spacing in non-graphitizable carbon is preferably 0.37 nm or more, and the (002) plane spacing in graphite is preferably 0.34 nm or less. More specifically, as the carbon material, for example, pyrolytic carbons; cokes such as pitch coke, needle coke, and petroleum coke; glassy carbon fibers; polymer compounds such as phenol resin and furan resin are fired at an appropriate temperature. Organic polymer compound fired bodies obtainable by (carbonization); activated carbon; carbon blacks. In addition, examples of the carbon material may include low crystalline carbon that has been heat-treated at a temperature of about 1000 ° C. or lower, or amorphous carbon. The shape of the carbon material may be any of a fibrous shape, a spherical shape, a granular shape, and a scale shape.

  Alternatively, as a material constituting the negative electrode, for example, a material containing one or more metal elements or metalloid elements as a constituent element (hereinafter referred to as “metal-based material”) may be mentioned. And thereby a high energy density can be obtained. The metal-based material may be any of a simple substance, an alloy, and a compound, or may be a material composed of two or more of these, or a material having at least one of these one or two or more phases. It may be. The alloy includes a material including one or more metal elements and one or more metalloid elements in addition to a material composed of two or more metal elements. The alloy may contain a nonmetallic element. Examples of the structure of the metal-based material include a solid solution, a eutectic (eutectic mixture), an intermetallic compound, and two or more kinds of these coexisting substances.

  Examples of metal elements and metalloid elements include metal elements and metalloid elements capable of forming an alloy with lithium. Specifically, for example, magnesium <Mg>, boron <B>, aluminum <Al>, 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>, platinum <Pt> Among these, silicon <Si> and tin <Sn> are preferable from the viewpoint that they have an excellent ability to occlude and release lithium, and a significantly high energy density can be obtained.

  Examples of the material containing silicon as a constituent element include a simple substance of silicon, a silicon alloy, and a silicon compound. The material may be composed of two or more of these, or one or more of these. A material having at least a part of the above phase may be used. Examples of the material containing tin as a constituent element include a simple substance of tin, a tin alloy, and a tin compound. The material may be composed of two or more of these, or one or more of these. A material having at least a part of the above phase may be used. The simple substance means a simple substance in a general sense, and may contain a small amount of impurities, and does not necessarily mean 100% purity.

As elements other than silicon constituting the silicon alloy or silicon compound, 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>, chromium <Cr>, carbon <C>, oxygen <O> It can also be mentioned. Specific examples of the silicon alloy or silicon compound include SiB ₄ , SiB ₆ , Mg ₂ Si, Ni ₂ Si, TiSi ₂ , MoSi ₂ , CoSi ₂ , NiSi ₂ , CaSi ₂ , CrSi ₂ , Cu ₅ Si, and FeSi _2. , MnSi ₂ , NbSi ₂ , TaSi ₂ , VSi ₂ , WSi ₂ , ZnSi ₂ , SiC, Si ₃ N ₄ , Si ₂ N ₂ O, SiO _v (0 <v ≦ 2, preferably 0.2 <v < 1.4), LiSiO can be exemplified.

As elements other than tin constituting the tin alloy or tin compound, silicon <Si>, nickel <Ni>, copper <Cu>, iron <Fe>, cobalt <Co>, manganese <Mn>, zinc <Zn>, indium <In>, silver <Ag>, titanium <Ti>, germanium <Ge>, bismuth <Bi>, antimony <Sb>, chromium <Cr>, carbon <C>, oxygen <O> It can also be mentioned. Specific examples of the tin alloy or tin compound include SnO _w (0 <w ≦ 2), SnSiO ₃ , LiSnO, and Mg ₂ Sn. In particular, the material containing tin as a constituent element is preferably a material containing a second constituent element and a third constituent element together with tin (first constituent element) (hereinafter referred to as “Sn-containing material”). As the second constituent element, for example, cobalt <Co>, iron <Fe>, magnesium <Mg>, titanium <Ti>, vanadium <V>, chromium <Cr>, manganese <Mn>, nickel <Ni>, copper <Cu>, zinc <Zn>, gallium <Ga>, zirconium <Zr>, niobium <Nb>, molybdenum <Mo>, silver <Ag>, indium <In>, cesium <Ce>, hafnium <Hf>, tantalum <Ta>, tungsten <W>, bismuth <Bi>, silicon <Si> can be mentioned, and as the third constituent element, for example, boron <B>, carbon <C>, aluminum <Al>, phosphorus <P > Can be mentioned. When the Sn-containing material contains the second constituent element and the third constituent element, high battery capacity, excellent cycle characteristics, and the like are obtained.

  Among these, the Sn-containing material is preferably a material containing tin <Sn>, cobalt <Co>, and carbon <C> as constituent elements (referred to as “SnCoC-containing material”). In the SnCoC-containing material, for example, the carbon content is 9.9 mass% to 29.7 mass%, and the content ratio of tin and cobalt {Co / (Sn + Co)} is 20 mass% to 70 mass%. It is. This is because a high energy density can be obtained. The SnCoC-containing material has a phase containing tin, cobalt, and carbon, and the phase is preferably low crystalline or amorphous. Since this phase is a reaction phase capable of reacting with lithium, excellent characteristics can be obtained due to the presence of the reaction phase. The half width (diffraction angle 2θ) of the diffraction peak obtained by X-ray diffraction of this reaction phase is 1 degree or more when CuKα ray is used as the specific X-ray and the insertion speed is 1 degree / minute. preferable. This is because lithium is occluded and released more smoothly and the reactivity with the non-aqueous electrolyte is reduced. The SnCoC-containing material may contain a phase containing a simple substance or a part of each constituent element in addition to a low crystalline or amorphous phase.

  Whether the diffraction peak obtained by X-ray diffraction corresponds to a reaction phase capable of reacting with lithium can be easily determined by comparing X-ray diffraction charts before and after electrochemical reaction with lithium. be able to. For example, if the position of the diffraction peak changes before and after the electrochemical reaction with lithium, it corresponds to a reaction phase capable of reacting with lithium. In this case, for example, a diffraction peak of a low crystalline or amorphous reaction phase is observed between 2θ = 20 degrees and 50 degrees. Such a reaction phase contains, for example, each of the above-described constituent elements, and is considered to be low crystallized or amorphous mainly due to the presence of carbon.

  In the SnCoC-containing material, it is preferable that at least a part of carbon as a constituent element is bonded to a metal element or a metalloid element. This is because aggregation and crystallization of tin and the like are suppressed. The bonding state of the elements can be confirmed using, for example, X-ray photoelectron spectroscopy (XPS) using Al—Kα rays or Mg—Kα rays as a soft X-ray source. When at least a part of carbon is bonded to a metal element, a metalloid element, or the like, the peak of the synthetic wave of the carbon 1s orbital (C1s) appears in a region lower than 284.5 eV. It is assumed that the energy is calibrated so that the peak of the gold atom 4f orbit (Au4f) is obtained at 84.0 eV. At this time, since surface-contaminated carbon is usually present on the surface of the substance, the C1s peak of the surface-contaminated carbon is set to 284.8 eV, and the peak is used as an energy reference. In the XPS measurement, the waveform of the C1s peak is obtained in a form including the surface contamination carbon peak and the carbon peak in the SnCoC-containing material. Therefore, for example, analysis may be performed using commercially available software, and both peaks may be separated. In the waveform analysis, the position of the main peak existing on the lowest bound energy side is used as the energy reference (284.8 eV).

  The SnCoC-containing material is not limited to a material (SnCoC) whose constituent elements are only tin, cobalt, and carbon. Examples of the SnCoC-containing material include silicon <Si>, iron <Fe>, nickel <Ni>, chromium <Cr>, indium <In>, niobium <Nb>, and germanium <Ge> in addition to tin, cobalt, and carbon. , Titanium <Ti>, molybdenum <Mo>, aluminum <Al>, phosphorus <P>, gallium <Ga>, bismuth <Bi> and the like may be included as a constituent element.

  In addition to SnCoC-containing materials, materials containing tin, cobalt, iron and carbon as constituent elements (hereinafter referred to as “SnCoFeC-containing materials”) are also preferable materials. The composition of the SnCoFeC-containing material is arbitrary. For example, when the iron content is set to be small, the carbon content is 9.9 mass% to 29.7 mass%, the iron content is 0.3 mass% to 5.9 mass%, The ratio of content of tin and cobalt {Co / (Sn + Co)} is 30% by mass to 70% by mass. When the iron content is set to be large, the carbon content is 11.9% to 29.7% by mass, and the ratio of the content of tin, cobalt and iron {(Co + Fe) / (Sn + Co + Fe)} 26.4% by mass to 48.5% by mass, and the ratio of content of cobalt and iron {Co / (Co + Fe)} is 9.9% by mass to 79.5% by mass. This is because a high energy density can be obtained in such a composition range. The physical properties (half width, etc.) of the SnCoFeC-containing material are the same as the physical properties of the above-described SnCoC-containing material.

  In addition, examples of the material constituting the negative electrode include metal oxides such as iron oxide, ruthenium oxide, and molybdenum oxide; and polymer compounds such as polyacetylene, polyaniline, and polypyrrole.

  Especially, it is preferable that the material which comprises a negative electrode contains both the carbon material and the metal type material for the following reasons. That is, a metal material, particularly a material containing at least one of silicon and tin as a constituent element has an advantage of high theoretical capacity, but easily expands and contracts violently during charge and discharge. On the other hand, the carbon material has an advantage that the theoretical capacity is low, but it is difficult to expand and contract during charging and discharging. Therefore, by using both the carbon material and the metal-based material, expansion / contraction during charging / discharging is suppressed while obtaining a high theoretical capacity (in other words, battery capacity).

As described above, the non-aqueous electrolyte suitable for use in the secondary battery of the present disclosure is not limited,
A compound represented by formula (1),
At least one of a compound represented by formula (2-A) and a compound represented by formula (2-B), and
At least one compound of compounds represented by formula (3-A) to formula (3-F);
Non-aqueous electrolyte solution containing can be mentioned. The content of the compound represented by the formula (1) in the non-aqueous electrolyte is 2.5 mol / liter to 6 mol / liter, preferably 3 mol / liter to 6 mol / liter. .

M ⁺ [(Z ¹ Y ¹ ) (Z ² Y ² ) N] ^- (1)
However, M is a metal element, and each of Z ¹ and Z ² is either a fluorine group <—F>, a monovalent hydrocarbon group, or a monovalent fluorinated hydrocarbon group, and Z ¹ and Z ² is at least one of a fluorine group <—F> and a monovalent fluorinated hydrocarbon group, and each of Y ¹ and Y ² is a sulfonyl group <—S (═O) ₂ —>, carbonyl Any of the groups <—C (═O) —>.

R ¹ -CN (2-A)
^{R 2 -X-CN (2-} B)
However, R ¹ is a monovalent hydrocarbon group, R ² is a monovalent hydrocarbon group, and X is one or more ether bonds <—O—> and one or two or more divalent hydrocarbon groups. A group in which a hydrocarbon group is bonded in any order.

Ｒ²²−（ＣＮ）_n （３−Ｆ）

_{^{R 22 - (CN) n (}} 3-F)

Here, in formula (3-A), each of R ³ and R ⁴ is either a hydrogen group <—H> or a monovalent hydrocarbon group. In the formula (3-B), each of R ⁵ , R ⁶ , R ⁷ and R ^{8 is} any one of a hydrogen group, a monovalent saturated hydrocarbon group, and a monovalent unsaturated hydrocarbon group, At least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is a monovalent unsaturated hydrocarbon group. Furthermore, in the formula (3-C), R ⁹ is a group represented by> CR ¹⁰ R ¹¹ , and each of R ¹⁰ and R ¹¹ is either a hydrogen group or a monovalent hydrocarbon group. is there. In the formula (3-D), each of R ¹² , R ¹³ , R ¹⁴ , and R ^{15 is} any one of a hydrogen group, a halogen group, a monovalent hydrocarbon group, and a monovalent halogenated hydrocarbon group. And at least one of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is any one of a halogen group and a monovalent halogenated hydrocarbon group. Furthermore, in the formula (3-E), each of R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ is a hydrogen group, a halogen group, a monovalent hydrocarbon group, or a monovalent halogenated group. Any one of hydrocarbon groups, and at least one of R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ is any one of a halogen group and a monovalent halogenated hydrocarbon group. In the formula (3-F), R ²² is an n-valent hydrocarbon group (where n is an integer of 2 or more). “> C” and “C <” indicate that two bonds extend from the carbon atom.

  Specifically, the nonaqueous electrolytic solution includes a first compound having a sulfonylimide structure, a second compound having an acetonitrile structure, and a third compound having a reactive group such as an unsaturated hydrocarbon group. Compound. Here, the non-aqueous electrolyte has such a composition because the following advantages are obtained. That is, the non-aqueous electrolyte contains the first compound, the second compound, and the third compound together, and the content of the first compound in the non-aqueous electrolyte is within the above range (2.5 mol / liter to 6 mol / liter), the chemical stability of the non-aqueous electrolyte is specifically improved by the synergistic action of the first compound, the second compound, and the third compound, and the non-aqueous electrolysis during charge / discharge The decomposition reaction of the liquid is suppressed. Therefore, even if charging / discharging is repeated, the discharge capacity is hardly reduced, and the battery characteristics of the secondary battery can be improved. In particular, whether or not the specific synergistic effect described here is obtained depends on the content of the first compound. Therefore, a specific synergistic action is obtained only when the content of the first compound is within the above range.

The 1st compound contains the 1 type (s) or 2 or more types of the compound represented by Formula (1). Since the first compound is a salt containing a cation (M ⁺ ) and an anion ([(Z ¹ Y ¹ ) (Z ² Y ² ) N] ⁻ ), it functions as a part of the electrolyte salt in the secondary battery. obtain.

  “M” in Formula (1) is not particularly limited as long as it is a metal element, and examples thereof include alkali metal elements and alkaline earth metal elements. Among them, “M” is an alkali metal element. Is preferred, whereby a high energy density can be obtained. Examples of the alkali metal element include lithium <Li>, sodium <Na>, potassium <K>, rubidium <Rb>, and cesium <Cs>. Among these, lithium <Li> is preferable. The alkali metal element is preferably the same as the alkali metal element constituting the electrode reactant, whereby a high energy density can be obtained. The electrode reactant is a substance involved in the electrode reaction, for example, lithium in a lithium ion secondary battery. For this reason, when used for a lithium ion secondary battery, “M” is preferably lithium.

Z ¹ and Z ² may be the same group or different groups. The monovalent hydrocarbon group in Z ¹ and Z ² is a general term for monovalent groups composed of carbon <C> and hydrogen <H>, and may be linear or 1 or 2 It may be branched having the above side chains. Further, the monovalent saturated hydrocarbon group may be a saturated hydrocarbon group not containing an unsaturated bond, or may be an unsaturated hydrocarbon group containing one or more unsaturated bonds. Good. The unsaturated bond is one or both of a carbon-carbon double bond (> C═C <) and a carbon-carbon triple bond (—C≡C—).

  Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and a group in which two or more of these are bonded so as to be monovalent. In other words, the monovalent saturated hydrocarbon group is, for example, an alkyl group, a cycloalkyl group, or a group in which two or more of these are bonded so as to be monovalent. The monovalent unsaturated hydrocarbon group is, for example, an alkenyl group, an alkynyl group, an aryl group, a group containing one or more of these, and a group in which two or more of these are bonded so as to be monovalent. As a group in which two or more types of monovalent hydrocarbon groups are bonded, a group in which an alkyl group and an alkenyl group are bonded, a group in which an alkyl group and an alkynyl group are bonded, a group in which an alkenyl group and an alkynyl group are bonded, alkyl Examples include a group in which a group and a cycloalkyl group are bonded, and a group in which an alkyl group and an aryl group are bonded. Examples of the group in which two or more kinds in the monovalent saturated hydrocarbon group are bonded include a group in which an alkyl group and a cycloalkyl group are bonded. Examples of the group in which two or more kinds of monovalent unsaturated hydrocarbon groups are bonded include a group in which an alkyl group and an alkenyl group are bonded, and a group in which an alkyl group and an alkenyl group are bonded.

As the alkyl group include a methyl group <-CH _3>, an ethyl group <-C ₂ H _5>, propyl <-C ₃ H _7>, n- butyl group <-C ₄ H _8>, t - it can be exemplified butyl _{<-C (CH 3) 2 -CH} 3>. Specific examples of the alkenyl group include a vinyl group <—CH═CH ₂ > and an allyl group <—CH ₂ —CH═CH ₂ >. Specific examples of the alkynyl group include an ethynyl group <—C≡CH>. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of the aryl group include a phenyl group and a naphthyl group. Specific examples of the group in which two or more types are bonded include a group in which a methyl group and an ethynyl group are bonded, a group in which a vinyl group and an ethynyl group are bonded, a group in which a methyl group and a cyclopropyl group are bonded, and a methyl group And a group in which a phenyl group is bonded.

  The monovalent fluorinated hydrocarbon group is a group obtained by substituting one or two or more hydrogen groups <—H> with a fluorine group <—F> in the above monovalent hydrocarbon group. As the monovalent fluorinated hydrocarbon group, specifically, a fluorinated alkyl group, a fluorinated alkenyl group, a fluorinated alkynyl group, a fluorinated cycloalkyl group, a fluorinated aryl group, and two or more of these are monovalent Examples of the group bonded in such a way can be given.

As a fluorinated alkyl group, specifically, fluoromethyl group <-CH ₂ F>, difluoromethyl group <-CHF _2>, perfluoromethyl group <-CF _3>, perfluoroethyl group <-C ₂ F ₅ >, perfluoropropyl group <-C ₃ F _7>, n- perfluorobutyl <-C ₄ F _8>, t- perfluorobutyl group <-C (CF _{3) 2} to illustrate the -CF _3> Can do. Specific examples of the fluorinated alkenyl group include a perfluorovinyl group <—CF═CF ₂ > and a perfluoroallyl group <—CF ₂ —CF═CF ₂ >. Specific examples of the fluorinated alkynyl group include a perfluoroethynyl group <—F≡CF>. Specific examples of the fluorinated cycloalkyl group include a perfluorocyclopropyl group, a perfluorocyclobutyl group, a perfluorocyclopentyl group, a perfluorocyclohexyl group, a perfluorocycloheptyl group, and a perfluorocyclooctyl group. it can. Specific examples of the fluorinated aryl group include a perfluorophenyl group and a perfluoronaphthyl group. Among them, the fluorinated alkyl group, fluorinated alkenyl group, fluorinated alkynyl group, fluorinated cycloalkyl group, and fluorinated aryl group are preferably perfluoro groups, and more preferably perfluoroalkyl groups. This is because they can be easily synthesized and a synergistic effect described later is easily obtained.

  The number of carbon atoms of the monovalent hydrocarbon group and the monovalent fluorinated hydrocarbon group is not particularly limited, but is preferably not excessively large. This is because the solubility and compatibility of the first compound are improved. Specifically, the carbon number of the fluorinated alkyl group is preferably 1 to 4. The fluorinated alkenyl group and the fluorinated alkynyl group preferably have 2 to 4 carbon atoms. The fluorinated cycloalkyl group and the fluorinated aryl group preferably have 6 to 12 carbon atoms.

In the formula (1), one or both of Z ¹ and Z ² is either a fluorine group <—F> or a monovalent fluorinated hydrocarbon group. This is because they can be easily synthesized and a synergistic effect described later is easily obtained. Accordingly, when ^one of Z ¹ and Z ² is a monovalent hydrocarbon group, the other is either a fluorine group <—F> or a monovalent fluorinated hydrocarbon group. That is, both Z ¹ and Z ² are not monovalent hydrocarbon groups.

In Formula (1), each of Y ¹ and Y ² is not particularly limited as long as it is either a sulfonyl group or a carbonyl group. Y ¹ and Y ² may be the same group or different groups.

Specifically, as the first compound, bisfluorosulfonylimide lithium <LiN (FSO ₂ ) ₂ >, bistrifluoromethylsulfonylimide lithium <LiN (CF ₃ SO ₂ ) ₂ >, fluorosulfonyltrifluoromethylsulfonylimide lithium < LiN (FSO ₂ ) (CF ₃ SO ₂ )>, fluorosulfonylpentafluoroethylsulfonylimide lithium <LiN (FSO ₂ ) (C ₂ F ₅ SO ₂ )>, fluorosulfonyl nonafluorobutylsulfonylimide lithium <LiN (FSO ₂₎ ) (C ₄ F ₉ SO ₂ )>, fluorosulfonylphenylsulfonylimide lithium <LiN (FSO ₂ ) (C ₆ H ₅ SO ₂ )>, fluorosulfonylpentafluorophenylsulfonylimide lithium <LiN (FSO ₂ ) (C ₆ F ₅ SO ₂ >, Can be exemplified fluorosulfonyl vinylsulfonyl imide _{<LiN (FSO 2) (C} 2 F 3 SO 2)>.

  The second compound described above includes either one or both of the compounds represented by formula (2-A) and formula (2-B). However, the 2nd compound may contain 2 or more types of the compound shown to Formula (2-A), and may contain 2 or more types of the compound shown to Formula (2-B).

The compound represented by the formula (2-A) is a mononitrile compound (non-oxygen-containing mononitrile compound) that does not include an ether bond. R ¹ is not particularly limited as long as it is a monovalent hydrocarbon group. The details regarding the monovalent hydrocarbon group are as described above. Specific examples of the non-oxygen-containing mononitrile compound include acetonitrile <CH ₃ CN>, propionitrile <C ₃ H ₇ CN>, and butyronitrile <C ₄ H ₉ CN>.

The compound represented by the formula (2-B) is a mononitrile compound (oxygen-containing mononitrile compound) containing an ether bond. R ² is not particularly limited as long as it is a monovalent hydrocarbon group. The details regarding the monovalent hydrocarbon group are as described above. In “X” in the formula (2-B), the divalent hydrocarbon group is a general term for divalent groups composed of carbon and hydrogen, and may be linear or 1 or It may be branched with two or more side chains. Specific examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, and a group in which two or more of these are bonded so as to be divalent. Can do. Specific examples of the group in which two or more types are bonded include a group in which an alkylene group and an alkenylene group are bonded, a group in which an alkyl group and an alkynylene group are bonded, a group in which an alkenylene group and an alkynylene group are bonded, and an alkylene group. Examples thereof include a group in which a cycloalkylene group is bonded and a group in which an alkylene group and an arylene group are bonded.

Specific examples of the alkylene group include a methylene group <—CH ₂ —>, an ethylene group <—C ₂ H ₄ —>, a propylene group <—C ₃ H ₆ —>, and an n-butylene group <—C ₄ H _8. ->, t-butylene _{<-C (CH 3) 2 -CH} 2 - can be exemplified>. Specific examples of the alkenylene group include a vinylene group <—CH═CH—> and an arylene group <—CH ₂ —CH═CH—>. Specific examples of the alkynylene group include an ethynylene group <—C≡C—>. Specific examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group. Specific examples of the arylene group include a phenylene group and a naphthylene group. Specific examples of the group in which two or more types are bonded include a group in which a methylene group and an ethynylene group are bonded, a group in which a vinylene group and an ethynylene group are bonded, a group in which a methylene group and a cyclopropylene group are bonded, and a methylene group. And a group in which a phenylene group is bonded.

  The number of carbon atoms of the divalent hydrocarbon group is not particularly limited, but is preferably not excessively large. This is because the solubility and compatibility of the second compound are improved. Specifically, the alkylene group preferably has 1 to 4 carbon atoms. The alkenylene group and the alkynylene group preferably have 2 to 4 carbon atoms. The cycloalkylene group and the arylene group preferably have 6 to 12 carbon atoms.

  “X” is not particularly limited as long as it is a group in which one or two or more ether bonds and one or two or more divalent hydrocarbon groups are bonded in any order. That is, the number of ether bonds contained in “X” may be 1 or 2 or more. Similarly, the number of divalent hydrocarbon groups contained in “X” may be 1 or 2 or more. When the number of divalent hydrocarbon groups is 2 or more, the two or more divalent hydrocarbon groups may be the same group or different groups. A part of two or more divalent hydrocarbon groups may be the same group. Since the order in which the ether bond and the divalent hydrocarbon group are bonded may be arbitrary, the ether bonds may be bonded to each other, the divalent hydrocarbon groups may be bonded to each other, A divalent hydrocarbon group may be combined.

Among these, “X” is preferably a group represented by —O—Y— (Y is a divalent hydrocarbon group). This is because they can be easily synthesized and a synergistic effect described later is easily obtained. The details regarding the divalent hydrocarbon group are as described above. However, in X (that is, —O—Y—) described here, an ether bond (—O—) is bonded to R ² and Y is bonded to a cyano group <—CN>. Specific examples of “X” include —O—CH ₂ —, —CH ₂ —O—, —O—CH ₂ —O—, and —O—C ₂ H ₅ —.

Specific examples of the oxygen-containing mono-nitrile compounds, methoxy acetonitrile _{<CH 3 -O-CH 2 -CN} >, ethoxy acetonitrile _{<C 2 H 5 -O-CH} 2 -CN>, propoxy acetonitrile <C ₃ H ₇ -O- it can be exemplified CH ₂ -CN>.

  The content of the second compound in the nonaqueous electrolytic solution is not particularly limited, but is preferably 20% by mass to 100% by mass, for example. This is because a synergistic effect described later is easily obtained. When the second compound contains both a non-oxygen-containing mononitrile compound and an oxygen-containing mononitrile compound, the content of the second compound is the content of the non-oxygen-containing mononitrile compound and the content of the oxygen-containing mononitrile compound. And the sum. This means that the content means the sum in the following.

  The third compound described above contains one or more of unsaturated cyclic carbonates, halogenated cyclic carbonates, and polynitrile compounds. However, the third compound may contain two or more types of unsaturated cyclic carbonates. The fact that two or more kinds may be contained in this way is the same for the halogenated cyclic carbonate and the polynitrile compound.

  The unsaturated cyclic carbonate contains one or more of the compounds represented by formula (3-A), formula (3-B), and formula (3-C). Here, the unsaturated cyclic carbonate is a cyclic carbonate containing one or more unsaturated bonds (carbon-carbon double bonds).

The compound shown in Formula (3-A) is a vinylene carbonate compound. Each of R ³ and R ⁴ is not particularly limited as long as it is either a hydrogen group or a monovalent hydrocarbon group. The details regarding the monovalent hydrocarbon group are as described above. R ³ and R ⁴ may be the same group or different groups.

  Specific examples of the vinylene carbonate compound include vinylene carbonate (1,3-dioxol-2-one), methyl vinylene carbonate (4-methyl-1,3-dioxol-2-one), ethyl vinylene carbonate (4-ethyl- 1,3-dioxol-2-one), 4,5-dimethyl-1,3-dioxol-2-one, 4,5-diethyl-1,3-dioxol-2-one, 4-fluoro-1,3 -Dioxol-2-one and 4-trifluoromethyl-1,3-dioxol-2-one can be exemplified, and among them, vinylene carbonate is preferable from the viewpoint of easy synthesis.

The compound represented by the formula (3-B) is a vinyl ethylene carbonate compound. Each of R ⁵ , R ⁶ , R ⁷ and R ⁸ is not particularly limited as long as it is any one of a hydrogen group, a monovalent saturated hydrocarbon group, and a monovalent unsaturated hydrocarbon group. The details regarding the monovalent saturated hydrocarbon group and the monovalent unsaturated hydrocarbon group are as described above. However, one or more of R ⁵ , R ⁶ , R ⁷ , and R ⁸ are monovalent unsaturated hydrocarbon groups. This is because the vinyl carbonate-based compound must contain one or more unsaturated bonds (carbon-carbon double bonds). R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same group or different groups. A part of R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same group.

  Specific examples of the vinyl carbonate-based compound include vinyl ethylene carbonate (4-vinyl-1,3-dioxolan-2-one), 4-methyl-4-vinyl-1,3-dioxolan-2-one, 4 -Ethyl-4-vinyl-1,3-dioxolan-2-one, 4-n-propyl-4-vinyl-1,3-dioxolan-2-one, 5-methyl-4-vinyl-1,3-dioxolane 2-one, 4,4-divinyl-1,3-dioxolan-2-one, and 4,5-divinyl-1,3-dioxolan-2-one can be exemplified, but among them, it can be easily synthesized. From the viewpoint of being, it is preferable to use vinyl ethylene carbonate.

The compound represented by the formula (3-C) is a methylene ethylene carbonate compound. R ⁹ is not particularly limited as long as it is a group represented by> CR ¹⁰ R ¹¹ . The details regarding the monovalent hydrocarbon group are as described above. R ¹⁰ and R ¹¹ may be the same group or different groups.

  Specific examples of methylene ethylene carbonate compounds include methylene ethylene carbonate (4-methylene-1,3-dioxolan-2-one), 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one. 4,4-diethyl-5-methylene-1,3-dioxolan-2-one.

In addition, the unsaturated cyclic carbonate may be a compound containing two methylene groups, or catechol carbonate (catechol carbonate) containing a benzene ring. The compounds containing two methylene groups in formula (3-C),> C = instead of R ^9> together comprise a C = CH _2,> instead of CH _2> with a compound containing a C = CH ₂ is there.

  The content of the unsaturated cyclic carbonate in the nonaqueous electrolytic solution is not particularly limited, but for example, it is preferably 0.01% by mass to 20% by mass with respect to the total sum excluding the unsaturated cyclic carbonate. .

  The halogenated cyclic carbonate contains one or more of the compounds represented by formula (3-D) and formula (3-E). The halogenated carbonate is a carbonate having one or more halogen groups.

The compound represented by the formula (3-D) is a halogenated cyclic carbonate. R ^{12 to} R ¹⁵ are not particularly limited as long as they are any one of a hydrogen group, a halogen group, a monovalent hydrocarbon group, and a monovalent halogenated hydrocarbon group. The details regarding the monovalent hydrocarbon group are as described above. However, one or two or more of R ^{12 to} R ¹⁵ is either a halogen group or a monovalent halogenated hydrocarbon group. This is because the halogenated cyclic carbonate must contain one or more halogen groups. R ^{12 to} R ¹⁵ may be the same group or different groups. A part of R ^{12 to} R ¹⁵ may be the same group.

  The monovalent halogenated hydrocarbon group is a group obtained by substituting one or two or more hydrogen groups with a halogen group in the above monovalent hydrocarbon group. The halogen group is not particularly limited. For example, the halogen group is any one of a fluorine group <-F>, a chlorine group <-Cl>, a bromine group <-Br>, an iodine group <-I>, etc. F> is preferable. This is because they can be easily synthesized and a synergistic effect described later is easily obtained. The number of halogen groups is preferably 2 rather than 1, and may be 3 or more. This is because a higher effect can be obtained.

  Specific examples of the monovalent halogenated hydrocarbon group include a halogenated alkyl group, a halogenated alkenyl group, a halogenated alkynyl group, a halogenated cycloalkyl group, and a halogenated aryl group. Examples of the group bonded in such a way can be given.

  Specific examples of the fluorinated alkyl group, the fluorinated alkenyl group, the fluorinated alkynyl group, the fluorinated cycloalkyl group, and the fluorinated aryl group among the halogenated alkyl groups are as described above. Specific examples of the chlorinated alkyl group, brominated alkyl group, and iodinated alkyl group are compounds in which the fluorine group in the above specific examples of the fluorinated alkyl group is changed to a chlorine group, a bromine group, or an iodine group. In this way, changing a fluorine group to a chlorine group, a bromine group, or an iodine group means that a chlorinated alkenyl group, a chlorinated alkynyl group, a chlorinated cycloalkyl group, a chlorinated aryl group, a brominated alkenyl group, a brominated group The same applies to alkynyl groups, brominated cycloalkyl groups, brominated aryl groups, iodinated alkenyl groups, iodinated alkynyl groups, iodinated cycloalkyl groups, and iodinated aryl groups.

  Specific examples of the halogenated cyclic carbonate include 4-fluoro-1,3-dioxolan-2-one, 4-chloro-1,3-dioxolan-2-one, 4,5-difluoro-1,3-dioxolane- 2-one, tetrafluoro-1,3-dioxolan-2-one, 4-chloro-5-fluoro-1,3-dioxolan-2-one, 4,5-dichloro-1,3-oxolan-2-one Tetrachloro-1,3-dioxolan-2-one, 4,5-bistrifluoromethyl-1,3-dioxolan-2-one, 4-trifluoromethyl-1,3-dioxolan-2-one, 4, 5-difluoro-4,5-dimethyl-1,3-dioxolan-2-one, 4,4-difluoro-5-methyl-1,3-dioxolan-2-one, 4-ethyl-5,5-difluor -1,3-dioxolan-2-one, 4-fluoro-5-trifluoromethyl-1,3-dioxolan-2-one, 4-methyl-5-trifluoromethyl-1,3-dioxolan-2-one 4-fluoro-4,5-dimethyl-1,3-dioxolan-2-one, 5-1,1-difluoroethyl-4,4-difluoro-1,3-dioxolan-2-one, 4,5- Dichloro-4,5-dimethyl-1,3-dioxolan-2-one, 4-ethyl-5-fluoro-1,3-dioxolan-2-one, 4-ethyl-4,5-difluoro-1,3- Illustrate dioxolan-2-one, 4-ethyl-4,5,5-trifluoro-1,3-dioxolan-2-one, 4-fluoro-4-methyl-1,3-dioxolan-2-one Can do. Specific examples of the halogenated cyclic carbonate described here include isomers (cis isomer and trans isomer).

The compound shown in Formula (3-E) is a halogenated chain carbonate. R ^{16 to} R ²¹ are not particularly limited as long as they are any one of a hydrogen group, a halogen group, a monovalent hydrocarbon group, and a monovalent halogenated hydrocarbon group. The details regarding the monovalent hydrocarbon group and the monovalent halogenated hydrocarbon group are as described above. However, for the same reason as in the above-mentioned halogenated cyclic carbonate, one or more of R ^{16 to} R ²¹ are either a halogen group or a monovalent halogenated hydrocarbon group. R ^{16 to} R ²¹ may be the same group or different groups. A part of R ^{16 to} R ²¹ may be the same group. Specific examples of the halogenated chain carbonate include fluoromethyl methyl carbonate, bisfluoromethyl carbonate, and difluoromethyl methyl carbonate. The content of the halogenated cyclic carbonate in the nonaqueous electrolytic solution is not particularly limited, but is preferably 0.01% by mass to 20% by mass, for example, based on the total amount excluding the halogenated cyclic carbonate. .

  The polynitrile compound contains one or more of the compounds represented by formula (3-F). The polynitrile compound is a compound containing two or more nitrile groups, and the second compound is not included in the polynitrile compound described here. This is because the second compound does not contain two or more nitrile groups.

R ²² is not particularly limited as long as it is an n-valent hydrocarbon group. For example, when R ²² has 1 carbon atom, the divalent hydrocarbon group may be —CH ₂ —, and the trivalent hydrocarbon group may be> CH—. Similarly, when R ²² has 2 carbon atoms, examples of the divalent hydrocarbon group include —CH ₂ —CH ₂ —, examples of the trivalent hydrocarbon group include> CH—CH ₂ —, and the like. Among these, R ²² is preferably a divalent hydrocarbon group. This is because the number of cyano groups <-CN> is 2, so that a synergistic effect described later is easily obtained. The details regarding the divalent hydrocarbon group are as described above.

  Specific examples of the polynitrile compound include malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimonitrile, suberonitrile, azeronitrile, sebacononitrile, undecandinitrile, dodecandinitrile, phthalonitrile, and tetracyanoquinodimethane. it can. The content of the polynitrile compound in the nonaqueous electrolytic solution is not particularly limited, but for example, it is preferably 0.01% by mass to 10% by mass with respect to the total sum excluding the polynitrile compound.

The nonaqueous electrolytic solution may contain one type or two or more types of other materials in addition to the first compound, the second compound, and the third compound. Specific examples of other materials include sulfonic acid esters, acid anhydrides, cyclic carboxylic acid esters (lactones), dialkyl sulfoxides, chain dicarbonates (see formula (10) below), and aromatic carbonates (see below). Formula (11)), cyclic carbonate (see formula (12) below), chain monocarbonate (see formula (13) below), chain carboxylate (see formula (14) below) , Phosphoric acid ester (see formula (15) below), lithium monofluorophosphate <Li ₂ PO ₃ F>, lithium difluorophosphate <LiPO ₂ F ₂ > Can do.

Here, each of R ²³ and R ²⁴ is a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group, and R ²⁵ is a divalent hydrocarbon group or a divalent halogenated carbon group. One of hydrogen groups. R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , and R ³⁵ are each a monovalent hydrocarbon group or a monovalent oxygen-containing hydrocarbon group. A monovalent nitrogen-containing hydrocarbon group, a monovalent halogenated hydrocarbon group, a monovalent halogenated oxygen-containing hydrocarbon group, a monovalent halogenated nitrogen-containing hydrocarbon group, and two or more of these are monovalent Any of the groups so attached. Further, each of R ³⁶ , R ³⁷ , R ³⁸ , and R ³⁹ is any one of a hydrogen group and a monovalent hydrocarbon group. Each of R ⁴⁰ and R ⁴¹ is either a hydrogen group or a monovalent hydrocarbon group. Further, each of R ⁴² and R ⁴³ is either a hydrogen group or a monovalent hydrocarbon group. Each of R ⁴⁴ , R ⁴⁵ and R ⁴⁶ is either a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group.

  Specific examples of the sulfonic acid ester include monosulfonic acid esters and disulfonic acid esters. The content of the sulfonic acid ester in the non-aqueous electrolyte solution is not particularly limited, but for example, it is preferably 0.01% by mass to 10% by mass with respect to the total of the total amount excluding the sulfonic acid ester.

The monosulfonic acid ester may be a cyclic monosulfonic acid ester or a chain monosulfonic acid ester. Specific examples of the cyclic monosulfonic acid ester include sultone such as propane sultone and propene sultone. Specific examples of the chain monosulfonic acid ester include compounds having a structure in which a cyclic monosulfonic acid ester is cleaved on the way. As an example, CH ₃ —CH ₂ —CH ₂ —SO ₃ —CH ₃ can be exemplified as a compound in which propane sultone is cleaved on the way. The direction of —SO ₃ — (— S (═O) ₂ —O—) is not particularly limited. That is, the above CH ₃ —CH ₂ —CH ₂ —SO ₃ —CH ₃ may be CH ₃ —CH ₂ —CH ₂ —S (═O) ₂ —O—CH ₃ , or CH ₃ — It may be CH ₂ —CH ₂ —O—S (═O) ₂ —CH ₃ .

The disulfonic acid ester may be a cyclic disulfonic acid ester or a chain disulfonic acid ester. Specific examples of the cyclic disulfonic acid ester include compounds represented by formula (16-1), formula (16-2), and formula (16-3). A chain disulfonic acid ester is a compound in which a cyclic disulfonic acid ester is cleaved on the way. Specific examples of the compound obtained by cleaving the compound represented by formula (16-2) include CH ₃ —SO ₃ —CH ₂ —CH ₂ —SO ₃ —CH ₃ . The directions of the two —SO ₃ — (— S (═O) ₂ —O—) are not particularly limited. That is, the above CH ₃ —SO ₃ —CH ₂ —CH ₂ —SO ₃ —CH ₃ is CH ₃ —S (═O) ₂ —O—CH ₂ —CH ₂ —S (═O) ₂ —O—. may be the _{CH 3, CH 3 -O-S} (= O) 2 -CH 2 -CH 2 -S (= O) may be the _{2 -O-CH 3, CH 3} -S (= O) 2 -O It may be —CH ₂ —CH ₂ —O—S (═O) ₂ —CH ₃ .

  Specific examples of acid anhydrides include carboxylic anhydrides such as benzoic anhydride, succinic anhydride, glutaric anhydride, and maleic anhydride; disulfonic anhydrides such as ethanedisulfonic anhydride and propanedisulfonic anhydride. Examples thereof include carboxylic acid sulfonic acid anhydrides such as sulfobenzoic acid anhydride, sulfopropionic acid anhydride, and sulfobutyric acid anhydride. The content of the acid anhydride in the non-aqueous electrolyte solution is not particularly limited, but for example, it is preferably 0.01% by mass to 10% by mass with respect to the total of the total amount excluding the acid anhydride.

  Specific examples of the cyclic carboxylic acid ester include γ-butyrolactone and γ-valerolactone. The content of the cyclic carboxylic acid ester in the nonaqueous electrolytic solution is not particularly limited, but for example, it is preferably 0.01% by mass to 10% by mass with respect to the total of the total amount excluding the cyclic carboxylic acid ester.

Specific examples of the dialkyl sulfoxide include dimethyl sulfoxide <(CH ₃ ) ₂ SO> and diethyl sulfoxide <(C ₂ H ₅ ) ₂ SO>. The content of the dialkyl sulfoxide in the nonaqueous electrolytic solution is not particularly limited, but for example, it is preferably 0.01% by mass to 10% by mass with respect to the total sum excluding the dialkyl sulfoxide.

The chain dicarbonate is any one compound or two or more compounds represented by the formula (10). R ²³ and R ²⁴ are not particularly limited as long as they are either a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group. R ²³ and R ²⁴ may be the same group or different groups. R ²⁵ is not particularly limited as long as it is either a divalent hydrocarbon group or a divalent halogenated hydrocarbon group. The details regarding the monovalent hydrocarbon group and the monovalent halogenated hydrocarbon group are as described above. A divalent halogenated hydrocarbon group is a group in which one or more hydrogen groups of a divalent hydrocarbon group are substituted with a halogen group. Details regarding the divalent hydrocarbon group and the halogen group are as described above. Specific examples of the divalent halogenated hydrocarbon group include a perfluoromethylene group <—CF ₂ —>, a perfluoroethylene group <—C ₂ F ₄ —>, and a perfluoropropylene group <—C ₃ F ₆ —. >, N-perfluorobutylene group <—C ₄ F ₈ —>, and t-perfluorobutylene group <—C (CF ₃ ) ₂ —CF ₂ —>. Specific examples of the chain dicarbonate include ethane-1,2-diyldimethyldicarbonate, ethane-1,2-diylethylmethyldicarbonate, ethane-1,2-diyldiethyldicarbonate, dimethyloxybisethane. Examples include -2,1-diyl dicarbonate, ethylmethyloxybisethane-2,1-diyl dicarbonate, and diethyloxybisethane-2,1-diyl dicarbonate. The content of the chain dicarbonate in the non-aqueous electrolyte solution is not particularly limited, but is preferably 0.01% by mass to 10% by mass, for example, with respect to the total sum excluding the chain dicarbonate. .

The aromatic carbonate is any one compound or two or more compounds represented by the above formula (11). R ^{26 to} R ³⁵ are a monovalent hydrocarbon group, a monovalent oxygen-containing hydrocarbon group, a monovalent nitrogen-containing hydrocarbon group, a monovalent halogenated hydrocarbon group, a monovalent halogenated oxygen-containing hydrocarbon. The group is not particularly limited as long as it is any one of a group, a monovalent halogenated nitrogen-containing hydrocarbon group, and a group in which two or more of these are bonded so as to be monovalent. R ^{26 to} R ³⁵ may be the same group or different groups. A part of R ^{26 to} R ³⁵ may be the same group. The details regarding the monovalent hydrocarbon group and the monovalent halogenated hydrocarbon group are as described above.

The monovalent oxygen-containing hydrocarbon group is a general term for monovalent groups composed of carbon, hydrogen, and oxygen, and may be linear or branched having one or more side chains. It may be. Specific examples of the monovalent oxygen-containing hydrocarbon group include an alkoxy group. Specific examples of the alkoxy group include a methoxy group <—OCH ₃ > and an ethoxy group <—OC ₂ H ₅ >. , it can be exemplified propoxy <-OC ₃ H _7>.

The monovalent nitrogen-containing hydrocarbon group is a general term for monovalent groups composed of carbon, hydrogen and nitrogen, and may be linear or branched having one or more side chains. It may be. Specific examples of the monovalent nitrogen-containing hydrocarbon group include an amino group <—NH ₂ >.

The monovalent halogenated oxygen-containing hydrocarbon group is a group in which one or more hydrogen groups of a monovalent oxygen-containing hydrocarbon group are substituted with a halogen group. Details regarding the monovalent oxygen-containing hydrocarbon group and the halogen group are as described above. Specific examples of the monovalent halogenated oxygen-containing hydrocarbon group include a perfluoromethoxy group <—OCF ₃ —> and a perfluoroethoxy group <—OC ₂ F ₄ —>.

The monovalent halogenated nitrogen-containing hydrocarbon group is a group in which one or more hydrogen groups of a monovalent nitrogen-containing hydrocarbon group are substituted with a halogen group. The details regarding the monovalent nitrogen-containing hydrocarbon group and the halogen group are as described above. Specific examples of the monovalent halogenated nitrogen-containing hydrocarbon group include a perfluoroamino group <—NF ₂ > and a perfluoromethylamino group <—CF ₂ —NF ₂ >.

Specifically, as a group in which two or more types are bonded, specifically, a group in which an alkyl group and an alkoxy group are bonded so as to be monovalent (alkylalkoxy group), and a bond in which an alkyl group and an amino group are monovalent Group (alkylamino group). Specific examples of the alkylalkoxy group include a methylmethoxy group <—CH ₂ —OCH ₃ >. Specific examples of the alkylamino group include a methylamino group <—CH ₂ —NH ₂ >.

  Specific examples of the aromatic carbonate include diphenyl carbonate, bis 4-methylphenyl carbonate, and bispentafluorophenyl carbonate.

  The content of the aromatic carbonate in the non-aqueous electrolytic solution is not particularly limited, but for example, it is preferably 0.01% by mass to 10% by mass with respect to the total sum excluding the aromatic carbonate.

The cyclic carbonate is any one compound or two or more compounds represented by the above formula (12). R ^{36 to} R ³⁹ are not particularly limited as long as they are any one of a hydrogen group and a monovalent hydrocarbon group. R ^{36 to} R ³⁹ may be the same group or different groups. A part of R ^{36 to} R ³⁹ may be the same group. The details regarding the monovalent hydrocarbon group are as described above. Specific examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, and butylene carbonate. The content of the cyclic carbonate in the nonaqueous electrolytic solution is not particularly limited, but is preferably 0.01% by mass to 80% by mass, for example.

The chain monocarbonate is any one compound or two or more compounds represented by the above formula (13). R ⁴⁰ and R ⁴¹ are not particularly limited as long as they are either a hydrogen group or a monovalent hydrocarbon group. R ⁴⁰ and R ⁴¹ may be the same group or different groups. A part of R ⁴⁰ and R ⁴¹ may be the same group. The details regarding the monovalent hydrocarbon group are as described above. Specific examples of the chain monocarbonate include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and methyl propyl carbonate. The content of the chain monocarbonate in the nonaqueous electrolytic solution is not particularly limited, but is preferably 0.01% by mass to 70% by mass, for example.

The chain carboxylic acid ester is any one kind or two or more kinds of compounds represented by the above formula (14). R ⁴² and R ⁴³ are not particularly limited as long as they are either a hydrogen group or a monovalent hydrocarbon group. R ⁴² and R ⁴³ may be the same group or different groups. The details regarding the monovalent hydrocarbon group are as described above. Specific examples of the chain carboxylic acid ester include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethyl acetate, and ethyl trimethyl acetate. The content of the chain carboxylic acid ester in the non-aqueous electrolyte solution is not particularly limited, but is preferably 0.01% by mass to 50% by mass with respect to the total of the chain carboxylic acid ester, for example. .

The phosphoric acid ester is any one compound or two or more compounds represented by the above formula (15). R ^{44 to} R ⁴⁶ are not particularly limited as long as they are any of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group. R ^{44 to} R ⁴⁶ may be the same group or different groups. A part of R ^{44 to} R ⁴⁶ may be the same group. The details regarding the monovalent hydrocarbon group and the monovalent halogenated hydrocarbon group are as described above. Specific examples of the phosphate ester include remethyl phosphate, triethyl phosphate, trifluoroethyl phosphate, and tripropyl phosphate. The content of the phosphate ester in the non-aqueous electrolyte solution is not particularly limited, but for example, it is preferably 0.01% by mass to 50% by mass with respect to the total sum excluding the phosphate ester.

  Furthermore, as another material, any one type or two or more types of solvents, such as a non-aqueous solvent (organic solvent), can be mentioned. However, other materials such as the above sulfonic acid esters are excluded from the non-aqueous solvents described herein.

  Moreover, as another material, any 1 type or 2 types or more of electrolyte salts, such as lithium salt, can be illustrated, for example. However, the electrolyte salt may contain a salt other than the lithium salt, for example. Examples of salts other than lithium salts include light metal salts other than lithium salts.

  Hereinafter, the lithium salt will be described as a specific example of the electrolyte salt, but the lithium salt may be changed to a salt other than the lithium salt. That is, for example, lithium hexafluorophosphate described below may be changed to other light metal salts such as sodium hexafluorophosphate and potassium hexafluorophosphate.

Specific examples of the lithium salt include the various lithium salts described above, and the internal resistance can be reduced. Among them, any one of lithium hexafluorophosphate <LiPF ₆ >, lithium tetrafluoroborate <LiBF ₄ >, lithium perchlorate <LiClO ₄ >, and lithium hexafluoroarsenate <LiAsF ₆ > Two or more types are preferred. This is because the internal resistance is further reduced. In particular, lithium hexafluorophosphate <LiPF ₆ > and lithium tetrafluoroborate <LiBF ₄ > are more preferable, and lithium hexafluorophosphate <LiPF ₆ > is even more preferable.

The electrolyte salt may be one kind or two or more kinds of compounds represented by the formula (17), the formula (18), and the formula (19). R ⁵¹ and R ⁵³ may be the same group or different groups. The same applies to R ⁶¹ , R ⁶² and R ⁶³ , and the same applies to R ⁷¹ and R ⁷² . Two of R ⁶¹ , R ⁶² and R ⁶³ may be the same group.

Here, X ⁵¹ is any one of Group 1 element, Group 2 element, and Al in the long-period periodic table. M ⁵¹ is a transition metal and any one of a group 13 element, a group 14 element, and a group 15 element in the long-period periodic table. R ⁵¹ is a halogen group. Y ⁵¹ is any one of —C (═O) —R ⁵² —C (═O) —, —C (═O) —CR ⁵³ ₂ —, —C (═O) —C (═O) —. It is. However, R ⁵² is any one of an alkylene group, a halogenated alkylene group, an arylene group, and a halogenated arylene group, and R ⁵³ is any one of an alkyl group, a halogenated alkyl group, an aryl group, and a halogenated aryl group. is there. A5 is an integer of 1 to 4, b5 is 0, 2, or 4, and c5, d5, m5, and n5 are integers of 1 to 3.

Here, X ⁶¹ is either a group 1 element or a group 2 element in the long-period periodic table. M ⁶¹ is a transition metal and any one of Group 13, Element 14 and Group 15 elements in the long-period periodic table. Y ⁶¹ represents —C (═O) — (CR ⁶¹ ₂ ) _b6 —C (═O) —, —R ⁶³ ₂ C— (CR ⁶² ₂ ) _c6 —C (═O) —, —R ⁶³ ₂ C _{^{- (CR 62 2) c6 -CR}} 63 2 -, - R 63 2 C- (CR 62 2) c6 -S (= O) 2 -, - S (= O) 2 - (CR 62 2) d6 -S (═O) ₂ —, —C (═O) — (CR ⁶² ₂ ) _{d 6} —S (═O) ₂ —. However, each of R ⁶¹ and R ⁶³ is any one of a hydrogen group, an alkyl group, a halogen group, and a halogenated alkyl group. However, R ⁶¹ is either a halogen group or a halogenated alkyl group, and R ⁶³ is either a halogen group or a halogenated alkyl group. R ⁶² is any one of a hydrogen group, an alkyl group, a halogen group, and a halogenated alkyl group. A6, e6, and n6 are integers of 1 or 2, b6 and d6 are integers of 1 to 4, c6 is an integer of 0 to 4, and f6 and m6 are integers of 1 to 3.

Here, ^X71 is either a group 1 element or a group 2 element in the long-period periodic table. M ⁷¹ is a transition metal and any one of Group 13, Element 14 and Group 15 elements in the long-period periodic table. R _f is either a fluorinated alkyl group or a fluorinated aryl group, and the fluorinated alkyl group and the fluorinated aryl group have 1 to 10 carbon atoms. Y ⁷¹ represents —C (═O) — (CR ⁷¹ ₂ ) _d7 —C (═O) —, —R ⁷² ₂ C— (CR ⁷¹ ₂ ) _d7 —C (═O) —, —R ⁷² ₂ C _{^{- (CR 71 2) d7 -CR}} 72 2 -, - R 72 2 C- (CR 71 2) d7 -S (= O) 2 -, - S (= O) 2 - (CR 71 2) e7 -S _{(= O) 2 -, -} C (= O) - (CR 71 2) e7 -S (= O) 2 - is either. However, R ⁷¹ is a hydrogen group, an alkyl group, a halogen group, or a halogenated alkyl group, R ⁷² is a hydrogen group, an alkyl group, a halogen group, or a halogenated alkyl group, R ⁷² Is either a halogen group or a halogenated alkyl group. A7, f7, and n7 are integers of 1 or 2, b7, c7, and e7 are integers of 1 to 4, d7 is an integer of 0 to 4, and g7 and m7 are integers of 1 to 3. is there.

  Group 1 elements are hydrogen <H>, lithium <Li>, sodium <Na>, potassium <K>, rubidium <Rb>, cesium <Cs>, and francium <Fr>. Group 2 elements are beryllium <Be>, magnesium <Mg>, calcium <Ca>, strontium <Sr>, barium <Ba>, and radium <Ra>. Group 13 elements are boron <B>, aluminum <Al>, gallium <Ga>, indium <In>, and thallium <Tl>. The group 14 elements are carbon <C>, silicon <Si>, germanium <Ge>, tin <Sn>, and lead <Pb>. The group 15 elements are nitrogen <N>, phosphorus <P>, arsenic <As>, antimony <Sb>, and bismuth <Bi>.

  Specific examples of the compound represented by Formula (17) include compounds represented by Formula (17-1) to Formula (17-6). Specific examples of the compound represented by Formula (18) include compounds represented by Formula (18-1) to Formula (18-8). Specific examples of the compound represented by the formula (19) include a compound represented by the formula (19-1).

  Moreover, the compound represented by Formula (20) or Formula (21) can also be illustrated as electrolyte salt. p, q, and r may be the same value or different values. Two of p, q, and r may be the same value.

但し、Ｒ⁸¹は炭素数２乃至４の直鎖状又は分岐状のパーフルオロアルキレン基である。

R ⁸¹ is a linear or branched perfluoroalkylene group having 2 to 4 carbon atoms.

LiC (C _p F _{2p + 1} SO ₂ ) (C _q F _{2q + 1} SO ₂ ) (C _r F _{2r + 1} SO ₂ ) (21)
However, p, q, and r are integers of 1 or more.

  The compound shown in Formula (20) is a cyclic imide compound. Specific examples of the cyclic imide compound include compounds represented by formula (20-1) to formula (20-4).

The compound represented by the formula (21) is a chain methide compound. Specific examples of the chain methide compound include lithium tristrifluoromethanesulfonyl methide <LiC (CF ₃ SO ₂ ) ₃ >.

  The content of the electrolyte salt is not particularly limited, but is preferably 0.3 mol / kg to 3.0 mol / kg with respect to the solvent from the viewpoint of obtaining high ion conductivity. When calculating content of electrolyte salt, you may include the quantity of said 1st compound, lithium monofluorophosphate, and lithium difluorophosphate in the quantity of electrolyte salt. In addition, the amount of the solvent includes the second compound, the third compound, the sulfonic acid ester, the acid anhydride, the cyclic carboxylic acid ester, the dialkyl sulfoxide, the chain dicarbonate, the aromatic carbonate, the cyclic carbonate, and the chain monocarbonate. The amount of ester, chain carboxylic acid ester, phosphate ester may be included.

  The intrinsic viscosity of the nonaqueous electrolytic solution is not particularly limited, but is preferably 10 mPa / s or less at 25 ° C. from the viewpoint of ensuring the dissociation property of the electrolyte salt, ion mobility, and the like.

  In particular, non-aqueous electrolytes include sulfonic acid esters, acid anhydrides, cyclic carboxylic acid esters, dialkyl sulfoxides, chain dicarbonates, aromatic carbonates, cyclic carbonates, chain monocarbonates, chain carboxylic acid esters. If any one or two or more of phosphoric acid ester, lithium monofluorophosphate, and lithium difluorophosphate are contained, a higher effect can be obtained.

  If the non-aqueous electrolyte contains at least one of lithium hexafluorophosphate and lithium tetrafluoroborate, higher effects can be obtained.

Ｒ²²−（ＣＮ）_n （３−Ｆ）
但し、
式（１）中、Ｍは金属元素であり、Ｚ¹及びＺ²のそれぞれは、フッ素基、１価の炭化水素基、１価のフッ素化炭化水素基のいずれかであり、Ｚ¹及びＺ²の少なくとも一方は、フッ素基、１価のフッ素化炭化水素基のいずれかであり、Ｙ¹及びＹ²のそれぞれは、スルホニル基、カルボニル基のいずれかであり、
式（２−Ａ）中、Ｒ¹は１価の炭化水素基であり、
式（２−Ｂ）中、Ｒ²は１価の炭化水素基であり、Ｘは、１又は２以上のエーテル結合と１又は２以上の２価の炭化水素基とが任意の順に結合した基であり、
式（３−Ａ）中、Ｒ³及びＲ⁴のそれぞれは、水素基、１価の炭化水素基のいずれかであり、
式（３−Ｂ）中、Ｒ⁵，Ｒ⁶，Ｒ⁷，Ｒ⁸のそれぞれは、水素基、１価の飽和炭化水素基、１価の不飽和炭化水素基のいずれかであり、Ｒ⁵，Ｒ⁶，Ｒ⁷，Ｒ⁸の少なくとも１つは、１価の不飽和炭化水素基であり、
式（３−Ｃ）中、Ｒ⁹は、＞ＣＲ¹⁰Ｒ¹¹で表される基であり、Ｒ¹⁰及びＲ¹¹のそれぞれは、水素基、１価の炭化水素基のいずれかであり、
式（３−Ｄ）中、Ｒ¹²，Ｒ¹³，Ｒ¹⁴，Ｒ¹⁵のそれぞれは、水素基、ハロゲン基、１価の炭化水素基、１価のハロゲン化炭化水素基のいずれかであり、Ｒ¹²，Ｒ¹³，Ｒ¹⁴，Ｒ¹⁵の少なくとも１つは、ハロゲン基、１価のハロゲン化炭化水素基のいずれかであり、
式（３−Ｅ）中、Ｒ¹⁶，Ｒ¹⁷，Ｒ¹⁸，Ｒ¹⁹，Ｒ²⁰，Ｒ²¹のそれぞれは、水素基、ハロゲン基、１価の炭化水素基、１価のハロゲン化炭化水素基のいずれかであり、Ｒ¹⁶，Ｒ¹⁷，Ｒ¹⁸，Ｒ¹⁹，Ｒ²⁰，Ｒ²¹の少なくとも１つは、ハロゲン基、１価のハロゲン化炭化水素基のいずれかであり、
式（３−Ｆ）中、Ｒ²²はｎ価（但し、ｎは２以上の整数）の炭化水素基である。
［Ｌ０２］Ｍは、アルカリ金属元素であり、
１価の炭化水素基は、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、アリール基、及び、これらの２種類以上が１価となるように結合した基のいずれかであり、
１価のフッ素化炭化水素基は、１価の炭化水素基の内の少なくとも１つの水素基がフッ素基によって置換された基であり、
２価の炭化水素基は、アルキレン基、アルケニレン基、アルキニレン基、シクロアルキレン基、アリーレン基、及び、これらの２種類以上が結合された基のいずれかであり、
１価の飽和炭化水素基は、アルキル基、シクロアルキル基、及び、これらが１価となるように結合された基のいずれかであり、
１価の不飽和炭化水素基は、アルケニル基、アルキニル基、アリール基、これらの１種類以上を含む基、及び、これらの２種類以上が１価となるように結合された基のいずれかであり、
ハロゲン基は、フッ素基、塩素基、臭素基、及び、ヨウ素基のいずれかであり、
１価のハロゲン化炭化水素基は、１価の炭化水素基の内の少なくとも１つの水素基がハロゲン基によって置換された基である［Ｌ０１］に記載の二次電池。
［Ｌ０３］Ｍはリチウムであり、
１価のフッ素化炭化水素基は、パーフルオロアルキル基であり、
Ｘは、−Ｏ−Ｙ−（但し、Ｙは、２価の炭化水素基）で表される基である［Ｌ０１］又は［Ｌ０２］に記載の二次電池。
［Ｌ０４］非水系電解液は、スルホン酸エステル、酸無水物、環状カルボン酸エステル、ジアルキルスルホキシド、式（１０）乃至式（１５）で表される化合物、モノフルオロリン酸リチウム、及び、ジフルオロリン酸リチウムの少なくとも１種を含む［Ｌ０１］乃至［Ｌ０３］のいずれか１項に記載の二次電池。

但し、
Ｒ²³及びＲ²⁴のそれぞれは、１価の炭化水素基、１価のハロゲン化炭化水素基のいずれかであり、
Ｒ²⁵は、２価の炭化水素基、２価のハロゲン化炭化水素基のいずれかであり、
Ｒ²⁶，Ｒ²⁷，Ｒ²⁸，Ｒ²⁹，Ｒ³⁰，Ｒ³¹，Ｒ³²，Ｒ³³，Ｒ³⁴，Ｒ³⁵のそれぞれは、１価の炭化水素基、１価の酸素含有炭化水素基、１価の窒素含有炭化水素基、１価のハロゲン化炭化水素基、１価のハロゲン化酸素含有炭化水素基、１価のハロゲン化窒素含有炭化水素基、これらの２種類以上が１価となるように結合した基のいずれかであり、
Ｒ³⁶，Ｒ³⁷，Ｒ³⁸，Ｒ³⁹のそれぞれは、水素基、１価の炭化水素基のいずれかであり、
Ｒ⁴⁰及びＲ⁴¹のそれぞれは、水素基、１価の炭化水素基のいずれかであり、
Ｒ⁴²及びＲ⁴³のそれぞれは、水素基、１価の炭化水素基のいずれかであり、
Ｒ⁴⁴，Ｒ⁴⁵，Ｒ⁴⁶のそれぞれは、１価の炭化水素基、１価のハロゲン化炭化水素基のいずれかである。
［Ｌ０５］２価のハロゲン化炭化水素基は、２価の炭化水素基の内の少なくとも１つの水素基がハロゲン基によって置換された基であり、
ハロゲン基は、フッ素基、塩素基、臭素基及びヨウ素基のいずれかであり、
１価の酸素含有炭化水素基は、アルコキシ基であり、
１価の窒素含有炭化水素基は、アルキルアミノ基であり、
１価のハロゲン化酸素含有炭化水素基は、１価の酸素含有炭化水素基の内の少なくとも１つの水素基がハロゲン基によって置換された基であり、
１価のハロゲン化窒素含有炭化水素基は、１価の窒素含有炭化水素基の内の少なくとも１つの水素基がハロゲン基によって置換された基である［Ｌ０４］に記載の二次電池。
［Ｌ０６］非水系電解液は、六フッ化リン酸リチウム及び四フッ化ホウ酸リチウムの内の少なくとも一方を含む［Ｌ０１］乃至［Ｌ０５］のいずれか１項に記載の二次電池。
［Ｌ０７］正極は、電極反応物質を吸蔵・放出可能である正極活物質を含み、
負極は、電極反応物質を吸蔵・放出可能である負極活物質を含み、
正極活物質と負極活物質との間に絶縁性材料を備え、
絶縁性材料は、絶縁性セラミックス及び絶縁性高分子化合物の少なくとも一方を含む［Ｌ０１］乃至［Ｌ０６］のいずれか１項に記載の二次電池。
［Ｌ０８］絶縁性セラミックスは、酸化アルミニウム、酸化ケイ素、酸化マグネシウム、酸化チタン、及び、酸化ジルコニウムの少なくとも１種を含み、
絶縁性高分子化合物は、フッ化ビニリデンの単独重合体及び共重合体の少なくとも一方を含む［Ｌ０７］に記載の二次電池。
［Ｌ０９］正極活物質の表面に、絶縁性材料を含む第１絶縁層が設けられている［Ｌ０７］又は［Ｌ０８］に記載の二次電池。
［Ｌ１０］負極の表面に、絶縁性材料を含む第２絶縁層が設けられている［Ｌ０７］又は［Ｌ０８］に記載の二次電池。
［Ｌ１１］セパレータの表面に、絶縁性材料を含む第３絶縁層が設けられている［Ｌ０７］又は［Ｌ０８］に記載の二次電池。
［Ｍ０１］《電池パック》
［Ａ０１］乃至［Ｌ１１］のいずれか１項に記載の二次電池、
二次電池の動作を制御する制御部、及び、
制御部の指示に応じて二次電池の動作を切り換えるスイッチ部、
を備えている電池パック。
［Ｍ０２］《電動車両》
［Ａ０１］乃至［Ｌ１１］のいずれか１項に記載の二次電池、
二次電池から供給された電力を駆動力に変換する変換部、
駆動力に応じて駆動する駆動部、及び、
二次電池の動作を制御する制御部、
を備えている電動車両。
［Ｍ０３］《電力貯蔵システム》
［Ａ０１］乃至［Ｌ１１］のいずれか１項に記載の二次電池、
二次電池から電力を供給される１又は２以上の電気機器、及び、
二次電池からの電気機器に対する電力供給を制御する制御部、
を備えている電力貯蔵システム。
［Ｍ０４］《電動工具》
［Ａ０１］乃至［Ｌ１１］のいずれか１項に記載の二次電池、及び、
二次電池から電力を供給される可動部、
を備えている電動工具。
［Ｍ０５］《電子機器》
［Ａ０１］乃至［Ｌ１１］のいずれか１項に記載の二次電池を電力供給源として備えている電子機器。 In addition, this indication can also take the following structures.
[A01] << Secondary battery: first embodiment >>
A secondary battery in which a structure in which a positive electrode, a separator, and a negative electrode are wound or stacked is housed in an exterior member and filled with an electrolyte,
The longitudinal direction of the structure is the X direction, the short direction of the structure is the Z direction, the thickness direction of the structure is the Y direction,
The outer surface along the XZ plane of the structure is the first surface of the structure and the second surface of the structure,
The inner surface of the exterior member facing the first surface of the structure is the first surface of the exterior member, the inner surface of the exterior member facing the second surface of the structure is the second surface of the exterior member,
When the dynamic friction coefficient of the first surface of the exterior member is μ ₁ and the dynamic friction coefficient of the second surface of the exterior member is μ ₂ ,
μ ₁ > μ ₂
Satisfying secondary battery.
[A02] The secondary battery according to [A01], wherein the first surface of the exterior member is made of a material different from the material constituting the second surface of the exterior member.
[A03] The combination of (material constituting the first surface of the exterior member, material constituting the second surface of the exterior member) is (polypropylene, nylon), (polypropylene, polyethylene), or (polyethylene, nylon). A secondary battery according to [A02].
[A04] The secondary battery according to [A01], wherein the first surface of the exterior member is subjected to a surface treatment different from that of the second surface of the exterior member.
[A05] The secondary battery according to [A04], in which the first surface of the exterior member is subjected to surface treatment, and the second surface of the exterior member is not subjected to surface treatment.
[A06] The secondary battery according to [A04] or [A05], wherein the first surface of the exterior member is made of the same material as that of the second surface of the exterior member.
[A07] The secondary battery according to any one of [A04] to [A06], in which the surface treatment is a roughening treatment.
[A08] The secondary battery according to [A07], in which the roughening treatment is chemical treatment, ultraviolet treatment, ozone treatment, or plasma treatment.
[A09] The secondary battery according to [A08], wherein the chemical treatment is an etching treatment.
[A10] The secondary battery according to [A07], in which the roughening treatment is an embossing treatment.
[A11] The secondary battery according to [A07], in which the roughening process is a blasting process.
[A12] The secondary battery according to [A01], wherein the first surface of the exterior member is rougher than the roughness of the second surface of the exterior member.
[A13] The secondary battery according to [A12], wherein unevenness is formed on the first surface of the exterior member, and the second surface of the exterior member is flat.
[A14] The secondary battery according to [A12], wherein the first surface of the exterior member has more irregularities per unit area than the irregularities formed on the second surface of the exterior member.
[A15] The secondary battery according to [A12], wherein the first surface of the exterior member has irregularities that are on average larger than the irregularities formed on the second surface of the exterior member.
[A16] The secondary battery according to any one of [A12] to [A15], wherein the first surface of the exterior member is made of the same material as that of the second surface of the exterior member.
[B01] << Secondary battery: second embodiment >>
A secondary battery in which a structure in which a positive electrode, a separator, and a negative electrode are wound or stacked is housed in an exterior member and filled with an electrolyte,
The longitudinal direction of the structure is the X direction, the short direction of the structure is the Z direction, the thickness direction of the structure is the Y direction,
The outer surface along the XZ plane of the structure is the first surface of the structure and the second surface of the structure,
When the inner surface of the exterior member facing the first surface of the structure is the first surface of the exterior member, and the inner surface of the exterior member facing the second surface of the structure is the second surface of the exterior member,
A secondary battery in which a first surface of the exterior member is subjected to a surface treatment different from that of the second surface of the exterior member.
[B02] The secondary battery according to [B01], in which the first surface of the exterior member is subjected to surface treatment, and the second surface of the exterior member is not subjected to surface treatment.
[B03] The secondary battery according to [B01] or [B02], in which the first surface of the exterior member is made of the same material as that of the second surface of the exterior member.
[B04] The secondary battery according to any one of [B01] to [B03], in which the surface treatment is a roughening treatment.
[B05] The secondary battery according to [B04], wherein the roughening treatment is chemical treatment, ultraviolet treatment, ozone treatment, or plasma treatment.
[B06] The secondary battery according to [B05], in which the chemical treatment is an etching treatment.
[B07] The secondary battery according to [B04], in which the roughening process is an embossing process.
[B08] The secondary battery according to [B04], in which the roughening process is a blasting process.
[B09] The secondary battery according to [B01] or [B02], in which the first surface of the exterior member is made of a material different from the material constituting the second surface of the exterior member.
The combination of [B10] (the material constituting the first surface of the exterior member and the material constituting the second surface of the exterior member) is (polypropylene, nylon), (polypropylene, polyethylene), or (polyethylene, nylon). A secondary battery according to [B09].
[C01] << secondary battery: second embodiment >>
A secondary battery in which a structure in which a positive electrode, a separator, and a negative electrode are wound or stacked is housed in an exterior member and filled with an electrolyte,
The longitudinal direction of the structure is the X direction, the short direction of the structure is the Z direction, the thickness direction of the structure is the Y direction,
The outer surface along the XZ plane of the structure is the first surface of the structure and the second surface of the structure,
When the inner surface of the exterior member facing the first surface of the structure is the first surface of the exterior member, and the inner surface of the exterior member facing the second surface of the structure is the second surface of the exterior member,
A secondary battery in which the first surface of the exterior member is rougher than the roughness of the second surface of the exterior member.
[C02] The secondary battery according to [C01], wherein unevenness is formed on the first surface of the exterior member, and the second surface of the exterior member is flat.
[C03] The secondary battery according to [C01], wherein the first surface of the exterior member has more unevenness per unit area than the unevenness formed on the second surface of the exterior member.
[C04] The secondary battery according to [C01], wherein the first surface of the exterior member has irregularities that are larger on average than the irregularities formed on the second surface of the exterior member.
[C05] The secondary battery according to any one of [C01] to [C04], wherein the first surface of the exterior member is made of the same material as that of the second surface of the exterior member.
[C06] The secondary battery according to [C01], wherein the first surface of the exterior member is made of a material different from the material constituting the second surface of the exterior member.
The combination of [C07] (the material constituting the first surface of the exterior member, the material constituting the second surface of the exterior member) is (polypropylene, nylon), (polypropylene, polyethylene), or (polyethylene, nylon). A secondary battery according to [C06].
[D01] << Secondary battery: third embodiment >>
A secondary battery in which a structure in which a positive electrode, a separator, and a negative electrode are wound or stacked is housed in an exterior member and filled with an electrolyte,
The longitudinal direction of the structure is the X direction, the short direction of the structure is the Z direction, the thickness direction of the structure is the Y direction,
The outer surface along the XZ plane of the structure is the first surface of the structure and the second surface of the structure,
When the inner surface of the exterior member facing the first surface of the structure is the first surface of the exterior member, and the inner surface of the exterior member facing the second surface of the structure is the second surface of the exterior member,
The combination of (material constituting the first surface of the exterior member, material constituting the second surface of the exterior member) is (polypropylene, nylon), (polypropylene, polyethylene), or (polyethylene, nylon). battery.
[E01] The structure according to any one of [A01] to [D01], wherein the larger expansion amount when the structure is expanded by charging is the first surface of the structure, and the smaller is the second surface of the structure. Secondary battery.
[E02] The secondary battery according to any one of [A01] to [E01], wherein the structure warps so that the first surface is convex when charged.
[E03] The secondary battery according to any one of [A01] to [E02], in which a Young's modulus of the exterior member is 5 × 10 ⁸ Pa to 7 × 10 ⁹ Pa.
[E04] The secondary battery according to any one of [A01] to [E03], wherein the exterior member has a stacked structure of a first resin layer, a metal layer, and a second resin layer.
[E05] The secondary battery according to any one of [A01] to [E04], wherein the electrolyte is a gel electrolyte.
[E06] The secondary battery according to any one of [A01] to [E05], in which a material constituting the separator is made of polypropylene resin, polyethylene resin, or polyimide resin.
[F01] << Secondary battery: Fourth aspect >>
A secondary battery in which a structure in which a positive electrode, a separator, and a negative electrode are wound or stacked is housed in an exterior member and filled with an electrolyte,
The exterior member is
A first exterior member, and
A second exterior member in which a recess for housing the structure is formed and an outer edge is fixed to the first exterior member;
Consisting of
A secondary battery in which a material constituting the first exterior member is different from a material constituting the second exterior member.
[F02] The secondary battery according to [F01], in which the first exterior member has a higher Young's modulus than the second exterior member.
[F03] The first exterior member has a laminated structure of a first A resin layer, a first metal layer, and a first B resin layer,
The second exterior member has a laminated structure of a second A resin layer, a second metal layer, and a second B resin layer,
The first metal layer is made of stainless steel,
The light emitting element according to [F01] or [F02], in which the second metal layer is made of aluminum or an aluminum alloy.
[F04] The first A resin layer and the first B resin layer are made of different materials,
The second A resin layer and the second B resin layer are made of different materials,
The first A resin layer and the second A resin layer are made of the same material, or alternatively, the first A resin layer and the second A resin layer are made of different materials,
The first B resin layer and the second B resin layer are made of the same material, or the first B resin layer and the second B resin layer are made of different materials,
The secondary battery according to [F03], in which the first metal layer and the second metal layer are made of different materials.
[F05] The thickness of the first metal layer is 1 × 10 ⁻⁵ m to 1.8 × 10 ⁻⁴ m,
The thickness of the second metal layer is the light-emitting element according to [F03] or [F04], which is 5 × 10 ⁻⁵ m to 2 × 10 ⁻⁴ m.
[F06] The secondary battery according to any one of [F01] to [F05], in which an outer edge of the second exterior member is thermally fused and fixed to the first exterior member.
[F07] When the structure is expanded by charging, the first surface of the structure is larger and the smaller surface is the second surface of the structure, and the first surface of the structure is convex during charging. [F01] to [F06] The secondary battery according to any one of [F01] to [W06].
[F08] The secondary battery according to any one of [F01] to [F07], in which the electrolyte is a gel electrolyte.
[F09] The secondary battery according to any one of [F01] to [F08], in which a material constituting the separator is made of polypropylene resin, polyethylene resin, or polyimide resin.
[G01] The longitudinal direction of the structure is the X direction, the lateral direction of the structure is the Z direction, the thickness direction of the structure is the Y direction, and the outer surface along the XZ plane of the structure is the first surface of the structure and The second surface of the structure is the first surface of the first exterior member that faces the first surface of the structure, and the inner surface of the second exterior member that faces the second surface of the structure. When the second surface of the second exterior member is the first surface and the first surface of the first exterior member is μ ₁ , and the second surface of the second exterior member is μ ₂ .
μ ₁ > μ ₂
The secondary battery according to any one of [F01] to [F09] that satisfies the following conditions.
[G02] The secondary battery according to [G01], wherein the first surface of the first exterior member is made of a material different from a material constituting the second surface of the second exterior member.
The combination of [G03] (the material constituting the first surface of the first exterior member, the material constituting the second surface of the second exterior member) is (polypropylene, nylon), (polypropylene, polyethylene), or (polyethylene) , Nylon), the secondary battery according to [G02].
[G04] The secondary battery according to [G01], wherein the first surface of the first exterior member is subjected to a surface treatment different from that of the second surface of the second exterior member.
[G05] The secondary battery according to [G04], in which the first surface of the first exterior member is subjected to surface treatment, and the second surface of the second exterior member is not subjected to surface treatment.
[G06] The secondary battery according to [G04] or [G05], wherein the first surface of the first exterior member is made of the same material as that of the second surface of the second exterior member.
[G07] The secondary battery according to any one of [G04] to [G06], in which the surface treatment is a roughening treatment.
[G08] The secondary battery according to [G07], wherein the roughening treatment is chemical treatment, ultraviolet treatment, ozone treatment, or plasma treatment.
[G09] The secondary battery according to [G08], in which the chemical treatment is an etching treatment.
[G10] The secondary battery according to [G07], wherein the roughening process is an embossing process.
[G11] The secondary battery according to [G07], wherein the roughening process is a blasting process.
[G12] The secondary battery according to [G01], wherein the first surface of the first exterior member is rougher than the roughness of the second surface of the second exterior member.
[G13] The secondary battery according to [G12], wherein unevenness is formed on the first surface of the first exterior member, and the second surface of the second exterior member is flat.
[G14] The first surface of the first exterior member has more irregularities per unit area than the irregularities formed on the second surface of the second exterior member. The secondary according to [G12] battery.
[G15] The secondary battery according to [G12], wherein the first surface of the first exterior member has irregularities that are on average larger than the irregularities formed on the second surface of the second exterior member.
[G16] The secondary battery according to any one of [G12] to [G15], wherein the first surface of the first exterior member is made of the same material as that constituting the second surface of the second exterior member.
[H01] The inner surface of the first exterior member facing the first surface of the structure is the first surface of the first exterior member, and the inner surface of the second exterior member facing the second surface of the structure is the second exterior member. When it is set as the second surface, the first surface of the first exterior member is subjected to surface treatment different from that of the second surface of the second exterior member, according to any one of [F01] to [F09]. Secondary battery.
[H02] The secondary battery according to [H01], wherein the first surface of the exterior member is subjected to surface treatment, and the second surface of the exterior member is not subjected to surface treatment.
[H03] The secondary battery according to [H01] or [H02], wherein the first surface of the exterior member is made of the same material as that of the second surface of the exterior member.
[H04] The secondary battery according to any one of [H01] to [H03], in which the surface treatment is a roughening treatment.
[H05] The secondary battery according to [H04], wherein the roughening treatment is chemical treatment, ultraviolet treatment, ozone treatment, or plasma treatment.
[H06] The secondary battery according to [H05], wherein the chemical treatment is an etching treatment.
[H07] The secondary battery according to [H04], wherein the roughening treatment is an embossing treatment.
[H08] The secondary battery according to [H04], in which the roughening process is a blasting process.
[H09] The secondary battery according to [H01] or [H02], wherein the first surface of the exterior member is made of a material different from a material constituting the second surface of the exterior member.
The combination of [H10] (material constituting the first surface of the exterior member, material constituting the second surface of the exterior member) is (polypropylene, nylon), (polypropylene, polyethylene), or (polyethylene, nylon). A secondary battery according to [H09].
[J01] The inner surface of the first exterior member facing the first surface of the structure is the first surface of the first exterior member, and the inner surface of the second exterior member facing the second surface of the structure is the second exterior member. The secondary battery according to any one of [F01] to [F09], in which the first surface of the first exterior member is rougher than the roughness of the second surface of the second exterior member when the second surface is used.
[J02] The secondary battery according to [J01], wherein the first surface of the exterior member is uneven, and the second surface of the exterior member is flat.
[J03] The secondary battery according to [J01], wherein the first surface of the exterior member has more irregularities per unit area than the irregularities formed on the second surface of the exterior member.
[J04] The secondary battery according to [J01], wherein the first surface of the exterior member has irregularities that are larger on average than the irregularities formed on the second surface of the exterior member.
[J05] The secondary battery according to any one of [J01] to [J04], wherein the first surface of the exterior member is made of the same material as that of the second surface of the exterior member.
[J06] The secondary battery according to [J01], wherein the first surface of the exterior member is made of a material different from the material constituting the second surface of the exterior member.
[J07] The combination of (material constituting the first surface of the exterior member, material constituting the second surface of the exterior member) is (polypropylene, nylon), (polypropylene, polyethylene), or (polyethylene, nylon). A secondary battery according to [J06].
[K01] The inner surface of the first exterior member facing the first surface of the structure is the first surface of the first exterior member, and the inner surface of the second exterior member facing the second surface of the structure is the second exterior member. When the second surface is used, the combination of (material constituting the first surface of the first exterior member, material constituting the second surface of the second exterior member) is (polypropylene, nylon), (polypropylene, polyethylene), Alternatively, the secondary battery according to any one of [F01] to [F09], which is (polyethylene, nylon).
[L01] The electrolyte is composed of a non-aqueous electrolyte,
Non-aqueous electrolyte is
A compound represented by formula (1),
At least one of a compound represented by formula (2-A) and a compound represented by formula (2-B), and
At least one compound of compounds represented by formula (3-A) to formula (3-F);
The content of the compound represented by the formula (1) is 2.5 mol / liter to 6 mol / liter, preferably 3 mol / liter to 6 mol / liter, [A01] to [K01] The secondary battery according to any one of the above.
M ⁺ [(Z ¹ Y ¹ ) (Z ² Y ² ) N] ^- (1)
R ¹ -CN (2-A)
^{R 2 -X-CN (2-} B)

_{^{R 22 - (CN) n (}} 3-F)
However,
In formula (1), M is a metal element, and each of Z ¹ and Z ² is either a fluorine group, a monovalent hydrocarbon group, or a monovalent fluorinated hydrocarbon group, and Z ¹ and Z ² is at least one of a fluorine group and a monovalent fluorinated hydrocarbon group, and each of Y ¹ and Y ² is either a sulfonyl group or a carbonyl group,
In formula (2-A), R ¹ is a monovalent hydrocarbon group,
In the formula (2-B), R ² is a monovalent hydrocarbon group, and X is a group in which one or two or more ether bonds and one or two or more divalent hydrocarbon groups are bonded in any order. And
In formula (3-A), each of R ³ and R ⁴ is either a hydrogen group or a monovalent hydrocarbon group,
In formula (3-B), each of R ⁵ , R ⁶ , R ⁷ , and R ^{8 is} any one of a hydrogen group, a monovalent saturated hydrocarbon group, and a monovalent unsaturated hydrocarbon group, and R ⁵ , R ⁶ , R ⁷ , R ⁸ are monovalent unsaturated hydrocarbon groups,
In formula (3-C), R ⁹ is a group represented by> CR ¹⁰ R ¹¹ , and each of R ¹⁰ and R ¹¹ is either a hydrogen group or a monovalent hydrocarbon group,
In formula (3-D), each of R ¹² , R ¹³ , R ¹⁴ , and R ^{15 is} any one of a hydrogen group, a halogen group, a monovalent hydrocarbon group, and a monovalent halogenated hydrocarbon group, At least one of R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ is any one of a halogen group and a monovalent halogenated hydrocarbon group;
In formula (3-E), each of R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ represents a hydrogen group, a halogen group, a monovalent hydrocarbon group, or a monovalent halogenated hydrocarbon group. And at least one of R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ is any one of a halogen group and a monovalent halogenated hydrocarbon group,
In formula (3-F), R ²² represents an n-valent hydrocarbon group (where n is an integer of 2 or more).
[L02] M is an alkali metal element,
The monovalent hydrocarbon group is any one of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and a group in which two or more of these are bonded so as to be monovalent,
The monovalent fluorinated hydrocarbon group is a group in which at least one of the monovalent hydrocarbon groups is substituted with a fluorine group,
The divalent hydrocarbon group is any one of an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, and a group in which two or more of these are bonded.
The monovalent saturated hydrocarbon group is any one of an alkyl group, a cycloalkyl group, and a group in which these are monovalent.
The monovalent unsaturated hydrocarbon group is any one of an alkenyl group, an alkynyl group, an aryl group, a group containing one or more of these, and a group bonded so that two or more of these are monovalent Yes,
The halogen group is any one of a fluorine group, a chlorine group, a bromine group, and an iodine group,
The secondary battery according to [L01], wherein the monovalent halogenated hydrocarbon group is a group in which at least one of the monovalent hydrocarbon groups is substituted with a halogen group.
[L03] M is lithium;
The monovalent fluorinated hydrocarbon group is a perfluoroalkyl group,
The secondary battery according to [L01] or [L02], wherein X is a group represented by —O—Y— (where Y is a divalent hydrocarbon group).
[L04] Non-aqueous electrolyte includes sulfonic acid ester, acid anhydride, cyclic carboxylic acid ester, dialkyl sulfoxide, compound represented by formula (10) to formula (15), lithium monofluorophosphate, and difluorophosphorus The secondary battery according to any one of [L01] to [L03], including at least one kind of lithium acid.

However,
Each of R ²³ and R ²⁴ is a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group;
R ²⁵ is a divalent hydrocarbon group or a divalent halogenated hydrocarbon group,
R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , and R ³⁵ are each a monovalent hydrocarbon group, a monovalent oxygen-containing hydrocarbon group, A monovalent nitrogen-containing hydrocarbon group, a monovalent halogenated hydrocarbon group, a monovalent halogenated oxygen-containing hydrocarbon group, a monovalent halogenated nitrogen-containing hydrocarbon group, and two or more of these are monovalent Any of the groups attached to
Each of R ³⁶ , R ³⁷ , R ³⁸ , and R ³⁹ is a hydrogen group or a monovalent hydrocarbon group,
Each of R ⁴⁰ and R ⁴¹ is either a hydrogen group or a monovalent hydrocarbon group,
Each of R ⁴² and R ⁴³ is either a hydrogen group or a monovalent hydrocarbon group,
Each of R ⁴⁴ , R ⁴⁵ and R ⁴⁶ is either a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group.
[L05] The divalent halogenated hydrocarbon group is a group in which at least one of the divalent hydrocarbon groups is substituted with a halogen group,
The halogen group is any one of a fluorine group, a chlorine group, a bromine group and an iodine group,
The monovalent oxygen-containing hydrocarbon group is an alkoxy group,
The monovalent nitrogen-containing hydrocarbon group is an alkylamino group,
The monovalent halogenated oxygen-containing hydrocarbon group is a group in which at least one of the monovalent oxygen-containing hydrocarbon groups is substituted with a halogen group,
The secondary battery according to [L04], wherein the monovalent halogenated nitrogen-containing hydrocarbon group is a group in which at least one of the monovalent nitrogen-containing hydrocarbon groups is substituted with a halogen group.
[L06] The secondary battery according to any one of [L01] to [L05], wherein the nonaqueous electrolytic solution includes at least one of lithium hexafluorophosphate and lithium tetrafluoroborate.
[L07] The positive electrode includes a positive electrode active material capable of occluding and releasing the electrode reactant,
The negative electrode includes a negative electrode active material capable of occluding and releasing an electrode reactant,
An insulating material is provided between the positive electrode active material and the negative electrode active material,
The secondary battery according to any one of [L01] to [L06], wherein the insulating material includes at least one of an insulating ceramic and an insulating polymer compound.
[L08] Insulating ceramics includes at least one of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, and zirconium oxide,
The insulating polymer compound according to [L07], wherein the insulating polymer compound includes at least one of a homopolymer and a copolymer of vinylidene fluoride.
[L09] The secondary battery according to [L07] or [L08], in which a first insulating layer including an insulating material is provided on a surface of the positive electrode active material.
[L10] The secondary battery according to [L07] or [L08], wherein a second insulating layer containing an insulating material is provided on a surface of the negative electrode.
[L11] The secondary battery according to [L07] or [L08], wherein a third insulating layer containing an insulating material is provided on a surface of the separator.
[M01] << Battery pack >>
The secondary battery according to any one of [A01] to [L11],
A control unit for controlling the operation of the secondary battery, and
A switch unit that switches the operation of the secondary battery in accordance with an instruction from the control unit,
Battery pack with
[M02] << Electric vehicle >>
The secondary battery according to any one of [A01] to [L11],
A conversion unit that converts electric power supplied from the secondary battery into driving force;
A driving unit for driving according to the driving force, and
A control unit for controlling the operation of the secondary battery,
Electric vehicle equipped with.
[M03] << Power storage system >>
The secondary battery according to any one of [A01] to [L11],
One or more electric devices supplied with power from the secondary battery, and
A control unit for controlling the power supply from the secondary battery to the electric device,
Power storage system equipped with.
[M04] << Power tool >>
The secondary battery according to any one of [A01] to [L11], and
A movable part to which power is supplied from the secondary battery,
Power tool equipped with.
[M05] << Electronic equipment >>
An electronic device comprising the secondary battery according to any one of [A01] to [L11] as a power supply source.

DESCRIPTION OF SYMBOLS 1,3 ... Structure, 1A ... 1st surface of a structure, 1B ... 2nd surface of a structure, 2, 2 "... exterior member, 2A ... 1st of exterior member Surface, 2A '... extended portion of exterior member, 2B ... second surface of exterior member, 4 ... positive electrode, 4A ... positive electrode current collector, 4B ... positive electrode active material layer, 5 ... Negative electrode, 5A ... Negative electrode current collector, 5B ... Negative electrode active material layer, 6 ... Separator, 7 ... First exterior member, 7A ... 1A resin layer, 7B ... 1B resin layer, 7C ... 1st metal layer, 8 ... 2nd exterior member, 8A ... 2A resin layer, 8B ... 2B resin layer, 8C ... 2nd metal layer 8a ... outer edge, 9 ... recess, 10 ... exterior member, 11 ... adhesion film, 20 ... wound electrode body (structure), 21 ... positive electrode lead, 22 ...・ Negative lead, 23 ... Electrode, 23A ... positive electrode current collector, 23B ... positive electrode active material layer, 24 ... negative electrode, 24A ... negative electrode current collector, 24B ... negative electrode active material layer, 25 ... separator, 26 ... Electrolyte layer, 27 ... Protective tape, 31 ... Power source, 32 ... Positive electrode lead, 33 ... Negative electrode lead, 34A, 34B ... Tab, 35 ... Circuit board, 36 ... Lead wire with connector, 37 ... Adhesive tape, 38 ... Label, 39 ... Insulating sheet, 41 ... Control part, 42 ... Switch part, 43 ... PTC element, 44 ... Temperature detection unit, 44A ... Temperature detection element, 45A ... Positive electrode terminal, 45B ... Negative electrode terminal, 50 ... Case, 51 ... Control unit, 52 ... Memory, 53 ... Voltage detection unit, 54 ... Current measurement unit, 54A ... Current detection resistor, 5 ...... Temperature detection unit, 55A ... Temperature detection element, 56 ... Switch control unit, 57 ... Switch unit, 58 ... Power supply, 59A ... Positive terminal, 59B ... Negative terminal, 60 ... casing, 61 ... control unit, 62 ... various sensors, 63 ... power supply, 71 ... engine, 72 ... generator, 73, 74 ... inverter, 75 ..Motor, 76 ... differential device, 77 ... transmission, 78 ... clutch, 81 ... front wheel drive shaft, 82 ... front wheel, 83 ... rear wheel drive shaft, 84 ... rear wheel, 90 ... house, 91 ... control unit, 92 ... power supply, 93 ... smart meter, 94 ... power hub, 95 ... electrical equipment (electronic equipment), 96 ... Private generator, 97 ... Electric vehicle, 98 ... Centralized power system, 100 ... Tool body 101: Control unit 102: Power source 103 ... Drill unit 211 ... Positive electrode active material 212 ... Active material insulating layer 213 ... Negative electrode insulating layer 214 ... Separator insulation layers

Claims (20)

A secondary battery in which a structure in which a positive electrode, a separator, and a negative electrode are wound or stacked is housed in an exterior member and filled with an electrolyte,
The longitudinal direction of the structure is the X direction, the short direction of the structure is the Z direction, the thickness direction of the structure is the Y direction,
The outer surface along the XZ plane of the structure is the first surface of the structure and the second surface of the structure,
The inner surface of the exterior member facing the first surface of the structure is the first surface of the exterior member, the inner surface of the exterior member facing the second surface of the structure is the second surface of the exterior member,
When the dynamic friction coefficient of the first surface of the exterior member is μ ₁ and the dynamic friction coefficient of the second surface of the exterior member is μ ₂ ,
μ ₁ > μ ₂
Satisfying secondary battery.   The secondary battery according to claim 1, wherein the first surface of the exterior member is made of a material different from a material constituting the second surface of the exterior member.   The secondary battery according to claim 1, wherein the first surface of the exterior member is subjected to a surface treatment different from that of the second surface of the exterior member. A secondary battery in which a structure in which a positive electrode, a separator, and a negative electrode are wound or stacked is housed in an exterior member and filled with an electrolyte,
The longitudinal direction of the structure is the X direction, the short direction of the structure is the Z direction, the thickness direction of the structure is the Y direction,
The outer surface along the XZ plane of the structure is the first surface of the structure and the second surface of the structure,
When the inner surface of the exterior member facing the first surface of the structure is the first surface of the exterior member, and the inner surface of the exterior member facing the second surface of the structure is the second surface of the exterior member,
A secondary battery in which a first surface of the exterior member is subjected to a surface treatment different from that of the second surface of the exterior member.   The secondary battery according to claim 4, wherein the first surface of the exterior member is subjected to surface treatment, and the second surface of the exterior member is not subjected to surface treatment.   The secondary battery according to claim 4, wherein the first surface of the exterior member is made of the same material as that of the second surface of the exterior member.   The secondary battery according to claim 4, wherein the surface treatment is a roughening treatment.   The secondary battery according to claim 7, wherein the roughening treatment is chemical treatment, ultraviolet treatment, ozone treatment, or plasma treatment.   The secondary battery according to claim 8, wherein the chemical treatment is an etching treatment.   The secondary battery according to claim 7, wherein the roughening process is an embossing process.   The secondary battery according to claim 7, wherein the roughening process is a blasting process. A secondary battery in which a structure in which a positive electrode, a separator, and a negative electrode are wound or stacked is housed in an exterior member and filled with an electrolyte,
The longitudinal direction of the structure is the X direction, the short direction of the structure is the Z direction, the thickness direction of the structure is the Y direction,
The outer surface along the XZ plane of the structure is the first surface of the structure and the second surface of the structure,
When the inner surface of the exterior member facing the first surface of the structure is the first surface of the exterior member, and the inner surface of the exterior member facing the second surface of the structure is the second surface of the exterior member,
The combination of (material constituting the first surface of the exterior member, material constituting the second surface of the exterior member) is (polypropylene, nylon), (polypropylene, polyethylene), or (polyethylene, nylon). battery.   The secondary battery according to claim 1, 4 or 12, wherein the larger expansion amount when the structure is expanded by charging is the first surface of the structure, and the smaller expansion surface is the second surface of the structure. .   The secondary battery according to claim 1, claim 4, or claim 12, wherein when the battery is charged, the structure warps such that the first surface is convex. The secondary battery according to claim 1, claim 4, or claim 12, wherein a Young's modulus of the exterior member is 5 × 10 ⁸ Pa to 7 × 10 ⁹ Pa.   The secondary battery according to claim 1, claim 4, or claim 12, wherein the exterior member has a laminated structure of a first resin layer, a metal layer, and a second resin layer. A secondary battery in which a structure in which a positive electrode, a separator, and a negative electrode are wound or stacked is housed in an exterior member and filled with an electrolyte,
The exterior member is
A first exterior member, and
A second exterior member in which a recess for housing the structure is formed and an outer edge is fixed to the first exterior member;
Consisting of
A secondary battery in which a material constituting the first exterior member is different from a material constituting the second exterior member.   The secondary battery according to claim 17, wherein the first exterior member has a higher Young's modulus than the second exterior member. The first exterior member has a laminated structure of a first A resin layer, a first metal layer, and a first B resin layer,
The second exterior member has a laminated structure of a second A resin layer, a second metal layer, and a second B resin layer,
The first metal layer is made of stainless steel,
The light emitting device according to claim 17, wherein the second metal layer is made of aluminum or an aluminum alloy. The thickness of the first metal layer is 1 × 10 ⁻⁵ m to 1.8 × 10 ⁻⁴ m,
The light emitting device according to claim 19, wherein the thickness of the second metal layer is 5 x 10 ^-5 m to 2 x 10 ^-4 m.

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