WO2015166620A1

WO2015166620A1 - Battery, battery pack, battery module, electronic device, electric vehicle, electricity storage device and electric power system

Info

Publication number: WO2015166620A1
Application number: PCT/JP2015/001283
Authority: WO
Inventors: 雄一郎浅川; 卓誠坂本; 翔高橋
Original assignee: ソニー株式会社
Priority date: 2014-05-02
Filing date: 2015-03-10
Publication date: 2015-11-05

Abstract

This battery is provided with: a positive electrode; a negative electrode containing a negative electrode active material; and an electrolyte containing an electrolyte solution that contains a nonaqueous solvent, an electrolyte salt and an additive. The negative electrode active material contains a titanium-containing inorganic oxide that contains at least titanium and oxygen as constituent elements. The nonaqueous solvent contains a chain sulfone compound, a carbonate compound or a cyclic carboxylic acid ester compound. The additive contains a silane coupling agent and/or a siloxane compound.

Description

Batteries, battery packs, battery modules, electronic devices, electric vehicles, power storage devices, and power systems

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

In secondary batteries such as lithium ion secondary batteries, there is an increasing demand for higher performance, and it is required to improve battery characteristics such as high capacity and high output. As a negative electrode material used for the negative electrode of the secondary battery, a high potential negative electrode material such as lithium titanate (Li ₄ Ti ₅ O ₁₂ ) is used in addition to the carbon-based negative electrode material. In recent years, secondary batteries using high-potential negative electrode materials and the like have been actively developed.

The following Patent Documents 1 to 9 and Non-Patent Document 1 disclose technologies related to secondary batteries.

JP 2011-222450 A JP 2011-77029 A JP 2013-97993 A JP 2012-199145 A JP 2013-4215 A JP 2001-93583 A JP-A-11-288741 JP 2013-80714 A JP 2011-165998 A

The purpose of this technology is as follows.

Batteries are required to improve high-temperature cycle characteristics and suppress gas generation during high-temperature storage.

Accordingly, an object of the present technology is to provide a battery, a battery pack, a battery module, an electronic device, an electric vehicle, a power storage device, and a power system that can improve high-temperature cycle characteristics and suppress gas generation during high-temperature storage. .

Batteries are required to have operational stability over a wide temperature range that can withstand use in regions with large differences in temperature and in cold regions. Accordingly, there is a demand for improving low temperature characteristics and suppressing high temperature cycle characteristics and gas generation during high temperature storage.

Therefore, an object of the present technology is to provide a battery, a battery pack, a battery module, an electronic device, an electric vehicle, a power storage device, and a power system that can improve low temperature characteristics and suppress gas generation during high temperature storage.

Accordingly, an object of the present technology is to provide a battery, a battery pack, a battery module, an electronic device, an electric vehicle, a power storage device, and a power system that can improve high-temperature cycle characteristics and low-temperature characteristics and can suppress gas generation during high-temperature storage. There is.

In order to solve the above-described problem, the present technology includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and an electrolyte including an electrolyte solution containing a nonaqueous solvent, an electrolyte salt, and an additive. The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements, the non-aqueous solvent includes a chain sulfone compound, and the additive includes at least a silane coupling agent and a siloxane compound. It is a battery containing any one compound.

The present technology includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and an electrolyte including an electrolyte containing a nonaqueous solvent and an electrolyte salt, and the negative electrode active material includes at least titanium and oxygen as constituent elements. The negative electrode is a battery including a first compound derived from a silane coupling agent or a siloxane compound and a chain sulfone compound.

The present technology includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and an electrolyte including an electrolyte solution containing a nonaqueous solvent, an electrolyte salt, and an additive. The negative electrode active material includes at least titanium. The battery includes a titanium-containing inorganic oxide containing oxygen as a constituent element, the non-aqueous solvent includes a carbonate compound, and the additive includes at least one of a silane coupling agent and a siloxane compound.

The present technology includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and an electrolyte including an electrolyte containing a nonaqueous solvent and an electrolyte salt, and the negative electrode active material includes at least titanium and oxygen as constituent elements. The negative electrode is a battery including a third compound derived from a silane coupling agent or a siloxane compound and a carbonate compound.

The present technology includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and an electrolyte including an electrolyte solution containing a nonaqueous solvent, an electrolyte salt, and an additive. The negative electrode active material includes at least titanium. A titanium-containing inorganic oxide containing oxygen as a constituent element, the non-aqueous solvent contains a cyclic carboxylic acid ester compound, the electrolyte salt contains a fluorine-containing lithium salt containing at least fluorine, and the additive is silane The battery includes at least one of a coupling agent and a siloxane compound.

The present technology includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and an electrolyte including an electrolyte containing a nonaqueous solvent and an electrolyte salt, and the negative electrode active material includes at least titanium and oxygen as constituent elements. The negative electrode is a fourth compound derived from a silane coupling agent or a siloxane compound, and a fifth derived from a silane coupling agent or a siloxane compound and a cyclic carboxylic acid ester compound. A battery comprising at least one of the compounds.

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

According to the present technology, any of the following effects can be achieved.
According to the present technology, it is possible to improve the high temperature cycle characteristics and to suppress the generation of gas during high temperature storage.
According to the present technology, it is possible to improve the low temperature characteristics and to suppress the generation of gas during high temperature storage.
According to the present technology, it is possible to improve the high-temperature cycle characteristics and the low-temperature characteristics and to suppress the generation of gas during high-temperature storage.

FIG. 1 is a cross-sectional view illustrating a configuration example of a battery according to an embodiment of the present technology. FIG. 2 is an enlarged cross-sectional view of a part of the spirally wound electrode body in FIG. FIG. 3 is an exploded perspective view showing a configuration example of the battery according to the embodiment of the present technology. 4 is a cross-sectional view taken along the line II of the spirally wound electrode body in FIG. FIG. 5A is a perspective view showing the appearance of the battery of the present technology. FIG. 5B is a perspective exploded view showing a structural example of a battery. FIG. 5C is a perspective view showing a configuration example of the lower surface of the battery shown in FIG. 5A. 6A and 6B are perspective views showing a configuration of a battery unit using a battery of the present technology. FIG. 7 is an exploded perspective view showing a configuration of a battery unit using the battery of the present technology. FIG. 8 is an exploded perspective view showing a configuration of a battery module using the battery of the present technology. FIG. 9 is a perspective view illustrating a configuration of an application example of a battery (battery pack: single battery). FIG. 10 is a block diagram showing the configuration of the battery pack shown in FIG. FIG. 11 is a block diagram illustrating a circuit configuration example of the battery pack according to the embodiment of the present technology. FIG. 12 is a schematic diagram illustrating an example applied to a residential power storage system using the battery of the present technology. FIG. 13 is a schematic diagram schematically illustrating an example of a configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied.

<First Embodiment to Second Embodiment>
(Outline of this technology)
First, in order to facilitate understanding of the present technology, an outline of the present technology will be described. In Patent Document 1 (Japanese Patent Laid-Open No. 2011-222450) described above, it is proposed to suppress high-temperature deterioration by using a silane compound having a fluoro group when nickel or an iron-based compound is used for the positive electrode. Patent Document 1 describes that the electrolyte solution contains a sulfone compound. However, as in the example of Patent Document 1, 0 Vvs. When graphite or carbon having a reaction potential in the vicinity of Li / Li ⁺ is used for the negative electrode, as described in Non-Patent Document 1 (Journal of The Electrochemical Society, 149 7 A920-A926 2002), the sulfone compound Causes reductive decomposition, resulting in insufficient long-term reliability.

In addition, the technique of Patent Document 1 does not suggest any effect when the lithium titanium composite acid compound is used for the negative electrode. In contrast, in the present technology, the reaction potential is 1.55 Vvs. By using Li / Li ⁺ and a sufficiently high lithium-titanium complex acid compound for the negative electrode, a sufficient long life can be obtained even when chain-like sulfone is used.

In Patent Document 2 (Japanese Patent Application Laid-Open No. 2011-77029), by containing a phosphate ester in an electrolyte, a reaction at a high temperature is suppressed, and a decomposition reaction at a high temperature storage or a high temperature charge / discharge is suppressed. It has been proposed to obtain internal resistance and high electrical capacity.

However, the thing of patent document 2 uses the carbon material and carboxylic acid compound with high crystallinity for a negative electrode, and what is suggested about the effect at the time of using a lithium titanium complex acid compound for a negative electrode is suggested. Absent.

Hereinafter, embodiments of the present technology will be described with reference to the drawings. The description will be given in the following order.
1. First embodiment (example of cylindrical battery)
2. Second Embodiment (Example of laminated film type battery)
The embodiments described below are suitable specific examples of the present technology, and the contents of the present technology are not limited to these embodiments. Moreover, the effect described in this specification is an illustration to the last, is not limited, and does not deny that the effect different from the illustrated effect exists.

1. First Embodiment (1-1) Battery Configuration A battery according to a first embodiment of the present technology will be described with reference to FIGS. 1 and 2. FIG. 1 shows a cross-sectional configuration of a battery according to the first embodiment of the present technology. FIG. 2 shows an enlarged part of the spirally wound electrode body 20 shown in FIG. This battery is a secondary battery that can be charged and discharged, for example, a non-aqueous electrolyte battery, for example, a lithium ion secondary battery, and the like.

This non-aqueous electrolyte battery mainly includes a wound electrode body 20 in which a positive electrode 21 and a negative electrode 22 are laminated and wound through a separator 23 inside a substantially hollow cylindrical battery can 11, and a pair of insulations. The plates 12 and 13 are accommodated. The battery structure using the cylindrical battery can 11 is called a cylindrical type.

The battery can 11 has, for example, a hollow structure in which one end is closed and the other end is opened, and is made of iron (Fe), aluminum (Al), or an alloy thereof. In the case where the battery can 11 is made of iron, for example, nickel (Ni) or the like may be plated on the surface of the battery can 11. The pair of insulating plates 12 and 13 are arranged so as to sandwich the wound electrode body 20 from above and below and to extend perpendicularly to the wound peripheral surface.

A battery lid 14, a safety valve mechanism 15, and a heat sensitive resistance element (Positive Temperature Coefficient: PTC element) 16 are caulked through a gasket 17 at the open end of the battery can 11, and the battery can 11 is sealed. ing. The battery lid 14 is made of, for example, the same material as the battery can 11. The safety valve mechanism 15 and the thermal resistance element 16 are provided inside the battery lid 14. The safety valve mechanism 15 is electrically connected to the battery lid 14 via the heat sensitive resistance element 16. In the safety valve mechanism 15, when the internal pressure becomes a certain level or more due to an internal short circuit or external heating, the disk plate 15 </ b> A is reversed and the electric power between the battery lid 14 and the wound electrode body 20 is reversed. Connection is cut off. The heat-sensitive resistance element 16 prevents abnormal heat generation caused by a large current by increasing resistance (limiting current) as the temperature rises. The gasket 17 is made of, for example, an insulating material, and for example, asphalt is applied to the surface thereof.

(Wound electrode body)
The wound electrode body 20 is obtained by laminating and winding a positive electrode 21 and a negative electrode 22 via a separator 23. A center pin 24 may be inserted in the center of the wound electrode body 20. In the wound electrode body 20, a positive electrode lead 25 made of aluminum or the like is connected to the positive electrode 21, and a negative electrode lead 26 made of nickel or the like is connected to the negative electrode 22. The positive electrode lead 25 is welded to the safety valve mechanism 15 and electrically connected to the battery lid 14, and the negative electrode lead 26 is welded to the battery can 11 and electrically connected thereto.

(Positive electrode)
For example, the positive electrode 21 is obtained by providing a positive electrode active material layer 21B on both surfaces of a positive electrode current collector 21A having a pair of surfaces. In addition, although illustration is abbreviate | omitted, the positive electrode 21 may have the area | region where the positive electrode active material layer 21B was provided only in the single side | surface of 21 A of positive electrode collectors.

The positive electrode current collector 21A is made of, for example, a metal material such as aluminum, nickel, or stainless steel.

The positive electrode active material layer 21 </ b> B contains one or more positive electrode materials capable of inserting and extracting lithium as a positive electrode active material. The positive electrode active material layer 21 </ b> B may contain other materials such as a binder and / or a conductive agent as necessary.

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

(Phosphate compounds containing lithium and transition metal elements)
As a phosphoric acid compound containing lithium and a transition metal element, for example, a lithium iron phosphate compound having an olivine structure containing at least lithium, phosphorus (P) and iron (Fe), lithium, phosphorus (P) and manganese ( And a lithium manganese phosphate compound having an olivine structure containing at least Mn). The lithium iron phosphate compound having an olivine structure, lithium iron phosphate compound (LiFePO _4), or lithium iron composite phosphate compound containing the different element _{_{(LiFe x M 1-x O}} 4: M is other than iron 1 or more types of metal elements, x is 0 <x <1, etc.). In addition, as said M, a transition element, a IIA group element, a IIIA group element, a IIIB group element, a IVB group element etc. are mentioned. In particular, M is at least one of cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), aluminum (Al), vanadium (V), and titanium (Ti) as a transition metal element. Is preferred. Examples of the lithium manganese phosphate compound having an olivine structure include a lithium manganese phosphate compound (LiMnPO ₄ ).

A typical example of the lithium iron phosphate compound having an olivine structure is a lithium phosphate compound represented by (Chemical Formula 1).
(Chemical formula 1)
_{_{_{Li u Fe r M1 (1-}}} r) PO 4
(In the formula, M1 is cobalt (Co), manganese (Mn), 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), at least one selected from the group consisting of r. , 0 <r ≦ 1, and u is a value within the range of 0.9 ≦ u ≦ 1.1 Note that the composition of lithium varies depending on the state of charge and discharge, and the value of u Represents the value in the fully discharged state.)

As the lithium phosphate compound represented by (Chemical Formula 1), typically, for example, Li _u FePO ₄ (u is as defined above), Li _u Fe _r Mn _(1-r) PO ₄ (u Is as defined above, and r is as defined above.

(Composite oxide containing lithium and transition metal element)
Examples of the composite oxide containing lithium and a transition metal element include lithium cobalt composite oxide (Li _x CoO ₂ ), lithium nickel composite oxide (Li _x NiO ₂ ), and lithium nickel cobalt composite oxide (Li _x Ni). _1-z Co _z O ₂ (z <1)), lithium nickel cobalt manganese composite oxide (Li _x Ni _(1-vw) Co _v Mn _w O ₂ (v + w <1)) and other lithium transitions having a layered structure Examples thereof include metal composite oxides, lithium manganese composite oxides having a spinel structure and containing at least lithium and manganese.

Examples of the spinel structure lithium manganese composite oxide include a lithium composite oxide represented by (Chemical Formula 2).
(Chemical formula 2)
Li _v Mn _(2-w) M2 _w O _s
(In the formula, M2 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), at least one selected from the group consisting of v, w and s are values within the range of 0.9 ≦ v ≦ 1.1, 0 ≦ w ≦ 0.6, 3.7 ≦ s ≦ 4.1, where the composition of lithium is the state of charge and discharge. And the value of v represents a value in a fully discharged state.)

Specifically, as the lithium composite oxide represented by (Chemical Formula 2), for example, Li _v Mn ₂ O ₄ (v is as defined above), lithium manganese nickel composite oxide (LiMn _2−t Ni _t O ₄ (t <2)) and the like.

The positive electrode material may be one in which a coating layer is formed on at least a part of the surface of the core particle made of the lithium-containing compound described above. The coating layer is provided on at least a part of the surface of the core particle of the lithium-containing compound as the base material, and has a composition element or composition ratio different from that of the lithium-containing compound particle as the base material. . For example, as the positive electrode material, another lithium-containing compound (for example, Ni, Mn, Li) is formed on the surface of the core particle made of any of the lithium-containing compounds from the viewpoint that higher electrode filling properties and cycle characteristics can be obtained. And a coating layer containing a phosphate compound (for example, lithium phosphate) may be formed. The covering layer may be a carbon material or the like.

In addition, examples of positive electrode materials capable of inserting and extracting lithium include oxides such as titanium oxide, vanadium oxide and manganese dioxide, disulfides such as titanium disulfide and molybdenum sulfide, and niobium selenide. And chalcogenides such as sulfur, polyaniline or polythiophene, and other conductive polymers.

(Conductive agent)
Examples of the conductive agent include carbon black produced by furnace method, acetylene method, contact method, thermal method, etc., carbon materials such as vapor-grown carbon, activated carbon, activated carbon fiber cloth, single wall or multi-wall carbon nanotube, carbon nanohorn, etc. In addition, those obtained by surface modification of these carbon materials by acid / alkali treatment or the like, or those obtained by physically or chemically bonding other elements can be used.

(Binder)
Examples of the binder include resin materials such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), styrene butadiene rubber (SBR), and carboxymethyl cellulose (CMC), and these resins. At least one selected from a copolymer mainly composed of materials is used.

(Negative electrode)
In the negative electrode 22, for example, a negative electrode active material layer 22B is provided on both surfaces of a negative electrode current collector 22A having a pair of surfaces. Although illustration is omitted, the negative electrode 22 may have a region where the negative electrode active material layer 22B is provided only on one surface of the negative electrode current collector 22A.

The negative electrode current collector 22A is made of a metal material such as aluminum foil, copper, nickel, or stainless steel, for example.

The negative electrode active material layer 22B contains one or more negative electrode materials capable of inserting and extracting lithium as a negative electrode active material. The negative electrode active material layer 22B may contain other materials such as at least one of a binder and a conductive agent as necessary. Note that the same binder and conductive agent as those described for the positive electrode can be used.

(Negative electrode active material)
As a negative electrode material capable of inserting and extracting lithium, for example, a titanium-containing inorganic oxide containing at least titanium (Ti) and oxygen (O) as constituent elements, or a metal sulfide can be used. . As the negative electrode material capable of inserting and extracting lithium, for example, the reaction potential of the negative electrode is 1.0 Vvs. More than Li / Li ⁺ , preferably 1.0 Vvs. Li / Li ⁺ more than 1.9Vvs. The material etc. which become Li / Li ⁺ or less are preferable.

Examples of the titanium-containing inorganic oxide include composite oxides having at least lithium and titanium as constituent elements (referred to as titanium-containing lithium composite oxides), and metal oxides having titanium and oxygen as constituent elements (referred to as titanium oxides). Etc. Among these, titanium-containing lithium composite oxide or titanium oxide is preferable.

As the titanium-containing lithium composite oxide, typically, for example, Li _x Ti _y O _z having a spinel structure (x represents a composition ratio of Li, y represents a composition ratio of Ti, and z represents a composition of O). A compound (lithium titanate) represented by the following formula: x> 0, y> 0, z> 0).

Specific examples of Li _x Ti _y O _z having a spinel structure include Li ₄ Ti ₅ O ₁₂ . The potential (V vs. Li / Li ⁺ ) for occluding and releasing lithium ions of Li _x Ti _y O _z having a spinel structure is, for example, about 1.55 V in the flat portion in the potential change pattern during charge / discharge of the battery. It is. Note that Li in Li _x Ti _y O _z may be Na, K, or the like.

As a titanium-containing lithium composite oxide, in addition, from the viewpoint that higher potential flatness and rate characteristics can be obtained, some of the constituent elements lithium, titanium, and oxygen are replaced with other elements such as Al and Mg. A substituted one may be used.

Examples of other elements that substitute a part of titanium include metal elements and metalloid elements capable of forming an alloy with lithium. Specifically, magnesium (Mg), boron (B), aluminum (Al), gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), Examples thereof include bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd), and platinum (Pt).

Typical examples of the titanium-containing lithium composite oxide in which a part of lithium, titanium, and oxygen are substituted with other elements include Li _3.75 Ti _4.875 Mg _0.375 O ₁₂ , Li _3.75 Ti _4.50 Al _0.75 O _{12, and the} like. Is mentioned.

(Titanium oxide)
The titanium oxide (which is p> 0, q> 0. ) Ti p O q a compound represented by (titanium oxide) and the like. Specific examples of this compound include TiO _{2 and the} like. The TiO ₂ may be any of anatase TiO ₂ [TiO ₂ (anatase)], rutile TiO ₂ [TiO ₂ (rutile)], B-type TiO ₂ [TiO ₂ (B)], and the like.

In addition, the titanium-containing inorganic oxide such as the titanium-containing lithium composite oxide may be coated with carbon. For example, by using a chemical vapor deposition (CVD) method or the like, hydrocarbons are decomposed and a carbon film is grown on the surface of the titanium-containing lithium composite oxide, whereby a titanium-containing inorganic oxide coated with carbon is obtained. Obtainable. The carbon coating method is not limited to the above.

The negative electrode 22 contains a compound derived from a chain sulfone compound and a silane coupling agent or a siloxane compound (hereinafter sometimes referred to as a silane / siloxane compound) contained in an electrolyte solution described later. The negative electrode 22 may further include a compound derived from a chain sulfone compound.

For example, the negative electrode 22 includes at least one disulfide compound having a disulfide bond (—SS—) represented by the formula (1) as a compound derived from a chain sulfone compound and a silane / siloxane compound. ing. The negative electrode 22 includes at least one disulfide compound having a disulfide bond (—SS—) represented by the formula (1) and a sulfonyl bond (—S (═O) ₂ represented by the formula (2). At least one of sulfonyl compounds having-) may be included. For example, at least one disulfide compound represented by the formula (1) and at least one sulfonyl compound represented by the formula (2) are typically active in the negative electrode active material layer 22B during charge / discharge. It is contained in a film formed on the surface of the substance particles. Side reactions can be suppressed by wrapping the active site of the negative electrode 22 with the coating. As a result, it is possible to suppress gas generation and improve cycle characteristics in a high temperature environment.

(In the formula, n is an integer of 1 to 8. R1, R2, R3 and R4 each independently represents a halogen group, an alkyl group, a halogenated alkyl group, an alkoxy group or a siloxane group.)

(In the formula, R5 is a halogen group, an alkyl group, a halogenated alkyl group or an alkoxy group. R6 is H or Li.)

In this technology, compared to a carbon-based negative electrode active material such as graphite, a negative electrode material in which the reaction potential of the negative electrode becomes a noble potential is used as the negative electrode active material. When a carbon-based negative electrode active material having a low negative electrode reaction potential is used, a solvent that decomposes and is not effective can be used effectively.

Examples of the disulfide compound represented by the formula (1) include compounds represented by the following formulas (1-1) to (1-25). Among these, from the viewpoint of battery characteristics, a compound represented by the formula (1-2) and a compound represented by the formula (1-4) are preferable.

Examples of the sulfonyl compound represented by the formula (2) include compounds represented by the following formulas (2-1) to (2-8). Among these, from the viewpoint of battery characteristics, a compound represented by the formula (2-2) and a compound represented by the formula (2-4) are preferable.

The negative electrode containing at least one compound represented by the formula (1) includes, for example, one produced from a silane / siloxane compound and a chain sulfone compound contained in the electrolytic solution impregnated in the negative electrode It is. The negative electrode containing at least one of the compounds represented by (2) includes, for example, one produced from a decomposition product of a chain sulfone compound contained in the electrolyte solution impregnated in the negative electrode.

The compound represented by the formula (1) is derived from a silane / siloxane compound and a chain sulfone compound. Typically, for example, it is produced by a reaction between a silane / siloxane compound and a decomposition product of a chain sulfone compound at the time of charge / discharge of the battery. The silane-siloxane compound is typically a silane coupling agent having a mercapto group (—SH), for example. The compound represented by the formula (2) is derived from a chain sulfone compound. Typically, for example, a decomposition product produced by the decomposition of a chain sulfone compound.

In order to confirm the compounds derived from the chain sulfone compound and the silane / siloxane compound and the compound derived from the chain sulfone compound formed in the battery such as in the negative electrode, for example, the battery is disassembled and the negative electrode is removed. After the electrode body including the electrode body is taken out, the formation ratio of the active material surface may be analyzed by observing the element distribution by an existing elemental analysis method, that is, energy dispersive X-ray spectroscopy (SEM-EDX). When using this method, in order to prevent unintentional analysis of unnecessary components in the electrolyte, the electrode surface may be washed after being washed with an organic solvent such as dimethyl carbonate (DMC). preferable.

In addition, the washed extract of the electrode body taken out was subjected to existing structural analysis methods, that is, infrared spectroscopy (IR), nuclear magnetic resonance (1H / 13C-NMR), gas or liquid chromatography mass spectrometry (GC / The formation ratio of each compound may be analyzed by analyzing the structure of the compound contained by LC-MS) or the like. Even when this method is used, the surface of the electrode is washed with an organic solvent such as dimethyl carbonate (DMC) in order to prevent unintentional analysis of unnecessary components in the electrolyte, and then each compound is extracted. And analyzing.

(Content of the compound represented by the formula (1))
By making content of the compound represented by Formula (1) into a predetermined range, the surface of the negative electrode active material can be more effectively coated while maintaining characteristics such as battery capacity. The compound represented by the formula (1) may be contained in the negative electrode and also in the electrolytic solution. The preferable content of the compound represented by the formula (1) is defined by the content of the compound represented by the formula (1) in the electrolytic solution. As content of the compound represented by Formula (1), it is preferable that it is 0.05 mass% or more and 0.5 mass% or less with respect to the mass of electrolyte solution from a viewpoint from which the more outstanding effect is acquired. .

The compound in the electrolytic solution can be confirmed by applying the disassembled battery to a centrifuge and analyzing the extracted electrolytic solution. Specifically, NMR (Nuclear magnetic resonance), IR (infrared absorption absorption spectrometry), Raman (Raman spectroscopy), GC-MS (Gas chromatography, mass spectrometry, LC-MS (Liquid chromatography, Mass spectrometry), etc. can be used. it can.

(Separator)
The separator 23 is a porous film composed of an insulating film having a high ion permeability and a predetermined mechanical strength. The separator 23 is impregnated with an electrolytic solution that is a liquid electrolyte. The electrolyte solution is held in the pores of the separator 23.

For example, a polyolefin resin such as polypropylene or polyethylene, an acrylic resin, a styrene resin, a polyester resin, or a nylon resin is preferably used as the resin material constituting the separator 23. In particular, polyethylene such as low density polyethylene, high density polyethylene and linear polyethylene, or their low molecular weight wax content, or polyolefin resin such as polypropylene is suitable because it has an appropriate melting temperature and is easily available. Moreover, it is good also as a porous film formed by melt-kneading the structure which laminated | stacked these 2 or more types of porous films, or 2 or more types of resin materials. A material including a porous film made of a polyolefin resin is excellent in separability between the positive electrode 21 and the negative electrode 22 and can further reduce a decrease in internal short circuit. Moreover, it is preferable to use a nonwoven fabric as the separator 23. Nonwoven fabrics have the feature that it is easy to ensure a sufficient pore diameter that is optimal for the permeation of Li ions, and high input / output can be obtained as a battery.

The thickness of the separator 23 can be arbitrarily set as long as it is equal to or greater than the thickness that can maintain the required strength. The separator 23 insulates between the positive electrode 21 and the negative electrode 22 to prevent a short circuit and the like, and has ion permeability for suitably performing a battery reaction via the separator 23, and the battery reaction in the battery. It is preferable to set the thickness so that the volumetric efficiency of the active material layer that contributes to the maximum can be increased.

(Electrolyte)
The electrolytic solution (nonaqueous electrolytic solution) includes an electrolyte salt, a nonaqueous solvent that dissolves the electrolyte salt, and a silane coupling agent or a siloxane compound as an additive. The electrolytic solution may contain both a silane coupling agent and a siloxane compound as additives.

(Non-aqueous solvent)
As the non-aqueous solvent, a solvent containing a main solvent and a chain sulfone compound is used.

(Main solvent)
As main solvents included in the present technology, cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC), chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC), Unsaturated carbonates having unsaturated bonds such as carbon-carbon double bonds such as vinylethylene carbonate (VC), 4-fluoro-1,3-dioxolan-2-one (FEC; fluoroethylene carbonate), 4,5 Halogenated carbonates such as difluoro-1,3-dioxolan-2-one (DFEC; difluoroethylene carbonate), 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), 2-methyltetrahydrofuran (Me-THF), 1,3-Geo Solan (DOL), 4-methyl-1,3-dioxolane (Me-DOL), diethyl ether (DEE), γ-butyrolactone (GBL), γ-valerolactone (GVL), 3-methyloxazolidinone (MOX), methyl formate (MF) ), Sulfolane (SL), 3-methylsulfolane (3MS), dimethyl sulfoxide (DMSO), acetonitrile (AN), dimethyl sulfoxide (DMSO), trimethyl phosphate (TMP), propionitrile (PN), glutaronitrile ( GLN), adiponitrile (ADN), methoxyacetonitrile (MAN), 3-methoxypropionitrile (MPN), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), N-methylpyrrolidinone ( NMP), N Methyl oxazolidinone (NMO), N, N'- dimethyl-imidazolidinone (DMI), nitromethane (NM), nitroethane (NE), and the like.

Among these, a chain carbonate and a cyclic carbonate, or a chain carboxylic acid ester and a cyclic carboxylic acid ester are preferable because they have various characteristics in a non-aqueous electrolyte secondary battery. Among these, ethylene carbonate and propylene carbonate are preferable. Dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone are more preferable, and ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and γ-butyrolactone are further included. preferable.

(Chain sulfone compound)
The electrolytic solution contains a chain sulfone compound as a solvent. The chain sulfone compound refers to a compound having a chain structure and having a sulfonyl group (—S (═O) ₂ —). Examples of chain sulfone compounds include dimethylsulfone [formula (3-1)], diethylsulfone [formula (3-2)], ethylmethylsulfone [formula (3-3)], methylisopropylsulfone [formula (3) -4)], ethyl isopropyl sulfone [formula (3-5)], ethyl isobutyl sulfone [formula (3-6)], isopropyl isobutyl sulfone [formula (3-7)], isopropyl s-butyl sulfone [formula (3 -8)] and butyl isobutyl sulfone [formula (3-9)] are preferred. Among these, ethyl isopropyl sulfone (formula (3-5); EiPS) is most preferable from the viewpoint of battery characteristics.

By containing a chain sulfone compound as a solvent in the electrolytic solution, a film containing a compound derived from the chain sulfone compound at the time of charge / discharge can be formed on the negative electrode using the titanium-containing inorganic oxide. Further, since the electrolytic solution further contains a silane / siloxane compound as an additive, a coating derived from the silane / siloxane compound and the chain sulfone compound can be formed on the negative electrode using the titanium-containing inorganic oxide. it can.

(Content)
Although content of the chain | strand-shaped sulfone compound in electrolyte solution is not specifically limited, 0.1 to 20 mass% is preferable with respect to the mass of electrolyte solution, and 0.3 to 8 mass% is preferable. More preferably, 0.5 mass% or more and 5 mass% or less is the most preferable. Within this range, the amount of gas generated from the carbonate, which is a solvent, is further reduced, and more excellent battery characteristics are exhibited at low and high temperatures.

(Additive)
The electrolytic solution contains a silane coupling agent or a siloxane compound (silane / siloxane compound) as an additive. The electrolytic solution may contain both a silane coupling agent and a siloxane compound. By containing the silane / siloxane compound in the electrolytic solution, at least one of the silane / siloxane compound and the compound derived from the silane / siloxane compound also has an effect of covering the active surface of the electrode active material, and the electrolytic solution is decomposed. Side reactions can be effectively suppressed, and a battery with high long-term reliability can be provided. Furthermore, when the electrolytic solution contains a silane / siloxane compound, it is possible to further improve the impregnation of the electrolytic solution into the electrode, and to obtain a more excellent effect that a high capacity can be expressed even in a low temperature environment. Can do.

(Silane coupling agent or siloxane compound)
As the silane coupling agent, for example, a silane coupling agent having a mercapto group (—SH), another silane coupling agent, or the like can be used. Examples of silane coupling agents having a mercapto group (—SH) include 3-mercaptopropyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ SH], 3-mercaptopropylmethyldimethoxysilane [(CH ₃ ). (CH ₃ O) ₂ Si (CH ₂ ) ₃ SH], 3-mercaptopropyldimethylmethoxysilane [(CH ₃ ) ₂ (CH ₃ O) Si (CH ₂ ) ₃ SH], 3-mercaptopropyltrimethylsilane [( CH ₃ ) ₃ ) Si (CH ₂ ) ₃ SH] and the like.

Other silane coupling agents include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) ) -3-Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxy Silyl-N- (1,3-dimethylbutylidene) propylamine, vinyltris (2-methoxyethoxy) silane, vinyltristrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropi Triethoxysilane, methyl triethoxysilane, methyl trimethoxysilane, phenyl triethoxysilane, and phenyl trimethoxysilane.

Examples of the siloxane compound include decamethylcyclopentanesiloxane, decamethyltetrasiloxane, octamethylcyclotetrasiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, hexamethyldisiloxane and the like.

Incidentally, a silane coupling agent, those having a structure _{_{_{[R x -Si (R y) n}}} (OR z) 3-n R x reactive functional group, R _y: hydrolyzable group: organic group, OR _z] If so, it is not limited to these. The siloxane compound is not limited to these as long as it has a siloxane structure. Further, the series of silane / siloxane compounds described above may be one kind, or two or more kinds may be mixed in any combination. Among these silane / siloxane compounds, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyltrimethylsilane, hexamethylcyclotrisiloxane, etc. are battery characteristics. From the viewpoint of obtaining

(Electrolyte salt)
Examples of the electrolyte salt contained in the electrolytic solution include lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium perchlorate (LiClO ₄ ), lithium hexafluoroarsenate ( LiAsF ₆ ), lithium tetraphenylborate (LiB (C ₆ H ₅ ) ₄ ), lithium methanesulfonate (LiCH ₃ SO ₃ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), lithium bis (fluorosulfonyl) imide (LiN (SO ₂ F) ₂ ), lithium (fluorosulfonyl) (trifluoromethylsulfonyl) imide (LiN (SO ₂ F) (SO ₂ CF ₃ )), lithium bis (trifluoromethylsulfonyl) imide (LiN (SO ₂ CF ₃₎ _2), lithium bis (oxalato) borate (LiC ₄ BO _8), Richiumujifu Oro like oxa Ratn borate (LiC _₂ BO ₄ F ₂₎ and the like.

These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio. Among these, at least one of the group consisting of lithium hexafluorophosphate (LiPF ₆ ) and lithium tetrafluoroborate (LiBF ₄ ) is preferable, and lithium tetrafluoroborate (LiBF ₄ ), lithium bis (Fluorosulfonyl) imide (LiN (SO ₂ F) ₂ ), lithium bis (trifluoromethanesulfonyl) imide (LiN (SO ₂ CF ₃ ) ₂ ), and lithium bis (oxalato) boric acid (LiC ₂ BO ₄ F ₂ ) It is more preferable to contain.

The concentration of the lithium salt in the electrolytic solution is not particularly limited, but is usually 0.5 mol / L or more, preferably 0.6 mol / L or more, more preferably 0.7 mol / L or more. Moreover, the upper limit is 2 mol / L or less normally, Preferably it is 1.8 mol / L or less, More preferably, it is 1.7 mol / L or less. If the concentration is too low, the electrical conductivity of the non-aqueous electrolyte may be insufficient. On the other hand, if the concentration is too high, the electrical conductivity may decrease due to an increase in viscosity, and the performance of the battery decreases. There is a case.

(1-2) Battery Manufacturing Method This nonaqueous electrolyte battery is manufactured, for example, by the following manufacturing method.

(Manufacture of positive electrode)
First, the positive electrode 21 is produced. First, a positive electrode material, a binder, and a conductive agent are mixed to obtain a positive electrode mixture, which is then dispersed in an organic solvent to obtain a paste-like positive electrode mixture slurry. Subsequently, the positive electrode mixture slurry is uniformly applied to both surfaces of the positive electrode current collector 21A by a doctor blade or a bar coater and dried. Finally, the positive electrode active material layer 21B is formed by compressing and molding the coating film with a roll press or the like while heating as necessary. In this case, compression molding may be repeated a plurality of times.

(Manufacture of negative electrode)
Next, the negative electrode 22 is produced. First, a negative electrode material, a binder, and a conductive agent as necessary are mixed to form a negative electrode mixture, which is then dispersed in an organic solvent to obtain a paste-like negative electrode mixture slurry. Subsequently, the negative electrode mixture slurry is uniformly applied to both surfaces of the negative electrode current collector 22A by a doctor blade or a bar coater and dried. Finally, the negative electrode active material layer 22B is formed by compression molding the coating film with a roll press or the like while heating as necessary.

(Preparation of electrolyte)
The above-described electrolytic solution is prepared. The electrolyte 22 is impregnated into the negative electrode 22 to form a compound derived from the chain sulfone compound and a compound derived from the chain sulfone compound and the silane / siloxane compound during charging and discharging of the battery. More specifically, for example, when the battery is charged and discharged, a decomposition product of the chain sulfone compound and a reaction product of the decomposition product of the chain sulfone compound and the silane / siloxane compound are formed.

More specifically, at the time of charge / discharge of the battery, for example, the compound represented by the formula (1) as the above reaction product and the compound represented by the formula (2) as the above decomposition product are formed, These compounds can be contained in the negative electrode 22. In addition, as a method of making the negative electrode 22 contain the compound represented by Formula (1) and the compound represented by Formula (2), various methods can be taken. For example, when forming the negative electrode active material layer 22B, a negative electrode mixture is prepared by mixing a compound represented by the formula (1) and a compound represented by the formula (2) with a negative electrode material or the like. Thus, the compounds represented by formula (1) and formula (2) may be contained in the negative electrode. Moreover, you may make it make the negative electrode 22 contain only the compound represented by Formula (1).

(Battery assembly)
The non-aqueous electrolyte battery is assembled as follows. First, the positive electrode lead 25 is attached to the positive electrode current collector 21A by welding or the like, and the negative electrode lead 26 is attached to the negative electrode current collector 22A by welding or the like. Subsequently, after the positive electrode 21 and the negative electrode 22 are stacked and wound through the separator 23 to produce the wound electrode body 20, the center pin 24 is inserted into the winding center. Subsequently, the wound electrode body 20 is housed in the battery can 11 while being sandwiched between the pair of insulating plates 12 and 13, and the tip of the positive electrode lead 25 is welded to the safety valve mechanism 15, and the tip of the negative electrode lead 26 is attached to the tip of the negative electrode lead 26. Weld to battery can 11.

Subsequently, the electrolytic solution described above is injected into the battery can 11 and impregnated in the separator 23 and the like. Finally, the battery lid 14, the safety valve mechanism 15, and the heat sensitive resistance element 16 are fixed to the opening end of the battery can 11 by caulking through the gasket 17. Thereby, the nonaqueous electrolyte battery shown in FIGS. 1 and 2 is completed.

2. Second Embodiment (2-1) Battery Configuration A nonaqueous electrolyte battery (battery) according to a second embodiment of the present technology will be described. FIG. 3 illustrates an exploded perspective configuration of the nonaqueous electrolyte battery according to the second embodiment of the present technology, and FIG. 4 is an enlarged cross-sectional view taken along line II of the spirally wound electrode body 30 illustrated in FIG. It shows.

This non-aqueous electrolyte battery is mainly one in which a wound electrode body 30 to which a positive electrode lead 31 and a negative electrode lead 32 are attached is housed in a film-shaped exterior member 40. The battery structure using the film-shaped exterior member 40 is called a laminate film type. This nonaqueous electrolyte battery is, for example, a secondary battery that can be charged and discharged, and is, for example, a lithium ion secondary battery.

The positive electrode lead 31 and the negative electrode lead 32 are led out in the same direction from the inside of the exterior member 40 to the outside, for example. The positive electrode lead 31 is made of, for example, a metal material such as aluminum, and the negative electrode lead 32 is made of, for example, a metal material such as copper, nickel, or stainless steel. These metal materials are, for example, in a thin plate shape or a mesh shape.

The exterior member 40 has a configuration in which resin layers are provided on both surfaces of a metal layer made of metal foil, such as an aluminum laminate film in which a nylon film, an aluminum foil, and a polyethylene film are bonded in this order. The general structure of the exterior member 40 has, for example, a laminated structure of an outer resin layer / a metal layer / an inner resin layer. For example, the exterior member 40 has a structure in which the outer edges of two rectangular aluminum laminate films are bonded to each other by fusion or an adhesive so that the inner resin layer faces the wound electrode body 30. Have. Each of the outer resin layer and the inner resin layer may be composed of a plurality of layers.

The metal material constituting the metal layer only needs to have a function as a moisture-permeable barrier film, and includes aluminum (Al) foil, stainless steel (SUS) foil, nickel (Ni) foil, and plated iron ( Fe) foil or the like can be used. Especially, it is preferable to use the aluminum foil which is thin and lightweight and excellent in workability. In particular, from the viewpoint of workability, for example, annealed aluminum (JIS A8021P-O), (JIS A8079P-O), or (JIS A1N30-O) is preferably used.

The thickness of the metal layer is typically preferably 30 μm or more and 150 μm or less, for example. When the thickness is less than 30 μm, the material strength tends to decrease. Moreover, when it exceeds 150 micrometers, while processing becomes remarkably difficult, the thickness of a laminate film will increase and it exists in the tendency for the volumetric efficiency of a nonaqueous electrolyte battery to reduce.

The inner resin layer is a part that is melted by heat and fused to each other, such as polyethylene (PE), non-axially oriented polypropylene (CPP), polyethylene terephthalate (PET), low density polyethylene (LDPE), high density polyethylene (HDPE), Linear low density polyethylene (LLDPE) or the like can be used, and a plurality of these can be selected and used.

As the outer resin layer, polyolefin resin, polyamide resin, polyimide resin, polyester, or the like is used because of its beautiful appearance, toughness, flexibility, and the like. Specifically, nylon (Ny), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polybutylene naphthalate (PBN) are used. Is also possible.

An adhesion film 41 is inserted between the exterior member 40 and the positive electrode lead 31 and the negative electrode lead 32 to prevent intrusion of outside air. The adhesion film 41 is made of a material having adhesion to the positive electrode lead 31 and the negative electrode lead 32. Examples of such a material include polyolefin resins such as polyethylene, polypropylene, modified polyethylene, and modified polypropylene.

The exterior member 40 may be constituted by a laminated film having another laminated structure instead of the aluminum laminated film having the laminated structure described above, or may be constituted by a polymer film such as polypropylene or a metal film. It may be.

FIG. 4 shows a cross-sectional configuration along the II line of the spirally wound electrode body shown in FIG. This wound electrode body 30 is formed by laminating and winding a belt-like positive electrode 33 and a belt-like negative electrode 34 via a belt-like separator 35 and an electrolyte 36, and the outermost periphery is protected by a protective tape 37. Has been.

(Positive electrode)
The positive electrode 33 has, for example, a structure in which a positive electrode active material layer 33B is provided on both surfaces of a positive electrode current collector 33A having a pair of surfaces. Although not shown, the positive electrode 33 may have a region where the positive electrode active material layer 33B is formed only on one surface of the positive electrode current collector 33A. The positive electrode current collector 33A and the positive electrode active material layer 33B are the same as the positive electrode current collector 21A and the positive electrode active material layer 21B in the first embodiment, respectively.

(Negative electrode)
The negative electrode 34 has, for example, a structure in which a positive electrode active material layer 33B is provided on both surfaces of a negative electrode current collector 34A having a pair of surfaces. Although not shown, the negative electrode 34 may have a region where the negative electrode active material layer 34B is formed only on one surface of the negative electrode current collector 34A. The negative electrode current collector 34A and the negative electrode active material layer 34B are the same as the negative electrode current collector 22A and the negative electrode active material layer 22B in the first embodiment, respectively.

(Separator)
The separator 35 is the same as the separator 23 in the first embodiment.

(Electrolytes)
The electrolyte 36 includes a nonaqueous electrolytic solution (electrolytic solution) and a polymer compound (matrix polymer compound) that holds the nonaqueous electrolytic solution. The electrolyte 36 is, for example, a so-called gel electrolyte. A gel electrolyte is preferable because high ion conductivity (for example, 1 mS / cm or more at room temperature) is obtained and liquid leakage is prevented.

(Nonaqueous electrolyte)
The nonaqueous electrolytic solution includes an electrolyte salt and a nonaqueous solvent that dissolves the electrolyte salt. The non-aqueous electrolyte is the same as in the first embodiment.

(Polymer compound)
As the polymer compound, those having a property compatible with a solvent can be used. Examples of such a polymer compound include polyacrylonitrile, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, and polyphosphazene. , Polysiloxane, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene, or polycarbonate. These may be single and multiple types may be mixed. Among these, polyacrylonitrile, polyvinylidene fluoride, polyhexafluoropropylene, or polyethylene oxide is preferable. This is because it is electrochemically stable.

(2-2) Battery Manufacturing Method This nonaqueous electrolyte battery is manufactured, for example, by the following three manufacturing methods (first to third manufacturing methods).

(First manufacturing method)
In the first manufacturing method, first, the positive electrode active material layer 33B is formed on both surfaces of the positive electrode current collector 33A, for example, by the same procedure as the manufacturing procedure of the positive electrode 21 and the negative electrode 22 of the first embodiment described above. Thus, the positive electrode 33 is manufactured. Further, the negative electrode active material layer 34B is formed on both surfaces of the negative electrode current collector 34A to produce the negative electrode 34.

Subsequently, a precursor solution containing an electrolytic solution, a polymer compound, and a solvent is prepared and applied to at least one of both surfaces of the positive electrode 33 and the negative electrode 34, and then the solvent is volatilized to form a gel electrolyte 36. . Subsequently, the positive electrode lead 31 is attached to the positive electrode current collector 33A, and the negative electrode lead 32 is attached to the negative electrode current collector 34A. Instead of forming the gel electrolyte 36 on both surfaces of the electrode, the gel electrolyte 36 may be formed on at least one surface of both surfaces of the separator.

Subsequently, the positive electrode 33 and the negative electrode 34 on which the electrolyte 36 is formed are stacked via the separator 35 and then wound in the longitudinal direction, and a protective tape 37 is adhered to the outermost peripheral portion to produce the wound electrode body 30. To do. Finally, for example, after the wound electrode body 30 is sandwiched between two film-shaped exterior members 40, the outer edge portions of the exterior member 40 are bonded to each other by heat fusion or the like, so that the wound electrode body 30 is Encapsulate. At this time, the adhesion film 41 is inserted between the positive electrode lead 31 and the negative electrode lead 32 and the exterior member 40. Thereby, the nonaqueous electrolyte battery shown in FIGS. 3 and 4 is completed.

(Second manufacturing method)
In the second manufacturing method, first, the positive electrode 33 and the negative electrode 34 are manufactured in the same manner as in the first manufacturing method. Next, the positive electrode lead 31 is attached to the positive electrode 33 and the negative electrode lead 32 is attached to the negative electrode 34. Subsequently, the positive electrode 33 and the negative electrode 34 are laminated and wound through a separator 35 coated with a polymer compound on both sides, and then a protective tape 37 is adhered to the outermost periphery thereof to form a wound electrode body. A wound body that is a precursor of 30 is produced.

Subsequently, after sandwiching the wound body between the two film-like exterior members 40, the remaining outer peripheral edge except for the outer peripheral edge on one side is bonded by thermal fusion or the like, so that the bag-shaped exterior is obtained. The wound body is accommodated in the member 40.

Examples of the polymer compound applied to the separator 35 include a polymer containing vinylidene fluoride as a component, that is, a homopolymer, a copolymer, a multi-component copolymer, and the like. Specifically, polyvinylidene fluoride, binary copolymers containing vinylidene fluoride and hexafluoropropylene as components, and ternary copolymers containing vinylidene fluoride, hexafluoropropylene and chlorotrifluoroethylene as components. A coalescence or the like is preferred. The polymer compound may contain one or more other polymer compounds together with the polymer containing vinylidene fluoride as a component.

The polymer compound on the separator 35 may form a porous polymer compound as follows, for example. That is, first, a solution in which a polymer compound is dissolved in a first solvent composed of a polar organic solvent such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, N, N-dimethylsulfoxide, etc. And this solution is applied onto the separator 35. Next, the separator 35 coated with the above solution is compatible with the above polar organic solvent such as water, ethyl alcohol, propyl alcohol, etc., and in the second solvent which is a poor solvent for the above polymer compound. Immerse. At this time, solvent exchange occurs, phase separation accompanied by spinodal decomposition occurs, and the polymer compound forms a porous structure. Thereafter, by drying, a porous polymer compound having a porous structure can be obtained.

Subsequently, an electrolytic solution is prepared and injected into the bag-shaped exterior member 40, and then the opening of the exterior member 40 is sealed by heat fusion or the like. Thereby, the electrolytic solution is impregnated into the polymer compound, and the polymer compound is gelled to form the gel electrolyte 36, thereby completing the nonaqueous electrolyte battery shown in FIGS.

(Third production method)
In the third manufacturing method, first, the positive electrode 33 and the negative electrode 34 are produced in the same manner as in the first manufacturing method. Next, the positive electrode lead 31 is attached to the positive electrode 33 and the negative electrode lead 32 is attached to the negative electrode 34. Subsequently, after the positive electrode 33 and the negative electrode 34 are laminated and wound via the separator 35, a protective tape 37 is adhered to the outermost peripheral portion thereof, and a wound body that is a precursor of the wound electrode body 30. Is made.

Subsequently, after sandwiching the wound body between the two film-like exterior members 40, the remaining outer peripheral edge except for the outer peripheral edge on one side is bonded by thermal fusion or the like, so that the bag-shaped exterior is obtained. The wound body is accommodated in the member 40. Subsequently, an electrolyte composition containing an electrolytic solution, a monomer that is a raw material of the polymer compound, a polymerization initiator, and other materials such as a polymerization inhibitor as necessary is prepared to form a bag-shaped exterior member. After injecting into the inside of 40, the opening of the exterior member 40 is sealed by heat sealing or the like. Finally, the gel electrolyte 36 is formed by thermally polymerizing the monomer to obtain a polymer compound. Thereby, the nonaqueous electrolyte battery shown in FIGS. 3 and 4 is completed.

[Modification 1]
In the example of the nonaqueous electrolyte battery according to the second embodiment described above, the configuration example using the gel electrolyte has been described. However, instead of the gel electrolyte, an electrolyte solution that is a liquid electrolyte is used. Also good. In this case, the exterior member 60 is filled with a non-aqueous electrolyte, and a wound body having a configuration in which the electrolyte 36 is omitted from the wound electrode body 30 is impregnated with the non-aqueous electrolyte. In this case, the nonaqueous electrolyte battery is manufactured as follows, for example.

[Method for producing non-aqueous electrolyte battery]
(Preparation of positive electrode, negative electrode, non-aqueous electrolyte)
In the same manner as the manufacturing method of an example of the nonaqueous electrolyte battery, the positive electrode 33 and the negative electrode 34 are produced, and the nonaqueous electrolytic solution is prepared.

(Assembling of non-aqueous electrolyte battery)
Next, the positive electrode lead 31 is attached to the end portion of the positive electrode current collector 33A by welding, and the negative electrode lead 32 is attached to the end portion of the negative electrode current collector 34A by welding.

Next, the positive electrode 33 and the negative electrode 34 are laminated and wound with the separator 35 interposed therebetween, and a protective tape 37 is adhered to the outermost peripheral portion to form a wound body that is a precursor of the wound electrode body 30. Next, the wound body is sandwiched between the exterior members 40, and the outer peripheral edge except for one side is heat-sealed to form a bag shape, which is then stored inside the exterior member 40.

Next, after injecting the non-aqueous electrolyte into the exterior member 40 and impregnating the wound body with the non-aqueous electrolyte, the opening of the exterior member 40 is heat-sealed in a vacuum atmosphere and sealed. As a result, the intended non-electrolyte secondary battery is obtained.

[Modification 2]
In the above-described example of the second embodiment and the first modification, the nonaqueous electrolyte battery in which the wound electrode body 30 is sheathed with the exterior member 60 has been described. However, as illustrated in FIGS. A laminated electrode body 70 may be used instead of the electrode body 30. FIG. 5A is an external view of a nonaqueous electrolyte battery in which the laminated electrode body 70 is accommodated. FIG. 5B is an exploded perspective view showing a state in which the laminated electrode body 70 is accommodated in the exterior member 60. FIG. 5C is an external view showing the external appearance of the nonaqueous electrolyte battery shown in FIG. 5A from the bottom surface side.

The laminated electrode body 70 uses a laminated electrode body 70 in which a rectangular positive electrode 73 and a rectangular negative electrode 74 are laminated via a rectangular separator 75 and fixed by a fixing member 76. Although not shown, when the electrolyte layer is formed, the electrolyte layer is provided in contact with the positive electrode 73 and the negative electrode 74. For example, an electrolyte layer (not shown) is provided between the positive electrode 73 and the separator 75 and between the negative electrode 74 and the separator 75. This electrolyte layer is the same as the electrolyte 36 described above. A positive electrode lead 71 connected to the positive electrode 73 and a negative electrode lead 72 connected to the negative electrode 74 are led out from the laminated electrode body 70, and the positive electrode lead 71, the negative electrode lead 72, and the exterior member 60 are in close contact with each other. A film 61 is provided.

In addition, the manufacturing method of a non-aqueous electrolyte battery produces a laminated electrode body in place of the wound electrode body 30, and a laminated body in place of the wound body (with an electrolyte layer omitted from the laminated electrode body 70). Is the same as the manufacturing method of the nonaqueous electrolyte battery of the example of the second embodiment and the modified example 1 except that is manufactured.

<Third to Fourth Embodiments>
(Outline of this technology)
First, in order to facilitate understanding of the present technology, an outline of the present technology will be described. In Patent Document 3 (Japanese Patent Laid-Open No. 2013-97993) described above, the object is to improve low-temperature characteristics, but the silane compound does not contain an amino group and a carbonate structure, and the structure is greatly different from the compound shown in the present technology. Moreover, the improvement of the low temperature characteristics was not sufficient.

Patent Document 4 (Japanese Patent Application Laid-Open No. 2012-199145) has a lithium titanate in the negative electrode and a compound having a SiR structure in the battery. The purpose of improvement is to suppress resistance increase and self-discharge. Is different. In addition, the prior art does not include a sulfonic solvent. Although the resistance rise can be suppressed, the initial resistance is high.

Patent Document 5 (Japanese Patent Laid-Open No. 2013-4215) attempts to improve the characteristics with a carbonate-structured coating, but the structure is different from the compound of the present technology and the purpose of the improvement is not to improve the low-temperature characteristics, but the low-temperature characteristics are improved. Not done.

In Patent Document 6 (Japanese Patent Laid-Open No. 2001-93583), the purpose of improvement is different from the present technology for the purpose of preventing an internal short circuit. Although it has a crosslinking agent in the negative electrode and a silane coupling agent is mentioned as a candidate for this, it is different from the compound shown in the present technology. In Patent Document 4, the negative electrode does not have lithium titanate, but in the present technology, the negative electrode has lithium titanate.

In Patent Document 7 (Japanese Patent Application Laid-Open No. 11-287441), an improvement in safety is an improvement objective. In Patent Document 5, the negative electrode does not have lithium titanate, but the present technology has negative electrode lithium titanate. Although a silane coupling agent is used for the negative electrode, the chemical structure is different from the compound represented by the present technology. Although cyclic sulfolane is contained in the electrolytic solution, the cyclic sulfolane has a high viscosity, so that the input / output characteristics including high resistance and low temperature are impaired. In the present technology, when a low-viscosity chain sulfolane is used, low resistance and low temperature characteristics can be improved without deteriorating input / output characteristics.

In Patent Document 1 (Japanese Patent Laid-Open No. 2011-222450), it is proposed to suppress high-temperature deterioration by using a silane compound having a fluoro group when nickel or an iron-based compound is used for the positive electrode. In Patent Document 6, it is described that the electrolyte solution contains a sulfone compound. However, as in the example of Patent Document 6, the negative electrode has 0 Vvs. When graphite or carbon having a reaction potential near Li / Li ⁺ is used, the sulfone compound undergoes reductive decomposition as described in Non-Patent Document 1 (Journal of The Electrochemical Society, 149 7 A920-A926 2002). Long-term reliability will be insufficient. In what was mentioned above, there is no suggestion about the effect at the time of using a lithium titanium complex acid compound for a negative electrode. In contrast, in this technique, the reaction potential is 1.55 Vvs. By using Li / Li ⁺ and a sufficiently high lithium-titanium complex acid compound for the negative electrode, when a chain sulfone is used, a more sufficient long-term life can be obtained.

Hereinafter, embodiments of the present technology will be described with reference to the drawings. The description will be given in the following order.
3. Third embodiment (example of cylindrical battery)
4). Fourth Embodiment (Example of laminated film type battery)
The embodiments described below are suitable specific examples of the present technology, and the contents of the present technology are not limited to these embodiments. Moreover, the effect described in this specification is an illustration to the last, is not limited, and does not deny that the effect different from the illustrated effect exists.

3. Third Embodiment (3-1) Battery Configuration A battery according to a third embodiment of the present technology will be described with reference to FIGS. 1 and 2. FIG. 1 shows a cross-sectional configuration of a battery according to a third embodiment of the present technology. FIG. 2 shows an enlarged part of the spirally wound electrode body 20 shown in FIG. This battery is a secondary battery that can be charged and discharged, for example, a non-aqueous electrolyte battery, for example, a lithium ion secondary battery, and the like.

The negative electrode 22 contains a compound derived from a carbonate solvent and a silane coupling agent or a siloxane compound (sometimes abbreviated as a silane / siloxane compound) contained in an electrolyte solution described later. The negative electrode 22 may further contain a compound derived from a chain sulfone compound.

For example, the negative electrode 22 includes, as such a compound, at least one of a compound represented by the formula (1A), a compound represented by the formula (2A), and a compound represented by the formula (3A). It is. The negative electrode 22 may further include a sulfonyl compound represented by the formula (4A) as a compound derived from the chain sulfone compound. Typically, these compounds are contained in a film or the like formed on the surface of the active material particles in the negative electrode active material layer 22B during charge / discharge. Side reactions can be suppressed by wrapping the active site of the negative electrode 22 with the coating. As a result, suppression of gas generation can be suppressed. In addition, since the negative electrode 22 contains at least one of the compound represented by the formula (1A), the compound represented by the formula (2A), and the compound represented by the formula (3A), Li can be obtained even in a low temperature environment. Ion diffusion is stable and high input / output characteristics can be obtained.

(In the formula, R1, R2 and R3 are each independently an alkyl group, a halogen group, a halogenated alkyl group or an alkoxy group. R4 is an alkali metal, alkaline earth metal, hydrogen group, halogen group or alkyl group. , Alkenyl group, alkynyl group, halogenated alkyl group, alkyl group bonded to alkali metal, alkyl group bonded to alkaline earth metal, alkenyl halide group, alkenyl group bonded to alkali metal, bonded to alkaline earth metal An alkenyl group, a halogenated alkynyl group, an alkynyl group bonded to an alkali metal, an alkynyl group bonded to an alkaline earth metal, or an alkoxy group, wherein R5 is an alkali metal, alkaline earth metal, hydrogen group, halogen group, alkyl group; Alkenyl group, alkynyl group, halogenated alkyl group, alkali metal Bonded alkyl group, alkyl group bonded to alkaline earth metal, halogenated alkenyl group, alkenyl group bonded to alkali metal, alkenyl group bonded to alkaline earth metal, halogenated alkynyl group, alkynyl group bonded to alkali metal , An alkynyl group bonded to an alkaline earth metal, an alkoxy group, a substituent represented by the following formula (A), a substituent represented by the following formula (B), and a formula (C) Substituents, substituents represented by the following formula (D), substituents represented by the following formula (E), substituents represented by the following formula (F), represented by the following formula (G) A substituent represented by the following formula (H), or a substituent represented by the following formula (I).

(Wherein R6, R7 and R8 are each independently an alkyl group, a halogen group, a halogenated alkyl group or an alkoxy group. R9, R10 and R11 are each independently an alkali metal, an alkaline earth metal, An alkyl group, a halogen group, a halogenated alkyl group, or a hydrogen group, and R12 is an alkyl group, a halogen group, a halogenated alkyl group, a substituent represented by the following formula (A), or a hydrogen group; )

(In the formula, R13, R14 and R15 each independently represents an alkyl group, a halogen group, a halogenated alkyl group or an alkoxy group. R16 represents an alkali metal, an alkaline earth metal, an alkyl group, a halogen group or a halogenated group. R 17 is an alkyl group, a halogen group, a halogenated alkyl group, a substituent represented by the following formula (A), or a hydrogen group.

(In the formula, R18 represents a halogen group, an alkyl group, a halogenated alkyl group or an alkoxy group. R19 represents H or Li.)

(Wherein R20 is an alkali metal, alkaline earth metal, alkyl group, halogen group, halogenated alkyl group or hydrogen group.)

Examples of the compound represented by the formula (1A) include compounds represented by the following formulas (1A-1) to (1A-78). Among these, from the viewpoint of battery characteristics, a compound represented by the formula (1A-25), a compound represented by the formula (1A-26), a compound represented by the formula (1A-27), a formula (1A- 28), a compound represented by formula (1A-29), a compound represented by formula (1A-30), a compound represented by formula (1A-32), a formula (1A-38) A compound represented by formula (1A-39), a compound represented by formula (1A-40), a compound represented by formula (1A-41), a formula (1A-42) Are preferred.

Examples of the compound represented by the formula (2A) include compounds represented by the following formulas (2A-1) to (2A-12). Among these, from the viewpoint of battery characteristics, a compound represented by the formula (2A-10), a compound represented by the formula (2A-11), and a compound represented by the formula (2A-12) are preferable.

Examples of the compound represented by the formula (3A) include compounds represented by the following formulas (3A-1) to (3A-3).

The negative electrode including at least one of the compound represented by the formula (1A), the compound represented by the formula (2A), and the compound represented by the formula (3A) is included in, for example, an electrolytic solution impregnated in the negative electrode. A silane coupling agent or a siloxane compound (hereinafter referred to as a silane / siloxane compound) and a carbonate solvent.

Each compound represented by Formula (1A), Formula (2A), and Formula (3A) is derived from a silane / siloxane compound and a carbonate solvent. Typically, for example, it is produced by a reaction between a silane / siloxane compound and a decomposition product of a carbonate solvent in charge / discharge of a battery. The silane siloxane compound is typically a silane siloxane compound having amino (—NH ₂ ).

In order to confirm the silane / siloxane compound and the compound derived from the carbonate solvent formed in the battery such as in the negative electrode, for example, after disassembling the battery and taking out the electrode body including the negative electrode, the active material The formation ratio of the surface may be analyzed by observing the element distribution by an existing elemental analysis method, that is, energy dispersive X-ray spectroscopy (SEM-EDX). When using this method, in order to prevent unintentional analysis of unnecessary components in the electrolyte, the electrode surface may be washed after being washed with an organic solvent such as dimethyl carbonate (DMC). preferable.

(Content of at least one compound represented by formula (1A) to compound represented by formula (3A))
By adjusting the content of at least one of the compound represented by the formula (1A) to the compound represented by the formula (3A) within a predetermined range, the negative electrode active material can be maintained while maintaining characteristics such as battery capacity. The surface can be coated more effectively. At least one of the compound represented by the formula (1A) to the compound represented by the formula (3A) may be contained in the negative electrode and also in the electrolytic solution. A preferable content of at least one of the compound represented by the formula (1A) to the compound represented by the formula (3A) is represented by the compound represented by the formula (1A) to the formula (3A) in the electrolytic solution. Defined by the content of at least one compound. The content of at least one of the compound represented by the formula (1A) to the compound represented by the formula (3A) is set to 0. 0 with respect to the total mass of the electrolytic solution from the viewpoint of obtaining a more excellent effect. More preferably, the content is from 05% by mass to 0.5% by mass.

Examples of the compound represented by the formula (4A) include compounds represented by the following formulas (4A-1) to (4A-8).

The compound in the electrolytic solution can be confirmed by applying the disassembled battery to a centrifuge and analyzing the extracted electrolytic solution. Specifically, NMR (Nuclear magnetic resonance), IR (infrared absorption spectroscopy), Raman (Raman spectroscopy), GC-MS (Gas chromatography, mass spectrometry), LC-MS (Liquid chromatography, Mass spectrometry), etc. can be used. it can.

(Non-aqueous solvent)
As the non-aqueous solvent, a solvent containing at least a carbonate solvent is used.

(Carbonate solvent)
Examples of the carbonate solvent included in the present technology include cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC), chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Unsaturated carbonates having unsaturated bonds such as carbon-carbon double bonds such as vinyl ethylene carbonate (VC), 4-fluoro-1,3-dioxolan-2-one (FEC; fluoroethylene carbonate), 4, Carbonate compounds such as halogenated carbonates such as 5-difluoro-1,3-dioxolan-2-one (DFEC; difluoroethylene carbonate) can be used.

(Other solvents)
The non-aqueous solvent may contain other solvents. Other solvents include 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), 2-methyltetrahydrofuran (Me-THF), 1,3-dioxolane (DOL), 4-methyl-1,3-dioxolane (Me -DOL), diethyl ether (DEE), γ-butyrolactone (GBL), γ-valerolactone (GVL), 3-methyloxazolidinone (MOX), methyl formate (MF), sulfolane (SL), 3-methylsulfolane (3MS), Dimethyl sulfoxide (DMSO), acetonitrile (AN), dimethyl sulfoxide (DMSO), trimethyl phosphate (TMP), propionitrile (PN), glutaronitrile (GLN), adiponitrile (ADN), methoxyacetonitrile (MAN), 3 -Methoxypro Pionitrile (MPN), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), N-methylpyrrolidinone (NMP), N-methyloxazolidinone (NMO), N, N'-dimethylimidazolidi Non (DMI), nitromethane (NM), nitroethane (NE) and the like can be mentioned.

The non-aqueous solvent may contain a chain sulfone compound as another solvent. The chain sulfone compound refers to a compound having a chain structure and having a sulfonyl group (—S (═O) ₂ —). Examples of chain sulfone compounds include dimethylsulfone [formula (5A-1)], diethylsulfone [formula (5A-2)], ethylmethylsulfone [formula (5A-3)], methylisopropylsulfone [formula (5A -4)], ethyl isopropyl sulfone [formula (5A-5)], ethyl isobutyl sulfone [formula (5A-6)], isopropyl isobutyl sulfone [formula (5A-7)], isopropyl s-butyl sulfone [formula (5A -8)] and butyl isobutyl sulfone [formula (5A-9)] are preferred. Among these, ethyl isopropyl sulfone (formula (5A-5); EiPS) is most preferable from the viewpoint of battery characteristics.

By containing a chain sulfone compound as a solvent in the electrolytic solution, a film containing a compound derived from the chain sulfone compound can be formed on the negative electrode during charging / discharging with respect to the negative electrode using a titanium-containing inorganic oxide. .

(Silane coupling agent or siloxane compound)
As the silane coupling agent, for example, a silane coupling agent having an amino group (—NH ₂ ), another silane coupling agent, or the like can be used. Examples of the silane coupling agent having an amino group (—NH ₂ ) include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ —NH ₂ )], 3-amino Examples thereof include propyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ NH ₂ ], 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like.

Other silane coupling agents include 3-mercaptopropyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ SH], 3-mercaptopropylmethyldimethoxysilane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ SH], 3-mercaptopropyldimethylmethoxysilane [(CH ₃ ) ₂ (CH ₃ O) Si (CH ₂ ) ₃ SH], 3-mercaptopropyltrimethylsilane [(CH ₃ ) ₃ Si ( CH ₂ ) ₃ SH], 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, vinyltris (2-methoxyethoxy) silane, vinyltristrimethoxysilane, vinyltriethoxysilane, vinyltrichloro Silane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysila 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycyl Sidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxy Cyclohexyl) ethyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, Le triethoxysilane, methyl trimethoxysilane, phenyl triethoxysilane, and phenyl trimethoxysilane.

Incidentally, a silane coupling agent, those having a structure _{_{_{[R x -Si (R y) n}}} (OR z) 3-n R x reactive functional group, R _y: hydrolyzable group: organic group, OR _z] If so, it is not limited to these. The siloxane compound is not limited to these as long as it has a siloxane structure. Further, the series of silane / siloxane compounds described above may be one kind, or two or more kinds may be mixed in any combination. Among these silane / siloxane compounds, from the viewpoint of battery characteristics, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N -2- (Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxy Silane and the like are preferable.

(Electrolyte salt)
Examples of the electrolyte salt contained in the electrolyte include lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium perchlorate (LiClO ₄ ), and lithium hexafluoroarsenate (LiAsF). _6), lithium tetraphenylborate (LiB (C ₆ H ₅₎ _4), methanesulfonic acid lithium (LiCH ₃ SO _3), lithium trifluoromethanesulfonate (LiCF ₃ SO _3), lithium bis (fluorosulfonyl) imide ( LiN (SO ₂ F) ₂ ), lithium (fluorosulfonyl) (trifluoromethylsulfonyl) imide (LiN (SO ₂ F) (SO ₂ CF ₃ )), lithium bis (trifluoromethylsulfonyl) imide (LiN (SO ₂ CF ₃₎ _2), lithium bis (oxalato) borate (LiC ₄ BO _8), Richiumujifu Oro like oxa Ratn borate (LiC _₂ BO ₄ F ₂₎ and the like.

These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio. Among these, at least one selected from the group consisting of lithium hexafluorophosphate (LiPF ₆ ) and lithium tetrafluoroborate (LiBF ₄ ) is preferable, and lithium tetrafluoroborate (LiBF ₄ ), lithium bis (Fluorosulfonyl) imide (LiN (SO ₂ F) ₂ ), lithium bis (trifluoromethanesulfonyl) imide (LiN (SO ₂ CF ₃ ) ₂ ), and lithium bis (oxalato) boric acid (LiC ₂ BO ₄ F ₂ ) It is more preferable to contain.

The electrolyte salt preferably contains lithium bis (fluorosulfonyl) imide (LiN (SO ₂ F) ₂ ) depending on the addition of the chain sulfone compound. In this case, if the ratio of the chain sulfone compound in the electrolyte solvent is X% and the total amount of the electrolyte salt is Ymol / L, the amount of lithium bis (fluorosulfonyl) imide (LiN (SO ₂ F) ₂ ) added: It is preferable that Zmol / L ≧ Ymol / L × X / 100 when Zmol / L is set.

For example, when ethyl isopropyl sulfone (formula (5A-5); EiPS) is 10% of the electrolyte solvent, if the total amount of the electrolyte salt is 1.0 mol / L, 0.1 mol / L or more of lithium bis (fluorosulfonyl) ) Imide (LiN (SO ₂ F) ₂ ) is desirable. Thereby, high electrical conductivity can be imparted in a wide temperature range including under a low temperature environment, and more excellent battery characteristics can be provided.

(3-2) Battery Manufacturing Method This nonaqueous electrolyte battery is manufactured, for example, by the following manufacturing method.

(Preparation of electrolyte)
The above-described electrolytic solution is prepared. The electrolyte is impregnated in the negative electrode, and a compound derived from a carbonate solvent (carbonate compound) and a silane / siloxane compound is formed during charging and discharging of the battery. More specifically, for example, a reaction product of a decomposition product of a carbonate solvent and a silane / siloxane compound is formed during charge / discharge of a battery.

Specifically, at the time of charge / discharge of the battery, for example, the compound represented by the formula (1A), the compound represented by the formula (2A), and the compound represented by the formula (3A) as the above-described reaction product And at least one of these compounds can be contained in the negative electrode 22. Various methods can be used as a method for causing the anode 22 to contain at least one of these compounds. For example, when forming the negative electrode active material layer 22B, at least one of a compound represented by the formula (1A), a compound represented by the formula (2A), and a compound represented by the formula (3A), and a negative electrode material At least one of a compound represented by the formula (1A), a compound represented by the formula (2A), and a compound represented by the formula (3A) by preparing a negative electrode mixture by mixing with May be contained in the negative electrode 22.

4). Fourth Embodiment (4-1) Battery Configuration A nonaqueous electrolyte battery (battery) according to a fourth embodiment of the present technology will be described. FIG. 3 shows an exploded perspective configuration of the nonaqueous electrolyte battery according to the fourth embodiment of the present technology. FIG. 4 is an enlarged cross-sectional view taken along line II of the spirally wound electrode body 30 shown in FIG. It shows.

(Positive electrode)
The positive electrode 33 has, for example, a structure in which a positive electrode active material layer 33B is provided on both surfaces of a positive electrode current collector 33A having a pair of surfaces. Although not shown, the positive electrode 33 may have a region where the positive electrode active material layer 33B is formed only on one surface of the positive electrode current collector 33A. The positive electrode current collector 33A and the positive electrode active material layer 33B are the same as the positive electrode current collector 21A and the positive electrode active material layer 21B in the third embodiment, respectively.

(Negative electrode)
The negative electrode 34 has, for example, a structure in which a positive electrode active material layer 33B is provided on both surfaces of a negative electrode current collector 34A having a pair of surfaces. Although not shown, the negative electrode 34 may have a region where the negative electrode active material layer 34B is formed only on one surface of the negative electrode current collector 34A. The negative electrode current collector 34A and the negative electrode active material layer 34B are the same as the negative electrode current collector 22A and the negative electrode active material layer 22B in the third embodiment, respectively.

(Separator)
The separator 35 is the same as the separator 23 in the third embodiment.

(Nonaqueous electrolyte)
The nonaqueous electrolytic solution includes an electrolyte salt and a nonaqueous solvent that dissolves the electrolyte salt. The non-aqueous electrolyte is the same as in the third embodiment.

(4-2) Battery Manufacturing Method This nonaqueous electrolyte battery is manufactured, for example, by the following three manufacturing methods (first to third manufacturing methods).

(First manufacturing method)
In the first manufacturing method, first, for example, the positive electrode active material layer 33B is formed on both surfaces of the positive electrode current collector 33A by the same procedure as the manufacturing procedure of the positive electrode 21 and the negative electrode 22 of the third embodiment described above. Thus, the positive electrode 33 is manufactured. Further, the negative electrode active material layer 34B is formed on both surfaces of the negative electrode current collector 34A to produce the negative electrode 34.

[Modification 1]
In the example of the nonaqueous electrolyte battery according to the fourth embodiment described above, the configuration example using the gel electrolyte has been described. However, instead of the gel electrolyte, an electrolyte solution that is a liquid electrolyte is used. Also good. In this case, the exterior member 60 is filled with a non-aqueous electrolyte, and a wound body having a configuration in which the electrolyte 36 is omitted from the wound electrode body 30 is impregnated with the non-aqueous electrolyte. In this case, the nonaqueous electrolyte battery is manufactured as follows, for example.

[Modification 2]
In the above-described example of the fourth embodiment and the first modification, the nonaqueous electrolyte battery in which the wound electrode body 30 is sheathed with the exterior member 60 has been described. However, as illustrated in FIGS. 5A to 5C, A laminated electrode body 70 may be used instead of the electrode body 30. FIG. 5A is an external view of a nonaqueous electrolyte battery in which the laminated electrode body 70 is accommodated. FIG. 5B is an exploded perspective view showing a state in which the laminated electrode body 70 is accommodated in the exterior member 60. FIG. 5C is an external view showing the external appearance of the nonaqueous electrolyte battery shown in FIG. 5A from the bottom surface side.

In addition, the manufacturing method of a non-aqueous electrolyte battery produces a laminated electrode body in place of the wound electrode body 30, and a laminated body in place of the wound body (with an electrolyte layer omitted from the laminated electrode body 70). Is the same as the manufacturing method of the nonaqueous electrolyte battery of the example of the fourth embodiment and the modification 1 except that the above is manufactured.

<Fifth to sixth embodiments>
(Outline of this technology)
First, in order to facilitate understanding of the present technology, an outline of the present technology will be described. In the above-mentioned Patent Document 8 (Japanese Patent Laid-Open No. 2013-80714, in order to suppress gas generation, an isocyanate compound is put in the electrolytic solution. When it is decomposed in the battery, it becomes a compound having an amino group. In the prior art, there is no purpose or mention of suppressing the deterioration by capturing the HF causing the deterioration. The application range of JP 2011-165998 A is a capacitor, and does not describe any effect in a lithium secondary battery.In Patent Document 2, trapped particles are used to supplement HF. In Patent Document 2, lithium titanate is not used for the negative electrode in the patent document 2. On the other hand, in this technology, patent documents such as lithium titanate are used for the negative electrode. 2 use different negative electrode active material and.

Hereinafter, embodiments of the present technology will be described with reference to the drawings. The description will be given in the following order.
5. Fifth embodiment (example of cylindrical battery)
6). Sixth embodiment (example of laminated film type battery)
The embodiments described below are suitable specific examples of the present technology, and the contents of the present technology are not limited to these embodiments. Moreover, the effect described in this specification is an illustration to the last, is not limited, and does not deny that the effect different from the illustrated effect exists.

5. Fifth Embodiment (5-1) Battery Configuration A battery according to a fifth embodiment of the present technology will be described with reference to FIGS. 1 and 2. FIG. 1 shows a cross-sectional configuration of a battery according to a fifth embodiment of the present technology. FIG. 2 shows an enlarged part of the spirally wound electrode body 20 shown in FIG. This battery is a secondary battery that can be charged and discharged, for example, a non-aqueous electrolyte battery, for example, a lithium ion secondary battery, and the like.

The negative electrode 22 is derived from a silane coupling agent or a siloxane compound (sometimes abbreviated as a silane / siloxane compound) contained in an electrolyte solution described later, and a cyclic carboxylic acid ester compound and a silane / siloxane compound. At least one of the compounds to be included.

For example, the negative electrode 22 includes, as such a compound, at least one of a compound represented by the formula (1B), a compound represented by the formula (2B), and a compound represented by the formula (3B). It is. Typically, these compounds are contained in a film or the like formed on the surface of the active material particles in the negative electrode active material layer 22B during charge / discharge. Side reactions can be suppressed by wrapping the active site of the negative electrode 22 with the coating. As a result, gas generation can be suppressed. Further, since the negative electrode 22 contains at least one of the compound represented by the formula (1B), the compound represented by the formula (2B), and the compound represented by the formula (3B), the Lithium is also Li even in a low temperature environment. Ion diffusion is stable and high input / output characteristics can be obtained.

(In the formula, R1, R2 and R3 are each independently an alkyl group, a fluorine group, a fluorinated alkyl group or an alkoxy group. N1 is an integer of 1-8)

(Wherein R4, R5 and R6 are each independently an alkyl group, a halogen group, a halogenated alkyl group or an alkoxy group. R7 and R8 are each independently a hydrogen group, an alkali metal or an alkaline earth metal) An alkyl group or a halogen group, n2 is an integer of 1 to 8, and n3 is an integer of 1 to 8.)

(Wherein R9, R10 and R11 are each independently an alkyl group, a halogen group, a halogenated alkyl group or an alkoxy group. R12 and R13 are each independently a hydrogen group alkyl group, a halogen group, or R14 is a hydrogen group, an alkali metal or an alkaline earth metal, n4 is an integer of 1 to 8, n5 is an integer of 1 to 8. n6 is 1 or more It is an integer of 8 or less.)

In this technology, compared with carbon-based negative electrode active materials such as graphite, a negative electrode material in which the reaction potential of the negative electrode becomes a noble potential is used as the negative electrode active material. A solvent or the like that decomposes and is not effective when an active material is used can also be used effectively.

Examples of the compound represented by the formula (1B) include compounds represented by the following formulas (1B-1) to (1B-5).

Examples of the compound represented by the formula (2B) include compounds represented by the following formulas (2B-1) to (2B-20). Among these, the compound represented by the formula (2B-1), the compound represented by the formula (2B-4), the compound represented by the formula (2B-5), and the formula (2B-6) A compound, a compound represented by the formula (2B-9), and a compound represented by the formula (2B-10) are preferable because they can impart high electrical conductivity and provide high input / output characteristics even in a low temperature environment.

Examples of the compound represented by the formula (3B) include compounds represented by the following formulas (3B-1) to (3B-20). Among these, the compound represented by the formula (3B-1), the compound represented by the formula (3B-4), the compound represented by the formula (3B-5), and the formula (3B-6) A compound, a compound represented by the formula (3B-9), and a compound represented by the formula (3B-10) are preferable because they can impart high electrical conductivity and provide high input / output characteristics even in a low temperature environment.

The negative electrode 22 including at least one of the compound represented by the formula (1B), the compound represented by the formula (2B), and the compound represented by the formula (3B) is included in, for example, an electrolytic solution impregnated in the negative electrode Silane coupling agents or siloxane compounds (hereinafter referred to as silane / siloxane compounds) and cyclic carboxylic acid ester compounds.

The compound represented by the formula (1B) is derived from a silane / siloxane compound, and effectively traps, for example, HF that causes various deteriorations in the battery generated by the reaction between an electrolyte salt and water. It is a thing. For example, HF derived from fluorine-containing lithium salt can be effectively trapped. Each compound represented by Formula (2B) and Formula (3B) is derived from a silane / siloxane compound and a cyclic carboxylic acid ester. Typically, for example, it is produced by a reaction between a silane / siloxane compound and a decomposition product of a cyclic carboxylic acid ester in charge / discharge of a battery. The silane-siloxane compound is typically a silane coupling agent having amino (—NH ₂ ).

In order to confirm the compounds derived from the silane / siloxane compound and the cyclic carboxylic acid ester formed in the battery such as in the negative electrode, for example, after disassembling the battery and taking out the electrode body including the negative electrode, The formation ratio of the active material surface may be analyzed by observing the element distribution with an existing elemental analysis method, that is, energy dispersive X-ray spectroscopy (SEM-EDX). When using this method, in order to prevent unintentional analysis of unnecessary components in the electrolyte, the electrode surface may be washed after being washed with an organic solvent such as dimethyl carbonate (DMC). preferable.

(Content of at least one compound represented by formula (1B) to compound represented by formula (3B))
By adjusting the content of at least one of the compound represented by the formula (1B) to the compound represented by the formula (3B) within a predetermined range, the negative electrode active material is further maintained while maintaining characteristics such as battery capacity. The surface can be coated more effectively. At least one of the compound represented by the formula (1B) to the compound represented by the formula (3B) may be contained in the negative electrode and also in the electrolytic solution. The preferable content of at least one of the compound represented by the formula (1B) to the compound represented by the formula (3B) is represented by the compound represented by the formula (1B) to the formula (3B) in the electrolytic solution. Defined by the content of at least one compound. The content of at least one of the compound represented by the formula (1B) to the compound represented by the formula (3B) is 0.05% with respect to the mass of the electrolytic solution from the viewpoint of obtaining a more excellent effect. It is more preferable that the content is not less than 0.5% by mass.

The negative electrode 22 may further contain a compound derived from a carbonate compound and a silane / siloxane compound in addition to the above-mentioned compound from the viewpoint of obtaining superior characteristics. The compound derived from the carbonate compound and the silane / siloxane compound contained in the negative electrode 22 is at least a compound represented by the formula (4B), a compound represented by the formula (5B), and a compound represented by the formula (6B). One type is mentioned.

Wherein R15, R16 and R17 are each independently an alkyl group, a halogen group, a halogenated alkyl group or an alkoxy group. R18 is an alkali metal, alkaline earth metal, hydrogen group, halogen group or alkyl group. , Alkenyl group, alkynyl group, halogenated alkyl group, alkyl group bonded to alkali metal, alkyl group bonded to alkaline earth metal, alkenyl halide group, alkenyl group bonded to alkali metal, bonded to alkaline earth metal An alkenyl group, a halogenated alkynyl group, an alkynyl group bonded to an alkali metal, an alkynyl group bonded to an alkaline earth metal, or an alkoxy group, wherein R19 is an alkali metal, alkaline earth metal, hydrogen group, halogen group, alkyl group; Alkenyl group, alkynyl group, halogenated alkyl group, Alkyl group bonded to potassium metal, alkyl group bonded to alkaline earth metal, halogenated alkenyl group, alkenyl group bonded to alkali metal, alkenyl group bonded to alkaline earth metal, alkynyl halide group, bonded to alkali metal An alkynyl group bonded to an alkaline earth metal, an alkoxy group, a substituent represented by the following formula (A), a substituent represented by the following formula (B), and the following formula (C): The substituent represented by the following formula (D), the substituent represented by the following formula (E), the substituent represented by the following formula (F), the following formula (G ), A substituent represented by the following formula (H), or a substituent represented by the following formula (I).)

(Wherein R20, R21 and R22 are each independently an alkyl group, a halogen group, a halogenated alkyl group or an alkoxy group. R23, R24 and R25 are each independently an alkali metal, an alkaline earth metal, An alkyl group, a halogen group, a halogenated alkyl group, or a hydrogen group, and R26 is an alkyl group, a halogen group, a halogenated alkyl group, a substituent represented by the following formula (A), or a hydrogen group. )

(Wherein R27, R28 and R29 each independently represents an alkyl group, a halogen group, a halogenated alkyl group or an alkoxy group. R30 represents an alkali metal, an alkaline earth metal, an alkyl group, a halogen group or a halogenated group. R 31 is an alkyl group, a halogen group, a halogenated alkyl group, a substituent represented by the following formula (A), or a hydrogen group.

(Wherein R32 is an alkali metal, alkaline earth metal, alkyl group, halogen group, halogenated alkyl group or hydrogen group.)

The negative electrode containing at least one of the compound represented by the formula (4B), the compound represented by the formula (5B), and the compound represented by the formula (6B) is included in, for example, an electrolytic solution impregnated in the negative electrode. A silane coupling agent or a siloxane compound (hereinafter referred to as a silane / siloxane compound) and a carbonate solvent.

Each compound represented by Formula (4B), Formula (5B), and Formula (6B) is derived from a silane / siloxane compound and a carbonate solvent. Typically, for example, it is produced by a reaction between a silane / siloxane compound and a decomposition product of a carbonate solvent in charge / discharge of a battery. The silane-siloxane compound is typically a coupling agent having amino (—NH ₂ ).

Examples of the compound represented by the formula (4B) include compounds represented by the following formulas (4B-1) to (4B-78). Among these, from the viewpoint of battery characteristics, a compound represented by the formula (4B-25), a compound represented by the formula (4B-26), a compound represented by the formula (4B-27), a formula (4B- 28), a compound represented by formula (4B-29), a compound represented by formula (4B-30), a compound represented by formula (4B-32), a formula (4B-38) A compound represented by formula (4B-39), a compound represented by formula (4B-40), a compound represented by formula (4B-41), a formula (4B-42) Are preferred.

Examples of the compound represented by the formula (5B) include compounds represented by the following formulas (5B-1) to (5B-12). Among these, from the viewpoint of battery characteristics, a compound represented by the formula (5B-10), a compound represented by the formula (5B-11), and a compound represented by the formula (5B-12) are preferable.

Examples of the compound represented by the formula (6B) include compounds represented by the following formulas (6B-1) to (6B-3).

(Non-aqueous solvent)
As the non-aqueous solvent, a solvent containing at least a cyclic carboxylic acid ester compound is used.

(Cyclic carboxylic acid ester compound)
Examples of cyclic carboxylic acid ester compounds include γ-butyrolactone (GBL), γ-valerolactone (GVL), and σ-valerolactone. These compounds and the like are preferable because ion conductivity at low temperature can be further improved.

(Carbonate solvent)
The non-aqueous solvent may contain a carbonate solvent. Examples of the carbonate solvent include cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC), chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC), vinyl ethylene carbonate ( VC) and the like, unsaturated carbonates having unsaturated bonds such as carbon-carbon double bonds, 4-fluoro-1,3-dioxolan-2-one (FEC; fluoroethylene carbonate), 4,5-difluoro-1 Carbonate compounds such as halogenated carbonates such as 1,3-dioxolan-2-one (DFEC; difluoroethylene carbonate) can be used.

(Other solvents)
The non-aqueous solvent may contain other solvents. Other solvents include 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), 2-methyltetrahydrofuran (Me-THF), 1,3-dioxolane (DOL), 4-methyl-1,3-dioxolane (Me -DOL), diethyl ether (DEE), 3-methyloxazolidinone (MOX), methyl formate (MF), sulfolane (SL), 3-methylsulfolane (3MS), dimethyl sulfoxide (DMSO), acetonitrile (AN), dimethyl sulfoxide (DMSO), trimethyl phosphate (TMP), propionitrile (PN), glutaronitrile (GLN), adiponitrile (ADN), methoxyacetonitrile (MAN), 3-methoxypropionitrile (MPN), N, N- Dimethylformamide (D F), N, N-dimethylacetamide (DMA), N-methylpyrrolidinone (NMP), N-methyloxazolidinone (NMO), N, N′-dimethylimidazolidinone (DMI), nitromethane (NM), nitroethane (NE) ) Etc.

(Content)
Although content of the cyclic carboxylic acid ester compound in electrolyte solution is not specifically limited, From a viewpoint of battery characteristics, 20 mass% or more is preferable with respect to the mass of electrolyte solution. By containing 20% by mass or more of the carboxylic acid ester compound in the electrolytic solution, it is possible to further secure ion conductivity at a low temperature. In addition, when prescribing | regulating an upper limit, 60 mass% or less is preferable.

(Additive)
The electrolytic solution contains a silane coupling agent or a siloxane compound (silane / siloxane compound) as an additive. The electrolytic solution may contain both a silane coupling agent and a siloxane compound. By containing the silane / siloxane compound in the electrolytic solution, at least one of the silane / siloxane compound and the compound derived from the silane / siloxane compound also has an effect of covering the active surface of the electrode active material, and the electrolytic solution is decomposed. Side reactions can be effectively suppressed, and a battery with high long-term reliability can be provided. Furthermore, when the electrolytic solution contains a silane / siloxane compound, it is possible to further improve the impregnation of the electrolytic solution into the electrode, and to obtain a more excellent effect that a high capacity can be expressed even in a low temperature environment. Can do. For example, when the content ratio of GBL or the like in the electrolytic solution is increased, the impregnation property of the electrolytic solution into the electrode tends to deteriorate. However, when the electrolytic solution contains a silane / siloxane compound, the electrolytic solution electrode It is possible to improve that the impregnation property into the resin deteriorates.

(Silane coupling agent or siloxane compound)
As the silane coupling agent, for example, a silane coupling agent having an amino group (—NH ₂ ), another silane coupling agent, or the like can be used. Among these, a silane coupling agent having an amino group (—NH ₂ ) is preferable. By capturing HF (hydrofluoric acid), which causes deterioration of the battery, by the silane coupling agent having an amino group, deterioration of the battery under a high temperature environment can be suppressed. Moreover, the compound derived from the silane compound which has the amino group which capture | acquired the fluorine becomes a good-quality film, and can further suppress degradation degradation reaction by covering the active active material surface. Examples of the silane coupling agent having an amino group (—NH ₂ ) include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ —NH ₂ )], 3-amino Examples thereof include propyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ NH ₂ ], 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like.

(Electrolyte salt)
As the electrolyte salt contained in the electrolytic solution, one containing at least a fluorine-containing lithium salt containing at least fluorine can be used. Examples of the fluorine-containing lithium salt include lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), and lithium trifluoromethanesulfonate (LiCF _3). SO ₃ ), lithium bis (fluorosulfonyl) imide (LiN (SO ₂ F) ₂ ), lithium (fluorosulfonyl) (trifluoromethylsulfonyl) imide (LiN (SO ₂ F) (SO ₂ CF ₃ )), lithium bis (Trifluoromethylsulfonyl) imide (LiN (SO ₂ CF ₃ ) ₂ ), lithium difluorooxalatoboric acid (LiC ₂ BO ₄ F ₂ ) and the like.

These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio. Among these, lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium bis (fluorosulfonyl) imide (LiN (SO ₂ F) ₂ ), lithium bis (trifluoromethanesulfonyl) At least one member selected from the group consisting of imide (LiN (SO ₂ CF ₃ ) ₂ ) and lithium bis (oxalato) boric acid (LiC ₂ BO ₄ F ₂ ) is preferable, and lithium bis (fluorosulfonyl) imide (LiN (SO ₂ F) ₂ ) and at least one selected from the group consisting of lithium bis (trifluoromethanesulfonyl) imide (LiN (SO ₂ CF ₃ ) ₂ ) are more preferred.

The electrolyte salt may contain other lithium salt together with the fluorine-containing lithium salt. Other lithium salts include lithium perchlorate (LiClO ₄ ), lithium tetraphenylborate (LiB (C ₆ H ₅ ) ₄ ), lithium methanesulfonate (LiCH ₃ SO ₃ ), lithium bis (oxalato) borate (LiC ₄ BO ₈ ), and the like.

(5-2) Battery Manufacturing Method This nonaqueous electrolyte battery is manufactured, for example, by the following manufacturing method.

(Preparation of electrolyte)
The above-described electrolytic solution is prepared. The electrolyte is impregnated in the negative electrode, and a compound derived from the cyclic carboxylic acid ester compound and the silane / siloxane compound is formed during charging and discharging of the battery. More specifically, for example, a reaction product of a decomposition product of a cyclic carboxylic acid ester compound and a silane / siloxane compound is formed at the time of charge / discharge of the battery.

Specifically, at the time of charge / discharge of a battery, for example, the compound represented by the formula (1B), the compound represented by the formula (2B), and the compound represented by the formula (3B) as the above reaction product And at least one of these compounds can be contained in the negative electrode 22. Various methods can be used as a method for causing the anode 22 to contain at least one of these compounds. For example, when forming the negative electrode active material layer 22B, at least one of a compound represented by the formula (1B), a compound represented by the formula (2B), and a compound represented by the formula (3B), and a negative electrode material At least one of a compound represented by the formula (1B), a compound represented by the formula (2B), and a compound represented by the formula (3B) by preparing a negative electrode mixture by mixing with May be contained in the negative electrode 22.

6). Sixth Embodiment (6-1) Battery Configuration A nonaqueous electrolyte battery (battery) according to a sixth embodiment of the present technology will be described. FIG. 3 shows an exploded perspective configuration of the nonaqueous electrolyte battery according to the sixth embodiment of the present technology, and FIG. 4 is an enlarged cross-sectional view taken along line II of the spirally wound electrode body 30 shown in FIG. It shows.

(Positive electrode)
The positive electrode 33 has, for example, a structure in which a positive electrode active material layer 33B is provided on both surfaces of a positive electrode current collector 33A having a pair of surfaces. Although not shown, the positive electrode 33 may have a region where the positive electrode active material layer 33B is formed only on one surface of the positive electrode current collector 33A. The positive electrode current collector 33A and the positive electrode active material layer 33B are the same as the positive electrode current collector 21A and the positive electrode active material layer 21B in the fifth embodiment, respectively.

(Negative electrode)
The negative electrode 34 has, for example, a structure in which a positive electrode active material layer 33B is provided on both surfaces of a negative electrode current collector 34A having a pair of surfaces. Although not shown, the negative electrode 34 may have a region where the negative electrode active material layer 34B is formed only on one surface of the negative electrode current collector 34A. The negative electrode current collector 34A and the negative electrode active material layer 34B are the same as the negative electrode current collector 22A and the negative electrode active material layer 22B in the fifth embodiment, respectively.

(Separator)
The separator 35 is the same as the separator 23 in the fifth embodiment.

(Nonaqueous electrolyte)
The nonaqueous electrolytic solution includes an electrolyte salt and a nonaqueous solvent that dissolves the electrolyte salt. The nonaqueous electrolytic solution is the same as that of the fifth embodiment.

(6-2) Battery Manufacturing Method This nonaqueous electrolyte battery is manufactured, for example, by the following three manufacturing methods (first to third manufacturing methods).

(First manufacturing method)
In the first manufacturing method, first, the positive electrode active material layer 33B is formed on both surfaces of the positive electrode current collector 33A, for example, by the same procedure as the manufacturing procedure of the positive electrode 21 and the negative electrode 22 of the fifth embodiment described above. Thus, the positive electrode 33 is manufactured. Further, the negative electrode active material layer 34B is formed on both surfaces of the negative electrode current collector 34A to produce the negative electrode 34.

[Modification 1]
In the example of the non-aqueous electrolyte battery according to the sixth embodiment described above, the configuration example using the gel electrolyte has been described. However, instead of the gel electrolyte, an electrolytic solution that is a liquid electrolyte is used. Also good. In this case, the exterior member 60 is filled with a non-aqueous electrolyte, and a wound body having a configuration in which the electrolyte 36 is omitted from the wound electrode body 30 is impregnated with the non-aqueous electrolyte. In this case, the nonaqueous electrolyte battery is manufactured as follows, for example.

[Modification 2]
In the above-described example of the sixth embodiment and Modification 1, the non-aqueous electrolyte battery in which the wound electrode body 30 is packaged by the exterior member 60 has been described. However, as illustrated in FIGS. A laminated electrode body 70 may be used instead of the electrode body 30. FIG. 5A is an external view of a nonaqueous electrolyte battery in which the laminated electrode body 70 is accommodated. FIG. 5B is an exploded perspective view showing a state in which the laminated electrode body 70 is accommodated in the exterior member 60. FIG. 5C is an external view showing the external appearance of the nonaqueous electrolyte battery shown in FIG. 5A from the bottom surface side.

In addition, the manufacturing method of a non-aqueous electrolyte battery produces a laminated electrode body in place of the wound electrode body 30, and a laminated body in place of the wound body (with an electrolyte layer omitted from the laminated electrode body 70). Is the same as the manufacturing method of the nonaqueous electrolyte battery of the example of the sixth embodiment and the modification 1 except that the above is manufactured.

<Seventh to Tenth Embodiments>
Hereinafter, embodiments of the present technology will be described with reference to the drawings. The description will be given in the following order.
7). Seventh embodiment (example of battery module)
8). Eighth embodiment (example of battery pack)
9. Ninth embodiment (example of battery pack)
10. Tenth embodiment (an example of a power storage system)

7). Seventh embodiment (example of battery module)
A seventh embodiment of the present technology will be described. In the seventh embodiment, a battery module using the above-described non-aqueous electrolyte battery and a battery module in which the battery unit is combined will be described.

(Battery unit)
6A to 6B are perspective views showing a configuration example of a battery unit using the nonaqueous electrolyte battery of the present technology. 6A and 6B show the battery unit 100 viewed from different sides. The side mainly shown in FIG. 6A is the front side of the battery unit 100, and is mainly shown in FIG. 6B. Let the side which is present be the back side of the battery unit 100. As shown in FIGS. 6A to 6B, the battery unit 100 includes non-aqueous electrolyte batteries 1-1 and 1-2, a bracket 110, and bus bars 120-1 and 120-2. Note that the bus bar 120-1 and the bus bar 120-2 are referred to as the bus bar 120 when they are not distinguished from each other. The nonaqueous electrolyte batteries 1-1 and 1-2 have, for example, the same structure as that of the second modification of the nonaqueous electrolyte battery according to the second embodiment, the fourth embodiment, and the sixth embodiment. Is.

The bracket 110 is a support for ensuring the strength of the non-aqueous electrolyte batteries 1-1 and 1-2. The non-aqueous electrolyte battery 1-1 is attached to the front side of the bracket 110, and the rear side of the bracket 110 is attached. A nonaqueous electrolyte battery 1-2 is mounted. The bracket 110 has substantially the same shape when viewed from either the front side or the back side, but a chamfered portion 111 is formed at one lower corner, and the chamfered portion 111 is located at the lower right. The side that can be seen is the front side, and the side where the chamfered portion 111 is seen in the lower left is the back side.

The bus bars 120-1 and 120-2 are substantially L-shaped metal members, and the connection portions connected to the tabs of the nonaqueous electrolyte batteries 1-1 and 1-2 are arranged on the side surface side of the bracket 110. The terminals connected to the outside of the battery unit 100 are mounted on both side surfaces of the bracket 110 so that the terminals are arranged on the upper surface of the bracket 110.

FIG. 7 is a perspective view showing a state where the battery unit 100 is disassembled. The upper side of FIG. 7 is the front side of the battery unit 100, and the lower side of FIG. 7 is the back side of the battery unit 100. Hereinafter, in the nonaqueous electrolyte battery 1-1, the convex portion in which the laminated electrode body is accommodated is referred to as a battery body 1-1A. Similarly, a convex portion in which the laminated electrode body is accommodated in the nonaqueous electrolyte battery 1-2 is referred to as a battery body 1-2A.

The nonaqueous electrolyte batteries 1-1 and 1-2 are attached to the bracket 110 in a state where the projecting battery main bodies 1-1A and 1-2A face each other. That is, the surface of the nonaqueous electrolyte battery 1-1 on which the positive electrode lead 3-1 and the negative electrode lead 4-1 are provided faces the front side, and the nonaqueous electrolyte battery 1-2 has the positive electrode lead 3-2 and the negative electrode lead 4-2. Is attached to the bracket 110 so that the surface on which the slab is provided faces the back side.

The bracket 110 has an outer peripheral wall 112 and a rib portion 113. The outer peripheral wall 112 is slightly wider than the outer periphery of the battery bodies 1-1A and 1-2A of the nonaqueous electrolyte batteries 1-1 and 1-2, that is, the nonaqueous electrolyte batteries 1-1 and 1-2 are mounted. It is formed so as to surround battery main bodies 1-1A and 1-2A. The rib portion 113 is formed on the inner side surface of the outer peripheral wall 112 so as to extend inward from the central portion in the thickness direction of the outer peripheral wall 112.

In the configuration example of FIG. 7, the nonaqueous electrolyte batteries 1-1 and 1-2 are inserted into the outer peripheral wall 112 from the front side and the back side of the bracket 110, and have double-sided tapes 130-1 and 130 having adhesiveness on both sides. -2 is attached to both surfaces of the rib portion 113 of the bracket 110. The double-sided tapes 130-1 and 130-2 have a substantially rectangular shape with a predetermined width along the outer peripheral ends of the nonaqueous electrolyte batteries 1-1 and 1-2. It is only necessary to provide an area where the tapes 130-1 and 130-2 are attached.

In this manner, the rib portion 113 is formed to extend inward from the inner side surface of the outer peripheral wall 112 by a predetermined width along the outer peripheral ends of the nonaqueous electrolyte batteries 1-1 and 1-2. The inside of the rib 113 is an opening. Accordingly, the nonaqueous electrolyte battery 1-1 is attached to the rib portion 113 by the double-sided tape 130-1 from the front side of the bracket 110, and is attached to the rib portion 113 by the double-sided tape 130-2 from the back side of the bracket 110. A gap is formed between the nonaqueous electrolyte battery 1-2 and the nonaqueous electrolyte battery 1-2.

That is, since the opening is formed in the central portion of the bracket 110, the nonaqueous electrolyte batteries 1-1 and 1-2 have the thickness of the rib portion 113 and the thickness of the double-sided tapes 130-1 and 130-2. The bracket 110 is attached with a gap having a total size.

(Battery module)
Next, a configuration example of the battery module 160 in which the battery unit 100 is combined will be described with reference to FIG. FIG. 8 is an exploded perspective view showing a configuration example of the battery module. As shown in FIG. 8, the battery module 160 includes a module case 150, a rubber sheet part 151, a battery part 152, a battery cover 154, a fixed sheet part 155, an electric part part 156, and a box cover 157. .

The module case 150 is a case for storing the battery unit 100 and mounting it on a device to be used. In the configuration example of FIG. 8, the module case 150 has a size that can store 24 battery units 100.

The rubber sheet portion 151 is a sheet that is laid on the bottom surface of the battery unit 100 to mitigate impact and the like. In the rubber sheet portion 151, one rubber sheet is provided for each of the three battery units 100, and eight rubber sheets are prepared to correspond to the 24 battery units 100.

In the configuration example of FIG. 8, the battery unit 152 is configured by combining 24 battery units 100. The battery unit 152 has a connection configuration in which three battery units 100 are connected in parallel to form a parallel block 153, and eight parallel blocks 153 are connected in series.

The battery cover 154 is a cover for fixing the battery part 152, and an opening corresponding to the bus bar 120 of the nonaqueous electrolyte battery 1 is provided.

The fixed sheet portion 155 is a sheet that is disposed on the upper surface of the battery cover 154 and is in close contact with and fixed to the battery cover 154 and the box cover 157 when the box cover 157 is fixed to the module case 150.

The electrical part unit 156 includes electrical components such as a charge / discharge control circuit that controls charging / discharging of the battery unit 100. For example, the charge / discharge control circuit is disposed in a space between the bus bars 120 forming two rows in the battery unit 152.

The box cover 157 is a cover for closing the module case 150 after each part is accommodated in the module case 150.

As described above, the battery unit 100 and the battery module 160 using the nonaqueous electrolyte battery of the present technology are configured.

8). Eighth Embodiment FIG. 9 shows a perspective configuration of a battery pack using single cells, and FIG. 10 shows a block configuration of the battery pack shown in FIG. In addition, in FIG. 9, the state which decomposed | disassembled the battery pack is shown.

The battery pack described here is a simple battery pack (so-called soft pack) using one secondary battery, and is built in, for example, an electronic device typified by a smartphone. For example, as shown in FIG. 10, the battery pack includes a power source 211 that is a laminated film type secondary battery according to the second embodiment, the fourth embodiment, or the sixth embodiment. And a circuit board 216 connected to the power supply 211.

A pair of

adhesive tapes

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

Further, for example, as shown in FIG. 10, the battery pack includes a power supply 211 and a circuit board 216. The circuit board 216 includes, for example, a control unit 221, a switch unit 222, a PTC 223, and a temperature detection unit 224. Since the power source 211 can be connected to the outside through the positive terminal 225 and the negative terminal 227, the power source 211 is charged / discharged through the positive terminal 225 and the negative terminal 227. The temperature detection unit 224 can detect the temperature using a temperature detection terminal (so-called T terminal) 226.

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

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

In addition, for example, when the battery voltage reaches the overdischarge detection voltage, the control unit 221 disconnects the switch unit 222 so that the discharge current does not flow in the current path of the power supply 211. For example, when a large current flows during discharge, the control unit 221 cuts off the discharge current by cutting the switch unit 222.

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

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

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

9. Ninth Embodiment FIG. 11 is a block diagram showing a circuit configuration example when the batteries according to the first to sixth embodiments of the present technology (hereinafter appropriately referred to as secondary batteries) are applied to a battery pack. FIG. The battery pack includes a switch unit 304 including an assembled battery 301, an exterior, a charge control switch 302a, and a discharge control switch 303a, a current detection resistor 307, a temperature detection element 308, and a control unit 310.

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

The assembled battery 301 is formed by connecting a plurality of secondary batteries 301a in series and / or in parallel. The secondary battery 301a is a secondary battery of the present technology. In addition, in FIG. 11, although the case where the six secondary batteries 301a are connected to 2 parallel 3 series (2P3S) is shown as an example, other n parallel m series (n and m are integers) Any connection method may be used.

The switch unit 304 includes a charge control switch 302a and a diode 302b, and a discharge control switch 303a and a diode 303b, and is controlled by the control unit 310. The diode 302b has a reverse polarity with respect to the charging current flowing from the positive terminal 321 in the direction of the assembled battery 301 and the forward polarity with respect to the discharging current flowing from the negative terminal 322 in the direction of the assembled battery 301. The diode 303b has a forward polarity with respect to the charging current and a reverse polarity with respect to the discharging current. In the example shown in FIG. 11, the switch unit 304 is provided on the + side, but may be provided on the − side.

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

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

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

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

As the charge / discharge switch, for example, a semiconductor switch such as a MOSFET can be used. In this case, the parasitic diode of the MOSFET functions as the

diodes

302b and 303b. When a P-channel FET is used as the charge / discharge switch, the switch control unit 314 supplies control signals DO and CO to the gates of the charge control switch 302a and the discharge control switch 303a, respectively. When the charge control switch 302a and the discharge control switch 303a are P-channel type, they are turned on by a gate potential that is lower than the source potential by a predetermined value or more. That is, in normal charging and discharging operations, the control signals CO and DO are set to the low level, and the charging control switch 302a and the discharging control switch 303a are turned on.

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

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

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

10. Tenth Embodiment According to the first to sixth embodiments of the present technology, the battery module according to the seventh embodiment, and the eighth to ninth embodiments. The battery pack can be used for mounting or supplying electric power to devices such as electronic devices, electric vehicles, and power storage devices.

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

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

Examples of power storage devices include power storage power supplies for buildings such as houses or power generation facilities.

Hereinafter, a specific example of a power storage system using a power storage device to which the above-described battery of the present technology is applied will be described among the application examples described above.

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

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

(10-1) Residential Power Storage System as Application Example An example in which a power storage device using a battery of the present technology is applied to a residential power storage system will be described with reference to FIG. For example, in a power storage system 400 for a house 401, power is stored from a centralized power system 402 such as a thermal power generation 402a, a nuclear power generation 402b, and a hydroelectric power generation 402c through a power network 409, an information network 412, a smart meter 407, a power hub 408, and the like. Supplied to the device 403. At the same time, power is supplied to the power storage device 403 from an independent power source such as the power generation device 404 in the home. The electric power supplied to the power storage device 403 is stored. Electric power used in the house 401 is supplied using the power storage device 403. The same power storage system can be used not only for the house 401 but also for buildings.

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

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

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

The power hub 408 performs processing such as branching of power lines and DC / AC conversion. Communication methods of the information network 412 connected to the control device 410 include a method using a communication interface such as UART (Universal Asynchronous Receiver-Transceiver), Bluetooth, ZigBee, Wi-Fi, NFC, etc. There is a method of using a sensor network based on a wireless communication standard. The Bluetooth method is applied to multimedia communication and can perform one-to-many connection communication. ZigBee uses the physical layer of IEEE (Institute of Electrical and Electronics Electronics) (802.15.4). IEEE802.15.4 is a name of a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN. NFC (Near Field Communication) is the name of short-range wireless communication technology.

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

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

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

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

(10-2) Power Storage System in Vehicle as Application Example An example in which the present technology is applied to a power storage system for a vehicle will be described with reference to FIG. FIG. 13 schematically shows an example of the configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied. A series hybrid system is a car that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power once stored in a battery.

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

Hybrid vehicle 500 travels using power driving force conversion device 503 as a power source. An example of the power / driving force conversion device 503 is a motor. The electric power / driving force converter 503 is operated by the electric power of the battery 508, and the rotational force of the electric power / driving force converter 503 is transmitted to the

driving wheels

504a and 504b. In addition, by using DC-AC (DC-AC) or reverse conversion (AC-DC conversion) at a required place, the power driving force converter 503 can be applied to either an AC motor or a DC motor. The various sensors 510 control the engine speed through the vehicle control device 509 and control the opening (throttle opening) of a throttle valve (not shown). Various sensors 510 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.

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

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

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

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

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

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

<Example 1-1>
According to the following procedure, lithium cobaltate (LiCoO ₂ ) as a positive electrode active material, and lithium titanate (Li ₄ Ti ₅₎ having a flat portion at a charge / discharge potential of about 1.55 V with respect to the lithium potential as a negative electrode active material. The laminate film type secondary battery shown in FIGS. 3 and 4 was produced using O ₁₂ ).

(Preparation of positive electrode)
First, 90 parts by mass of lithium cobaltate (LiCoO ₂ ) as a positive electrode active material, 5 parts by mass of ketjen black as a conductive agent, and 5 parts by mass of polyvinylidene fluoride as a binder were mixed homogeneously to obtain N-methylpyrrolidone. The positive electrode mixture slurry was obtained.

Next, this positive electrode mixture slurry is uniformly coated on both sides of an aluminum foil having a thickness of 10 μm, dried and compression-molded, and a positive electrode active material layer having a thickness of 30 μm per side (volume density of the active material layer) : 3.5 g / cc). This was cut into a shape having a width of 50 mm and a length of 300 mm to obtain a positive electrode.

(Preparation of negative electrode)
85 parts by mass of lithium titanate (Li ₄ Ti ₅ O ₁₂ ) as a negative electrode active material, 5 parts by mass of polyvinylidene fluoride as a binder, and 10 parts by mass of ketjen black as a conductive agent are mixed uniformly. -Methylpyrrolidone was added to obtain a negative electrode mixture slurry.

Next, this negative electrode mixture slurry is uniformly applied to one side of an aluminum foil having a thickness of 10 μm to be a negative electrode current collector, dried and compression-molded, and a negative electrode active material layer having a thickness of 30 μm per side is formed. Formed. This was cut into a shape having a width of 50 mm and a length of 300 mm to obtain a negative electrode (volume density of the mixture: 1.8 g / cc).

(Separator)
As the separator, a microporous polyethylene film having a thickness of 16 μm was used.

(Preparation of electrolyte)
As an electrolytic solution (nonaqueous electrolytic solution) that is a liquid nonaqueous electrolyte, a solvent is prepared, lithium hexafluorophosphate (LiPF ₆ ) is dissolved to 1.0 mol / kg, and an additive is further added. , 3-mercaptopropyltrimethoxysilane [(CH ₃ O) ₃ ) Si (CH ₂ ) ₃ SH] added at 1% by mass was used. The solvent is propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and ethyl isopropyl sulfone (EiPS), and PC: EMC: VC: EiPS = 37: 56: 1: 5 (mass ratio). The mixed solvent mixed in was used.

In the battery using this electrolytic solution, the compound [(CH ₃ O) ₃ Si (CH ₂ ) ₃ SS (═O) ₂ CH ₂ CH ₃ ] represented by the formula (1-2) is electrolyzed. The liquid contains 0.05 mass% as a percentage by mass with respect to the electrolytic solution, and the negative electrode also contains the compound represented by the same formula (1-2) as in the electrolytic solution. The compound represented by the formula (1-2) is a compound derived from 3-mercaptotrimethoxysilane and ethylisopropylsulfone, and is produced from a decomposition product of 3-mercaptotrimethoxysilane and ethylisopropylsulfone.

(Battery assembly)
After winding the positive electrode and the negative electrode through a separator, the positive electrode and the negative electrode were put in a bag-shaped exterior member made of an aluminum laminate film, and then 2 g of an electrolyte was injected, and then the bag was heat-sealed. Thus, a laminated film type battery of Example 1-1 was produced.

<Example 1-2 to Example 1-3>
Table 1 shows the mass ratio (PC: EMC: VC: EiPS) of propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and ethyl isopropyl sulfone (EiPS) in the electrolytic solution. I changed it to the street. The concentration of 3-mercaptopropyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ SH] was varied as shown in Table 1 below. The concentration of the compound represented by formula (1-2) [(CH ₃ O) Si (CH ₂ ) ₃ —SS (═O) ₂ CH ₂ CH ₃ ] was changed as shown in Table 1 below. It was. Except for the above, a laminated film type battery was produced in the same manner as in Example 1-1.

<Example 1-4 to Example 1-6>
The additive in the electrolyte was changed to 3-mercaptopropylmethyldimethoxysilane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ SH]. The compound in the negative electrode is changed to the compound represented by the formula (1-4) [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ —SS (═O) ₂ C (CH ₃ ) ₂ ]. changed. Except for the above, laminate film type batteries were produced in the same manner as in Examples 1-1 to 1-5.

<Comparative Example 1-1>
As the electrolytic solution, one containing no ethyl isopropyl sulfone (EiPS) and 3-mercaptopropyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ SH] was used. That is, a solvent mixture of propylene carbonate (PC), ethyl methyl carbonate (EMC), and vinylene carbonate (VC) in a ratio of PC: EMC: VC = 40: 59: 1 (mass ratio) is used as a solvent for the electrolytic solution. Using. 3-mercaptopropyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ SH] was not added. Except for the above, a laminated film type battery was produced in the same manner as in Example 1-1.

<Comparative Example 1-2 to Comparative Example 1-4>
As the electrolytic solution, one containing no chain sulfone compound was used. That is, a solvent mixture of propylene carbonate (PC), ethyl methyl carbonate (EMC), and vinylene carbonate (VC) in a ratio of PC: EMC: VC = 39: 59: 1 (mass ratio) is used as a solvent for the electrolytic solution. Using. As an additive, 3-mercaptopropyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ SH] was added to 1% by mass. The compound contained in the negative electrode was 3-mercaptopropyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ SH]. Except for the above, a laminate film type battery was produced in the same manner as in Examples 1-1 to 1-3.

<Comparative Example 1-5 to Comparative Example 1-7>
The additive in the electrolyte was changed to 3-mercaptopropylmethyldimethoxysilane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ SH]. The compound contained in the negative electrode was changed to [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ SH]. Except for the above, a laminate film type battery was produced in the same manner as in Comparative Examples 1-2 to 1-4.

<Comparative Example 1-8 to Comparative Example 1-10>
As the electrolytic solution, one containing no additive was used. That is, as a solvent, propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and ethyl isopropyl sulfone (EiPS), PC: EMC: VC: EiPS = 38: 56: 1: 5 (mass) The electrolytic solution to which 3-mercaptopropyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ SH] was not added was used. The compound contained in the negative electrode was a compound represented by the formula (2-2) [HS (= O) ₂ C ₂ H ₅ ]. Except for the above, a laminate film type battery was produced in the same manner as in Examples 1-1 to 1-3.

<Comparative Example 1-11 to Comparative Example 1-13>
An electrolyte solution containing no silane / siloxane compound was used. That is, as a solvent, propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and ethyl isopropyl sulfone (EiPS), PC: EMC: VC: EiPS = 40: 59: 1: 1 (mass) The electrolytic solution to which 3-mercaptopropyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ SH] was not added was used. The compound contained in the negative electrode was a compound represented by the formula (2-4) [HS (= O) ₂ CH (CH ₃ ) ₂ ]. Except for the above, a laminate film type battery was produced in the same manner as in Examples 1-1 to 1-3.

<Comparative Example 1-14>
A laminate film type battery was produced in the same manner as in Example 1-2, except that graphite ((C ₆ ; Graphite)) was used as the negative electrode active material.

(Evaluation)
The following evaluation was performed about each produced battery.

(High temperature cycle test)
First, each battery was charged and discharged for 2 cycles at a current of 0.2 C in an atmosphere of 23 ° C., and the discharge capacity at the second cycle was measured. Subsequently, 300 cycles of charge and discharge were repeated in an atmosphere at 65 ° C., and the discharge capacity maintenance rate at 300 cycles with respect to the discharge capacity at the second cycle was calculated as (discharge capacity at 300th cycle / discharge capacity at the second cycle) × 100. (%).

The charge / discharge conditions are constant current and constant voltage charge up to the upper limit voltage at a current of 0.2 C, and further charge until the current value reaches 0.05 C at a constant voltage at the upper limit voltage, and then ends at a current of 0.2 C. A constant current was discharged to the voltage. This “0.2 C” is a current value at which the theoretical capacity can be discharged in 5 hours. The upper limit voltage was set to 2.7V. The battery using lithium manganese phosphate described below (Example 3-3) was set to 2.7 V, and the battery using lithium iron phosphate (Example 3-2 etc.) was set to 2.4 V.

(Measures swelling when stored at high temperature)
Each battery after the initial capacity measurement is charged for 3 hours at the same upper limit voltage as described above in an atmosphere at 23 ° C., and then stored in a constant temperature bath at 80 ° C. for 24 hours in a charged state. From the difference from the previous battery thickness, the increase rate of the cell thickness during high temperature storage was determined as follows.
Increase rate of cell thickness during high temperature storage (%) = {("Battery thickness after storage"-"Battery thickness before storage") / "Battery thickness before storage"} x 100 (%)

Table 1 shows the evaluation results.

As shown in Table 1, in Examples 1-1 to 1-6, gas generation during high-temperature storage could be suppressed and increase in battery cell thickness could be reduced. In these batteries, by using an electrolytic solution containing a chain sulfone compound and a silane coupling agent, the negative electrode contains the compound represented by the formula (1-2) or the formula (1-14), thereby increasing the temperature. The cycle characteristics could be improved, gas generation during high temperature storage could be suppressed, and the increase in battery cell thickness could be reduced. The same effect can be obtained when another chain sulfone compound is used as the chain sulfone compound. The same effect can be obtained when another silane coupling agent is used as the silane coupling agent. Similar effects can be obtained when a siloxane compound is used instead of the silane coupling agent. Compounds having other disulfide bonds at the negative electrode (eg, compounds of formula (1-1), formula (1-3) to formula (1-13), formula (1-15) to formula (1-25), etc.) The same effect can be obtained also when including. (The same applies to the following examples) In Example 1-1, the compound represented by the formula (1-2), the compound represented by the formula (2-2), the formula, The compound represented by (2-6) may coexist. In Example 1-4, the compound represented by the formula (1-14), the compound represented by the formula (2-4), and the compound represented by the formula (2-8) in the electrolytic solution and the negative electrode And may coexist.

<Example 2-1 to Example 2-5>
A laminated film type battery of Example 2-4 was produced in the same manner as Example 1-2. Example 2-1 to Example 2 were carried out in the same manner as Example 2-4, except that the composition of the chain sulfone compound, ethyl isopropyl sulfone (EiPS) in the electrolytic solution was changed as shown in Table 2 below. -2, laminate film type batteries of Examples 2-3 to 2-5 were produced.

(Evaluation)
Each of the fabricated batteries was evaluated in the same manner as in Example 1-1. The evaluation results are shown in Table 2.

As shown in Table 2, in Examples 2-1 to 2-5, high-temperature cycle characteristics can be improved, gas generation during high-temperature storage can be suppressed, and an increase in battery cell thickness can be reduced. did it. In addition, when the concentration of the chain sulfone compound in the electrolytic solution is 0.5% by mass or more and 5% by mass or less, the high-temperature cycle maintenance rate becomes higher, and gas generation during high-temperature storage can be further suppressed. It could be confirmed.

<Example 3-1>
A laminated film type battery was produced in the same manner as Example 1-2.

<Example 3-2>
A laminated film type battery was produced in the same manner as in Example 3-1, except that olivine type lithium iron phosphate (LiFePO ₄ ) was used as the positive electrode active material.

<Example 3-3>
A laminate film type battery was produced in the same manner as in Example 3-1, except that olivine-type lithium iron manganese phosphate (LiFe _0.25 Mn _0.75 PO ₄ ) was used as the positive electrode active material.

(Evaluation)
Each of the fabricated batteries was evaluated in the same manner as in Example 1-1. The evaluation results are shown in Table 3.

As shown in Table 3, in Examples 3-1 to 3-3, high-temperature cycle characteristics can be improved, gas generation during high-temperature storage can be suppressed, and increase in battery cell thickness can be reduced. did it. According to Example 3-1 to Example 3-3, as the positive electrode active material species, lithium iron phosphate (LiFePO ₄ ) having an olivine structure, lithium manganese iron phosphate (LiMnFePO ₄ ) was used. A better effect was obtained.

<Example 4-1>
A laminated film type battery was produced in the same manner as in Example 3-2.

<Example 4-2>
A battery was fabricated in the same manner as in Example 4-1, except that titanium oxide (TiO ₂ ) was used as the negative electrode active material.

(Evaluation)
Each of the fabricated batteries was evaluated in the same manner as in Example 1-1. The evaluation results are shown in Table 4.

As shown in Table 4, in Examples 4-1 to 4-2, high-temperature cycle characteristics can be improved, gas generation during high-temperature storage can be suppressed, and increase in battery cell thickness can be reduced. did it. According to Example 4-1 to Example 4-2, even when the negative electrode active material species is titanium oxide (TiO ₂ ), it is possible to obtain the same effect as the negative electrode active material species as Li ₄ Ti ₅ O _12. did it.

<Example 5-1>
A laminated film type battery was produced in the same manner as in Example 3-2.

<Example 5-2>
A laminated film type battery was produced in the same manner as in Example 5-1, except that lithium bis (fluorosulfonyl) imide (LiFSI) was used as the electrolyte salt.

<Example 5-3>
A laminate film type battery was produced in the same manner as in Example 5-1, except that lithium bis (trifluorosulfonyl) imide (LiTFSI) was used as the electrolyte salt.

(Evaluation)
Each of the fabricated batteries was evaluated in the same manner as in Example 1-1. The evaluation results are shown in Table 5.

As shown in Table 5, in Examples 5-1 to 5-3, high-temperature cycle characteristics can be improved, gas generation during high-temperature storage can be suppressed, and increase in battery cell thickness can be reduced. did it. According to Examples 5-2 to 5-3, when the electrolyte salt species is LiFSI or LiTFSI, there is no deterioration due to HF derived from LiPF ₆ , high-temperature cycle characteristics, and suppression of gas generation during high-temperature storage. The effect was more excellent.

<Example 6-1>
A laminated film type battery was produced in the same manner as in Example 1-2.

<Example 6-2>
A laminated film type battery was produced in the same manner as in Example 3-2.

<Comparative Example 6-1>
Graphite ((C ₆ ; Graphite)) was used as the negative electrode active material. The electrolytic solution shown in Table 6 below was used. Except for the above, a laminated film type battery was produced in the same manner as in Example 6-1.

<Comparative Example 6-2>
Olivine type lithium iron phosphate (LiFePO ₄ ) was used as the positive electrode active material. Graphite was used as the negative electrode active material. The electrolytic solution shown in Table 6 below was used. Except for the above, a laminated film type battery was produced in the same manner as in Example 6-1.

<Comparative Example 6-3>
Olivine type lithium iron phosphate (LiFePO ₄ ) was used for the positive electrode. A laminated film type battery was produced in the same manner as in Comparative Example 6-1.

<Comparative Example 6-4>
A laminated film type battery was produced in the same manner as in Example 6-1 except that the electrolytic solution shown in Table 6 below was used.

(Cycle (5C) test)
When investigating the cycle characteristics (5C), charge and discharge the battery for one cycle in a normal temperature (23 ° C.) environment in order to stabilize the battery state, and then charge and discharge the battery for another cycle in the same environment. The discharge capacity was measured.

Subsequently, charge and discharge were repeated until the total number of cycles under the same environment reached 1000 cycles, and the discharge capacity was measured.

From this result, 5C cycle capacity retention rate (%) = (discharge capacity at 1000th cycle / discharge capacity at 2nd cycle) × 100 was calculated.

During charging, constant current charging was performed up to the upper limit voltage at a current of 5.0 C, and then constant voltage charging was performed until the current reached 0.05 C at the upper limit voltage. “Upper limit voltage−end voltage” are as follows: Example 6-1 and Comparative Example 6-3: 4.3V-3.0V, Example 6-2 and Comparative Example 6-4: 2.4V-0.5V Comparative Example 6-1: 4.2V-2.5V, Comparative Example 6-2: 3.6V-2.0V. “5.0 C” and “0.05 C” are current values at which the battery capacity (theoretical capacity) can be discharged in 12 minutes and 20 hours, respectively.

Table 6 shows the evaluation results.

As shown in Table 6, in Examples 6-1 to 6-2, lithium titanate (Li ₄ Ti ₅ O ₁₂ ) was used as the negative electrode active material species, and the chain sulfone compound and the silane coupling agent were used. By using the electrolyte solution containing the compound represented by the formula (1-2) in the negative electrode, the high output cycle characteristics could be further improved. In the case of the positive electrode: lithium cobalt oxide (LiCoO ₂ ) and the negative electrode: graphite as in Comparative Example 6-1, the cycle retention ratio when a high current value equivalent to 5 C is applied is significantly reduced.

<Example 1A-1>
According to the following procedure, lithium cobaltate (LiCoO ₂ ) as a positive electrode active material, and lithium titanate (Li ₄ Ti ₅₎ having a flat portion at a charge / discharge potential of about 1.55 V with respect to the lithium potential as a negative electrode active material. The laminate film type secondary battery shown in FIGS. 3 and 4 was produced using O ₁₂ ).

(Preparation of electrolyte)
As an electrolytic solution (nonaqueous electrolytic solution) that is a liquid nonaqueous electrolyte, a solvent is prepared, lithium hexafluorophosphate (LiPF ₆ ) is dissolved to 1.0 mol / kg, and an additive is further added. 3-aminopropylmethyldimethoxysilane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ —NH ₂ )] added at 1% by mass was used. The solvent is propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and ethyl isopropyl sulfone (EiPS), and PC: EMC: VC: EiPS = 37: 56: 1: 5 (mass ratio). The mixed solvent mixed in was used.

In the battery using this electrolytic solution, the compound represented by the formula (1A-25) is contained in the electrolytic solution in a mass percentage of 0.05% by mass with respect to the electrolytic solution. A compound represented by the same formula (1A-25) as in the liquid is included. The compound represented by the formula (1A-25) is a compound derived from 3-aminopropylmethyldimethoxysilane and a carbonate solvent, and is generated from a decomposition product of 3-aminopropylmethyldimethoxysilane and a carbonate solvent.

(Battery assembly)
After winding the positive electrode and the negative electrode through a separator, the positive electrode and the negative electrode were put in a bag-shaped exterior member made of an aluminum laminate film, and then 2 g of an electrolyte was injected, and then the bag was heat-sealed. Thus, a laminate film type battery of Example 1A-1 was produced.

<Example 1A-2 to Example 1A-3>
Table 7 below shows the mass ratio (PC: EMC: VC: EiPS) of propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and ethyl isopropyl sulfone (EiPS) in the electrolyte. Changed as shown. The concentration of 3-aminopropylmethyldimethoxysilane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ —NH ₂ )] was varied as shown in Table 7 below. The concentration of the compound represented by the formula (1A-25) was changed as shown in Table 7 below. Except for the above, a laminated film type battery was produced in the same manner as in Example 1A-1.

<Example 1A-4 to Example 1A-6>
The compound in the negative electrode was changed to a compound represented by the formula (2A-10). Except for the above, laminated film type batteries were produced in the same manner as in Examples 1A-1 to 1A-3.

<Example 1A-7 to Example 1A-9>
The compound in the negative electrode was changed to a compound represented by the formula (3A-1). Except for the above, laminated film type batteries were produced in the same manner as in Examples 1A-1 to 1A-3.

<Example 1A-10 to Example 1A-12>
As the electrolytic solution, one containing no chain sulfone compound was used. That is, a solvent mixture of propylene carbonate (PC), ethyl methyl carbonate (EMC), and vinylene carbonate (VC) in a ratio of PC: EMC: VC = 39: 59: 1 (mass ratio) is used as a solvent for the electrolytic solution. Using. As an additive, 3-aminopropyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ NH ₂ ] was added to 1% by mass. The compound in the negative electrode was changed to a compound represented by the formula (1A-26). Except for the above, laminated film type batteries were produced in the same manner as in Examples 1A-1 to 1A-3.

<Example 1A-13 to Example 1A-15>
As the electrolytic solution, one containing no chain sulfone compound was used. That is, a solvent mixture of propylene carbonate (PC), ethyl methyl carbonate (EMC), and vinylene carbonate (VC) in a ratio of PC: EMC: VC = 39: 59: 1 (mass ratio) is used as a solvent for the electrolytic solution. Using. As an additive, 3-aminopropyltriethoxysilane [(C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NH ₂ ] was added to 1% by mass. The compound in the negative electrode was changed to a compound represented by the formula (2A-12). Except for the above, laminated film type batteries were produced in the same manner as in Examples 1A-1 to 1A-3.

<Comparative Example 1A-1>
As the electrolytic solution, one containing no ethyl isopropyl sulfone (EiPS) and 3-aminopropylmethyldimethoxysilane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ —NH ₂ )] was used. That is, propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and ethyl isopropyl sulfone (EiPS) were used as the solvent of the electrolytic solution, and PC: EMC: VC = 40: 59: 1 (mass ratio). ) Was used. 3-aminopropylmethyldimethoxysilane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ —NH ₂ )] was not added. Except for the above, a laminated film type battery was produced in the same manner as in Example 1A-1.

<Comparative Example 1A-2 to Comparative Example 1A-4>
As the electrolytic solution, one containing no additive was used. That is, as a solvent, propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and ethyl isopropyl sulfone (EiPS), PC: EMC: VC: EiPS = 38: 56: 1: 5 (mass) The electrolytic solution in which 3-aminopropylmethyldimethoxysilane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ —NH ₂ ]] was not added was used. Except for the above, laminated film type batteries were produced in the same manner as in Examples 1A-1 to 1A-3.

<Comparative Example 1A-5>
A laminated film type battery was produced in the same manner as in Example 1A-2 except that graphite ((C ₆ ; Graphite)) was used as the negative electrode active material.

(Measurement of low temperature – 30 ° C discharge capacity retention rate)
Each charged battery is allowed to stand at the measured temperature for 1 hour or longer, and after the battery reaches a predetermined temperature, the battery is discharged at a constant discharge current of 0.6 A, and the discharge capacity until the cell lower limit voltage reaches 0.5 V. Was measured. The ambient temperature was increased from −30 ° C. every 10 ° C. The low temperature −30 ° C. discharge capacity retention ratio in Table 7 represents a percentage when the discharge capacity at an ambient temperature of 25 ° C. is defined as 100.

(Measures swelling when stored at high temperature)
Each battery after the initial capacity measurement is charged at an upper limit voltage for 3 hours in an atmosphere at 23 ° C., and then stored in a constant temperature bath at 80 ° C. for 24 hours in a charged state. The battery thickness after storage and the battery thickness before storage From this difference, the rate of increase in cell thickness during high temperature storage was determined as follows.
Increase rate of cell thickness during high temperature storage (%) = {("Battery thickness after storage"-"Battery thickness before storage") / "Battery thickness before storage"} x 100 (%)

Table 7 shows the evaluation results.

As shown in Table 7, in Examples 1A-1 to 1A-15, the low temperature characteristics can be improved, gas generation during high temperature storage can be suppressed, and the increase in battery cell thickness can be reduced. It was. In these batteries, an electrolyte containing an amino group-containing silane coupling agent is used, so that the negative electrode has the formula (1A-25), formula (2A-10), formula (3A-1), formula (1A-26). ) Or the compound represented by the formula (2A-12) can improve low-temperature characteristics, suppress gas generation during high-temperature storage, and reduce the increase in battery cell thickness. . The same effect can be obtained when another chain sulfone compound is used as the chain sulfone compound. The same effect can be obtained when another silane coupling agent is used as the silane coupling agent. Similar effects can be obtained when a siloxane compound is used instead of the silane coupling agent. Other compounds (for example, compounds of formula (1A-1) to formula (1A-24), formula (1A-25) to formula (1A-78), formula (2A-1) to formula (2A-9)) ), Compounds of formula (2A-11) to formula (2A-12), compounds of formula (3A-2) to formula (3A-3), etc.), the same effect can be obtained. (The same applies to the following examples)

<Example 2A-1 to Example 2A-5>
A laminated film type battery of Example 2A-4 was produced in the same manner as Example 1A-5. Example 2A-1 to Example 2A were the same as Example 2A-4 except that the composition of the chain sulfone compound, ethyl isopropyl sulfone (EiPS) in the electrolyte was changed as shown in Table 8 below. -2, laminate film type batteries of Examples 2A-3 to 2A-5 were produced.

(Evaluation)
Each battery produced was evaluated in the same manner as in Example 1A-1. The evaluation results are shown in Table 8.

As shown in Table 8, in Examples 2A-1 to 2A-5, the low temperature characteristics can be improved, the generation of gas during high temperature storage can be suppressed, and the increase in battery cell thickness can be reduced. It was.

<Example 3A-1>
A laminated film type battery was produced in the same manner as Example 1A-5.

<Example 3A-2>
A laminate film type battery was produced in the same manner as in Example 3A-1, except that olivine type lithium iron phosphate (LiFePO ₄ ) was used as the positive electrode active material.

<Example 3A-3>
A laminated film type battery was produced in the same manner as in Example 3A-1, except that olivine-type lithium iron manganese phosphate (LiFe _0.25 Mn _0.75 PO ₄ ) was used as the positive electrode active material.

(Evaluation)
Each battery produced was evaluated in the same manner as in Example 1A-1. Table 9 shows the evaluation results.

As shown in Table 9, in Examples 3A-1 to 3A-3, the low temperature characteristics can be improved, the generation of gas during high temperature storage can be suppressed, and the increase in battery cell thickness can be reduced. It was. According to Example 3A-1 to Example 3A-3, as the positive electrode active material species, lithium iron phosphate (LiFePO ₄ ) having an olivine structure and lithium manganese iron phosphate (LiMnFePO ₄ ) were used. A better effect was obtained.

<Example 4A-1>
A laminated film type battery was produced in the same manner as Example 3A-2.

<Example 4A-2>
A battery was fabricated in the same manner as in Example 4A-1, except that titanium oxide (TiO ₂ ) was used as the negative electrode active material.

(Evaluation)
Each battery produced was evaluated in the same manner as in Example 1A-1. Table 10 shows the evaluation results.

As shown in Table 10, in Examples 4A-1 to 4A-2, the low temperature characteristics can be improved, the generation of gas during high temperature storage can be suppressed, and the increase in battery cell thickness can be reduced. It was. According to Example 4A-1 to Example 4A-2, even when the negative electrode active material species is titanium oxide (TiO ₂ ), it is possible to obtain the same effect as that of the negative electrode active material species as Li ₄ Ti ₅ O _12. did it.

<Example 5A-1>
A laminated film type battery was produced in the same manner as Example 3A-2.

<Example 5A-2>
Example 5A-1 except that lithium hexafluorophosphate (LiPF ₆ ) and lithium bis (fluorosulfonyl) imide (LiFSI) were used as electrolyte salts at concentrations shown in Table 11 below. A laminate film type battery was produced.

<Example 5A-3>
Example 5A-1 except that lithium hexafluorophosphate (LiPF ₆ ) and lithium bis (trifluorosulfonyl) imide (LiTFSI) were used as electrolyte salts at the concentrations shown in Table 11 below. Thus, a laminated film type battery was produced.

(Evaluation)
Each battery produced was evaluated in the same manner as in Example 1A-1. The evaluation results are shown in Table 11.

As shown in Table 11, in Examples 5A-1 to 5A-3, the low temperature characteristics can be improved, gas generation during high temperature storage can be suppressed, and the increase in battery cell thickness can be reduced. It was. According to Example 5A-2 to Example 5A-3, when the electrolyte salt species is LiFSI or LiTFSI, deterioration due to LiPF ₆ -derived HF can be suppressed, and low temperature characteristics and gas generation suppression during high temperature storage can be suppressed. The effect was more excellent.

<Example 6A-1>
A laminated film type battery was produced in the same manner as Example 1A-5.

<Example 6A-2>
A laminated film type battery was produced in the same manner as Example 3A-2.

<Comparative Example 6A-1>
Graphite ((C ₆ ; Graphite)) was used as the negative electrode active material. As the electrolytic solution, one containing no chain sulfone compound and no silane coupling agent was used. Except for the above, a laminated film type battery was produced in the same manner as in Example 6A-1.

<Comparative Example 6A-2>
Graphite ((C ₆ ; Graphite)) was used as the negative electrode active material. As the electrolytic solution, one containing no chain sulfone compound and no silane coupling agent was used. Except for the above, a laminated film type battery was produced in the same manner as in Example 6A-2.

<Comparative Example 6A-3>
As the electrolytic solution, one containing no chain sulfone compound and no silane coupling agent was used. Except for the above, a laminated film type battery was produced in the same manner as in Example 6A-1.

<Comparative Example 6A-4>
As the electrolytic solution, one containing no chain sulfone compound and no silane coupling agent was used. Except for the above, a laminated film type battery was produced in the same manner as in Example 6A-2.

(Cycle (5C) test)
When investigating the cycle characteristics (5C), in order to stabilize the battery state, after charging and discharging the secondary battery in a normal temperature (23 ° C.) environment for one cycle, the secondary battery is further cycled in the same environment. The discharge capacity was measured by charging and discharging.

During charging, constant current charging was performed up to the upper limit voltage at a current of 5.0 C, and then constant voltage charging was performed until the current reached 0.05 C at the upper limit voltage. “Upper limit voltage−end voltage” are as follows: Example 6-1 and Comparative Example 6A-3: 4.3V-3.0V, Example 6A-2 and Comparative Example 6A-4: 2.4V-0.5V Comparative Example 6A-1: 4.2V-2.5V, Comparative Example 6A-2: 3.6V-2.0V. “5.0 C” and “0.05 C” are current values at which the battery capacity (theoretical capacity) can be discharged in 12 minutes and 20 hours, respectively.

Table 12 shows the evaluation results.

As shown in Table 12, in Examples 6A-1 to 6A-2, lithium titanate (Li ₄ Ti ₅ O ₁₂ ) was used as the negative electrode active material species, and an electrolytic solution containing a silane coupling agent was used. In addition, by including the compound represented by the formula (2A-10) in the negative electrode, the high output cycle characteristics could be further improved. In the case of the positive electrode: lithium cobalt oxide (LiCoO ₂ ) and the negative electrode: graphite as in Comparative Example 6A-1, the cycle retention ratio when a high current value equivalent to 5C is applied is significantly reduced.

<Example 1B-1>
According to the following procedure, lithium cobaltate (LiCoO ₂ ) as a positive electrode active material, and lithium titanate (Li ₄ Ti ₅₎ having a flat portion at a charge / discharge potential of about 1.55 V with respect to the lithium potential as a negative electrode active material. The laminate film type secondary battery shown in FIGS. 3 and 4 was produced using O ₁₂ ).

(Preparation of electrolyte)
As an electrolytic solution (nonaqueous electrolytic solution) that is a liquid nonaqueous electrolyte, a solvent is prepared, and lithium hexafluorophosphate (LiPF ₆ ) that is a fluorine-containing lithium salt is dissolved so as to be 1.0 mol / kg. Further, as an additive, one added with 1% by mass of 3-aminopropyltrimethoxysilane [(CH ₃ ) ₃ Si (CH ₂ ) ₃ —NH ₂ ] was used. The solvent is propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and gamma butyrolactone (GBL), with PC: EMC: VC: GBL = 31: 47: 1: 20 (mass ratio). A mixed solvent mixture was used.

In the battery using this electrolytic solution, the compound represented by the formula (1B-4) is contained in the electrolytic solution in a mass percentage of 0.05% by mass with respect to the electrolytic solution. A compound represented by the same formula (1B-4) as in the liquid is included. The compound represented by the formula (1B-4) is a compound derived from 3-aminopropyltrimethoxysilane.

(Battery assembly)
After winding the positive electrode and the negative electrode through a separator, the positive electrode and the negative electrode were put in a bag-shaped exterior member made of an aluminum laminate film, and then 2 g of an electrolyte was injected, and then the bag was heat-sealed. Thus, a laminated film type battery of Example 1B-1 was produced.

<Example 1B-2 to Example 1B-3>
Table 13 shows mass ratios (PC: EMC: VC: GBL) of propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and gamma butyrolactone (GBL) in the electrolytic solution. Changed to the street. 3-aminopropyltrimethoxysilane was changed to 3-aminopropylmethyldimethoxysilane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ —NH ₂ ]. The concentration of 3-aminopropylmethyldimethoxysilane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ —NH ₂ ] was varied as shown in Table 13 below. The concentration of the compound represented by the formula (1B-4) was changed as shown in Table 13 below. Except for the above, a laminated film type battery was produced in the same manner as in Example 1B-1.

<Example 1B-4 to Example 1B-6>
As a solvent of the electrolytic solution, propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and gamma butyrolactone (GBL) are used as PC: EMC: VC: GBL = 31: 47: 1: 20 (mass). Ratio) was used. As an additive, 3-aminopropylmethyldimethoxy silane [(CH ₃ ) (CH ₃ O) ₂ Si (CH ₂ ) ₃ NH ₂ ] was added to 1% by mass. The compound in the negative electrode was changed to a compound represented by the formula (2B-1). The compound represented by the formula (2B-1) is a compound derived from a carboxylic acid ester compound and 3-aminopropylmethyldimethoxysilane. Except for the above, laminated film type batteries were produced in the same manner as in Examples 1B-1 to 1B-3.

<Example 1B-7 to Example 1B-9>
As a solvent of the electrolytic solution, propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and gamma butyrolactone (GBL) are used as PC: EMC: VC: GBL = 31: 47: 1: 20 (mass). Ratio) was used. As an additive, 3-aminopropyltriethoxysilane [(C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NH ₂ ] was added to 1% by mass. The compound in the negative electrode was changed to a compound represented by formula (3B-5). The compound represented by the formula (2B-1) is a compound derived from a carboxylic acid ester compound and 3-aminopropyltriethoxysilane. Except for the above, laminated film type batteries were produced in the same manner as in Examples 1B-1 to 1B-3.

<Comparative Example 1B-1>
As the electrolytic solution, one containing no gamma-butyrolactone (GBL) and 3-aminopropyltrimethoxysilane was used. That is, propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and gamma butyrolactone (GBL) were used as the solvent of the electrolytic solution, and PC: EMC: VC = 40: 59: 1 (mass ratio). The mixed solvent mixed in was used. 3-aminopropyltrimethoxysilane was not added. Except for the above, a laminated film type battery was produced in the same manner as in Example 1B-1.

<Comparative Example 1B-2 to Comparative Example 1B-4>
As the electrolytic solution, one containing no cyclic carboxylic acid ester was used. That is, a solvent mixture of propylene carbonate (PC), ethyl methyl carbonate (EMC), and vinylene carbonate (VC) in a ratio of PC: EMC: VC = 39: 59: 1 (mass ratio) is used as a solvent for the electrolytic solution. Using. As an additive, 3-aminopropyltrimethoxysilane [(CH ₃ O) ₃ Si (CH ₂ ) ₃ NH ₂ ] was added to 1% by mass. The compound in the negative electrode was changed to a compound represented by formula (3B-9). Except for the above, laminated film type batteries were produced in the same manner as in Examples 1B-1 to 1B-3.

<Comparative Example 1B-5 to Comparative Example 1B-7>
As the electrolytic solution, one containing no additive was used. That is, as a solvent, propylene carbonate (PC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), and gamma butyrolactone (GBL), and PC: EMC: VC: GBL = 31.5: 47.5: 1: Using a mixed solvent mixed at 20 (mass ratio), an electrolytic solution to which 3-aminopropyltrimethoxysilane was not added was used. Except for the above, laminated film type batteries were produced in the same manner as in Examples 1B-1 to 1B-3.

<Comparative Example 1B-8>
Instead of lithium hexafluorophosphate (LiPF ₆ ) as an electrolyte salt, 1.0 mol / kg of lithium bis (oxalato) boric acid [LiC ₄ BO ₈ (LiBOB)], which is a lithium salt containing no fluorine, was dissolved. An electrolytic solution was used. A laminate film type battery was produced in the same manner as in Example 1B-2 except for the above.

<Comparative Example 1B-9>
A laminated film type battery was produced in the same manner as in Example 1B-2 except that graphite ((C ₆ ; Graphite)) was used as the negative electrode active material.

The charge / discharge conditions are constant current and constant voltage charge up to the upper limit voltage at a current of 0.2 C, and further charge until the current value reaches 0.05 C at a constant voltage at the upper limit voltage, and then ends at a current of 0.2 C. A constant current was discharged to the voltage. This “0.2 C” is a current value at which the theoretical capacity can be discharged in 5 hours. The upper limit voltage was set to 2.7V. The battery using lithium manganese phosphate described below (Example 3B-3) was set to 2.7 V, and the battery using lithium iron phosphate (Example 3B-2 etc.) was set to 2.4 V.

(Measurement of low temperature – 30 ° C discharge capacity retention rate)
Each charged battery is allowed to stand at the measured temperature for 1 hour or longer, and after the battery reaches a predetermined temperature, the battery is discharged at a constant discharge current of 0.6 A, and the discharge capacity until the cell lower limit voltage reaches 0.5 V. Was measured. The ambient temperature was increased from −30 ° C. every 10 ° C. The low temperature −30 ° C. discharge capacity retention ratio in Table 13 represents a percentage when the discharge capacity at an ambient temperature of 25 ° C. is defined as 100.

Table 13 shows the evaluation results.

As shown in Table 13, in Examples 1B-1 to 1B-9, high temperature cycle characteristics and low temperature characteristics can be improved, gas generation during high temperature storage can be suppressed, and increase in battery cell thickness is reduced. We were able to. In these batteries, the compound represented by the formula (1B-4), the formula (2B-1), or the formula (3B-5) is used for the negative electrode by using an electrolytic solution containing a silane coupling agent having an amino group. Including, the high-temperature cycle characteristics and low-temperature characteristics can be improved, gas generation during high-temperature storage can be suppressed, and the increase in battery cell thickness can be reduced. As a mechanism for suppressing gas generation, the total amount of CO ₂ gas was reduced by reducing the amount of carbonate solvent that generates CO ₂ by hydrolysis with OH-, which is a decomposition product of water, at the negative electrode. Can be considered. Further, the compound represented by the formula (1B-1), the compound represented by the formula (2B-1), or the compound represented by the formula (3B-5) covers the active negative electrode surface, so that It is considered that reductive decomposition of the liquid solvent is suppressed. Further, in Examples 1B-1 to 1-3, it is conceivable that deterioration of characteristics can be suppressed by effectively trapping HF (generated by the reaction of LiPF ₆ and water) that causes various deteriorations in the battery. . In addition, the same effect is acquired also when another cyclic carboxylic acid ester compound is used as a cyclic carboxylic acid ester compound. The same effect can be obtained when another silane coupling agent is used as the silane coupling agent. Similar effects can be obtained when a siloxane compound is used instead of the silane coupling agent. Other compounds (for example, compounds of formula (1B-1) to formula (1B-2), formula (1B-3), formula (1B-5), formula (2B-2) to formula (2B-20) ), Compounds of formula (3B-1) to formula (3B-4), formula (3B-6) to formula (3B-20), etc.), the same effect can be obtained. (The same applies to the following examples)

<Example 2B-1 to Example 2B-4>
A laminated film type battery of Example 2B-2 was produced in the same manner as Example 1B-2. Example 2B-1, Example 2B-3 to Example 2B were the same as Example 2B-2 except that the composition of gamma-butyrolactone (GBL) in the electrolyte was changed as shown in Table 14 below. -4 laminate film type battery was produced.

(Evaluation)
Each battery fabricated was evaluated in the same manner as in Example 1B-1. The evaluation results are shown in Table 14.

As shown in Table 14, in Examples 2B-1 to 2B-4, high-temperature cycle characteristics and low-temperature characteristics can be improved, gas generation during high-temperature storage can be suppressed, and increase in battery cell thickness is reduced. We were able to.

<Example 3B-1>
A laminated film type battery was produced in the same manner as Example 1B-2.

<Example 3B-2>
A laminated film type battery was produced in the same manner as in Example 3B-1, except that olivine type lithium iron phosphate (LiFePO ₄ ) was used as the positive electrode active material.

<Example 3B-3>
A laminated film type battery was produced in the same manner as in Example 3B-1, except that olivine-type lithium manganese iron phosphate (LiFe _0.25 Mn _0.75 PO ₄ ) was used as the positive electrode active material.

(Evaluation)
Each battery fabricated was evaluated in the same manner as in Example 1B-1. The evaluation results are shown in Table 15.

As shown in Table 15, in Examples 3B-1 to 3B-3, the high-temperature cycle characteristics and the low-temperature characteristics can be improved, gas generation during high-temperature storage can be suppressed, and the increase in battery cell thickness is reduced. We were able to. According to Example 3B-1 to Example 3B-3, as the positive electrode active material species, lithium iron phosphate (LiFePO ₄ ) having an olivine structure and lithium manganese iron phosphate (LiMnFePO ₄ ) were used. A better effect was obtained.

<Example 4B-1>
A laminated film type battery was produced in the same manner as Example 3B-2.

<Example 4B-2>
A battery was fabricated in the same manner as in Example 4B-1, except that titanium oxide (TiO ₂ ) was used as the negative electrode active material.

(Evaluation)
Each battery fabricated was evaluated in the same manner as in Example 1B-1. The evaluation results are shown in Table 16.

As shown in Table 16, in Examples 4B-1 to 4B-2, high temperature cycle characteristics and low temperature characteristics can be improved, gas generation during high temperature storage can be suppressed, and the increase in battery cell thickness is reduced. We were able to. According to Examples 4B-1 to 4B-2, even when the negative electrode active material species is titanium oxide (TiO ₂ ), the same effect as that of the Li ₄ Ti ₅ O ₁₂ negative electrode active material species can be obtained. did it.

<Example 5B-1>
A laminated film type battery was produced in the same manner as Example 3B-2.

<Example 5B-2>
A laminate film type battery was produced in the same manner as in Example 5B-1, except that lithium bis (fluorosulfonyl) imide (LiFSI) was used as the electrolyte salt at the concentrations shown in Table 17 below.

<Example 5B-3>
A laminate film type battery was produced in the same manner as in Example 5B-1, except that lithium bis (trifluorosulfonyl) imide (LiTFSI) was used as the electrolyte salt at the concentrations shown in Table 17 below.

(Evaluation)
Each battery fabricated was evaluated in the same manner as in Example 1B-1. The evaluation results are shown in Table 17.

As shown in Table 17, in Examples 5B-1 to 5B-3, high temperature cycle characteristics and low temperature characteristics can be improved, gas generation during high temperature storage can be suppressed, and an increase in battery cell thickness is reduced. We were able to. According to Example 5B-2 to Example 5B-3, when the electrolyte salt species is LiFSI or LiTFSI, deterioration due to LiPF ₆ -derived HF can be suppressed, high-temperature cycle characteristics and gas generation during high-temperature storage The suppression effect was more excellent.

<Example 6B-1>
A laminated film type battery was produced in the same manner as in Example 1B-5.

<Example 6B-2>
A laminated film type battery was produced in the same manner as Example 3B-2.

<Comparative Example 6B-1>
Graphite ((C ₆ ; Graphite)) was used as the negative electrode active material. As the electrolytic solution, a solution containing no cyclic carboxylic acid ester compound and no silane coupling agent was used. Except for the above, a laminated film type battery was produced in the same manner as in Example 6B-1.

<Comparative Example 6B-2>
Graphite ((C ₆ ; Graphite)) was used as the negative electrode active material. As the electrolytic solution, a solution containing no cyclic carboxylic acid ester compound and no silane coupling agent was used. Except for the above, a laminated film type battery was produced in the same manner as in Example 6B-2.

<Comparative Example 6B-3>
As the electrolytic solution, a solution containing no cyclic carboxylic acid ester compound and no silane coupling agent was used. Except for the above, a laminated film type battery was produced in the same manner as in Example 6B-1.

<Comparative Example 6B-4>
As the electrolytic solution, a solution containing no cyclic carboxylic acid ester compound and no silane coupling agent was used. Except for the above, a laminated film type battery was produced in the same manner as in Example 6B-2.

During charging, constant current charging was performed up to the upper limit voltage at a current of 5.0 C, and then constant voltage charging was performed until the current reached 0.05 C at the upper limit voltage. “Upper limit voltage−Ending voltage” are as follows: Example 6-1 and Comparative Example 6B-3: 4.3V-3.0V, Example 6B-2 and Comparative Example 6B-4: 2.4V-0.5V Comparative Example 6B-1: 4.2V-2.5V, Comparative Example 6B-2: 3.6V-2.0V. “5.0 C” and “0.05 C” are current values at which the battery capacity (theoretical capacity) can be discharged in 12 minutes and 20 hours, respectively.

Table 18 shows the evaluation results.

As shown in Table 18, in Examples 6B-1 to 6B-2, lithium titanate (Li ₄ Ti ₅ O ₁₂ ) was used as the negative electrode active material species, and an electrolytic solution containing a silane coupling agent was used. In addition, by including the compound represented by the formula (2B-1) or the formula (1B-4) in the negative electrode, the high output cycle characteristics could be further improved. In the case of the positive electrode: lithium cobaltate (LiCoO ₂ ) and the negative electrode: graphite as in Comparative Example 6B-1, the cycle retention ratio when a high current value equivalent to 5C is applied is significantly reduced.

11. Other Embodiments The present technology is not limited to the above-described embodiments and examples of the present technology, and various modifications and applications can be made without departing from the gist of the present technology.

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

Further, the configurations, methods, processes, shapes, materials, numerical values, and the like of the above-described embodiments and examples can be combined with each other without departing from the gist of the present technology.

In the above-described embodiments and examples, the laminated film type, cylindrical type battery, and the like have been described. However, a square type, coin type, button type, or the like may be used. Further, in the above-described embodiments and examples, the case where lithium is used for the electrode reaction has been described. However, other alkali metals such as sodium (Na) or potassium (K), or alkalis such as magnesium or calcium (Ca) are used. The present technology can also be applied to the case where an earth metal or other light metal such as aluminum is used, and the same effect can be obtained.

Moreover, although the said embodiment and Example demonstrate the appropriate range derived | led-out from the result of the Example about the combination of the compound in the battery of this technique, the description may become other than the above-mentioned combination. Is not completely denied. In other words, the appropriate range described above is a particularly preferable range for obtaining the effects of the present technology, and is not limited to the above range as long as the effects of the present technology can be obtained.

This technique can also take the following composition.
[1]
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing an electrolyte solution containing a nonaqueous solvent, an electrolyte salt, and an additive;
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The non-aqueous solvent includes a chain sulfone compound,
The battery, wherein the additive comprises at least one of a silane coupling agent and a siloxane compound.
[2]
The battery according to [1], wherein the one compound is a silane coupling agent having a mercapto group.
[3]
The battery according to any one of [1] to [2], wherein the content of the chain sulfone compound is 0.1% by mass or more and 20% by mass or less with respect to the electrolytic solution.
[4]
The positive electrode active material has an olivine structure, a phosphate compound containing at least one of lithium, a transition metal element, and phosphorus, or a spinel structure, and containing at least lithium and manganese. The battery according to any one of [1] to [3], which is a lithium manganese composite oxide.
[5]
Any of [1] to [4], wherein the titanium-containing inorganic oxide is a titanium-containing lithium composite oxide having at least lithium and titanium as constituent elements, or a titanium oxide having titanium and oxygen as constituent elements. The battery described in 1.
[6]
The battery according to any one of [1] to [5], wherein the electrolyte salt includes at least one of lithium bis (fluoro) sulfonylimide and lithium bis (trifluoromethylsulfonyl) imide.
[7]
The battery according to any one of [1] to [6], wherein the electrolyte further includes a polymer compound that holds the electrolytic solution.
[8]
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing a non-aqueous solvent and an electrolyte solution containing an electrolyte salt,
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The battery includes a first compound derived from a silane coupling agent or a siloxane compound and a chain sulfone compound.
[9]
The battery according to [8], wherein the silane coupling agent is a silane coupling agent having a mercapto group.
[10]
The battery according to any one of [8] to [9], further comprising a second compound derived from a chain sulfone compound.
[11]
The battery according to any one of [8] to [10], wherein the first compound includes at least one disulfide compound represented by the formula (1).

(In the formula, n is an integer of 1 to 8. R1, R2, R3 and R4 are each independently a halogen group, an alkyl group, a halogenated alkyl group, an alkoxy group or a siloxane group.)
[12]
The content of the disulfide compound represented by the formula (1) contained in the electrolyte is 0.05% by mass or more and 0.5% by mass or less based on the mass of the electrolytic solution [11]. battery.
[13]
The battery according to [10], wherein the second compound includes at least one sulfonyl compound represented by the formula (2).

(In the formula, R5 is a halogen group, an alkyl group, a halogenated alkyl group or an alkoxy group. R6 is H or Li.)
[14]
[1] A battery module having a plurality of the batteries according to any one of [13].
[15]
The battery according to any one of [1] to [13];
A control unit for controlling the battery;
A battery pack having an exterior housing the battery.
[16]
[1] An electronic device comprising the battery according to any one of [13] and receiving power supply from the battery.
[17]
The battery according to any one of [1] to [13];
A conversion device that receives supply of electric power from the battery and converts it into driving force of a vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the battery.
[18]
[1] A power storage device that includes the battery according to any one of [13] and supplies electric power to an electronic device connected to the battery.
[19]
A power information control device that transmits and receives signals to and from other devices via a network,
The power storage device according to [18], wherein charge / discharge control of the battery is performed based on information received by the power information control device.
[20]
[1] A power system that receives power from the battery according to any one of [13] or that supplies power to the battery from a power generation device or a power network

This technique can also take the following composition.
[1]
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing an electrolyte solution containing a nonaqueous solvent, an electrolyte salt, and an additive;
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The non-aqueous solvent includes a carbonate compound,
The battery, wherein the additive comprises at least one of a silane coupling agent and a siloxane compound.
[2]
The battery according to [1], wherein the one compound is a silane coupling agent having an amino group.
[3]
The battery according to any one of [1] to [2], wherein the non-aqueous solvent further includes a chain sulfone compound.
[4]
The battery according to [3], wherein the content of the chain sulfone compound is 0.1% by mass or more and 20% by mass or less with respect to the electrolytic solution.
[5]
The positive electrode active material has an olivine structure, a phosphate compound containing at least one of lithium, a transition metal element, and phosphorus, or a spinel structure, and containing at least lithium and manganese. The battery according to any one of [1] to [4], which is a lithium manganese composite oxide.
[6]
Any of [1] to [5], wherein the titanium-containing inorganic oxide is a titanium-containing lithium composite oxide having at least lithium and titanium as constituent elements, or a titanium oxide having titanium and oxygen as constituent elements. The battery described in 1.
[7]
The battery according to any one of [1] to [6], wherein the electrolyte salt includes at least one of lithium bis (fluoro) sulfonylimide and lithium bis (trifluoromethylsulfonyl) imide.
[8]
The battery according to any one of [1] to [7], wherein the electrolyte further includes a polymer compound that holds the electrolytic solution.
[9]
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing a non-aqueous solvent and an electrolyte solution containing an electrolyte salt,
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The negative electrode is a battery including a silane coupling agent or a first compound derived from a siloxane compound and a carbonate compound.
[10]
The battery according to [9], wherein the silane coupling agent is a silane coupling agent having an amino group.
[11]
The first compound includes at least one of a compound represented by the formula (1A), a compound represented by the formula (2A), and a compound represented by the formula (3A). The battery according to any one of the above.

[12]
The content of at least one of the compound represented by the formula (1A), the compound represented by the formula (2A) and the compound represented by the formula (3A) contained in the electrolyte depends on the mass of the electrolytic solution. On the other hand, the battery according to [11], which is 0.05% by mass or more and 0.5% by mass or less.
[13]
[1] A battery module having a plurality of the batteries according to any one of [12].
[14]
The battery according to any one of [1] to [12];
A control unit for controlling the battery;
A battery pack having an exterior housing the battery.
[15]
[1] An electronic device comprising the battery according to any one of [12] and receiving power supply from the battery.
[16]
The battery according to any one of [1] to [12];
A conversion device that receives supply of electric power from the battery and converts it into driving force of a vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the battery.
[17]
[1] A power storage device that includes the battery according to any one of [12] and supplies electric power to an electronic device connected to the battery.
[18]
A power information control device that transmits and receives signals to and from other devices via a network,
The power storage device according to [17], wherein charge / discharge control of the battery is performed based on information received by the power information control device.
[19]
[1] A power system that receives power supply from the battery according to any one of [12], or that supplies power to the battery from a power generation device or a power network.

This technique can also take the following composition.
[1]
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing an electrolyte solution containing a nonaqueous solvent, an electrolyte salt, and an additive;
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The non-aqueous solvent includes a cyclic carboxylic acid ester compound,
The electrolyte salt includes a fluorine-containing lithium salt containing at least fluorine,
The battery, wherein the additive comprises at least one of a silane coupling agent and a siloxane compound.
[2]
The battery according to [1], wherein the one compound is a silane coupling agent having an amino group.
[3]
The battery according to any one of [1] to [2], wherein the content of the cyclic carboxylic acid ester compound is 20% by mass or more based on the electrolytic solution.
[4]
The battery according to any one of [1] to [3], wherein the non-aqueous solvent further includes a carbonate compound.
[5]
The positive electrode active material has an olivine structure, a phosphate compound containing at least one of lithium, a transition metal element, and phosphorus, or a spinel structure, and containing at least lithium and manganese. The battery according to any one of [1] to [4], which is a lithium manganese composite oxide.
[6]
Any of [1] to [5], wherein the titanium-containing inorganic oxide is a titanium-containing lithium composite oxide having at least lithium and titanium as constituent elements, or a titanium oxide having titanium and oxygen as constituent elements. The battery described in 1.
[7]
The battery according to any one of [1] to [6], wherein the fluorine-containing lithium salt includes at least one of lithium bis (fluoro) sulfonylimide and lithium bis (trifluoromethylsulfonyl) imide.
[8]
The battery according to any one of [1] to [7], wherein the electrolyte further includes a polymer compound that holds the electrolytic solution.
[9]
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing a non-aqueous solvent and an electrolyte solution containing an electrolyte salt,
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The negative electrode is a first compound derived from a silane coupling agent or a siloxane compound, and
A battery comprising at least one of a second compound derived from a silane coupling agent or a siloxane compound and a cyclic carboxylic acid ester compound.
[10]
The battery according to [9], wherein the silane coupling agent is a silane coupling agent having an amino group.
[11]
The first compound includes at least one compound represented by the formula (1B),
The battery according to any one of [9] to [10], wherein the second compound includes at least one of a compound represented by formula (2B) and a compound represented by formula (3B).

(Wherein R9, R10 and R11 are each independently an alkyl group, a halogen group, a halogenated alkyl group or an alkoxy group. R12 and R13 are each independently a hydrogen group alkyl group, a halogen group, or R14 is a hydrogen group, an alkali metal or an alkaline earth metal, n4 is an integer of 1 to 8, n5 is an integer of 1 to 8. n6 is 1 or more It is an integer of 8 or less.)
[12]
The content of at least one of the compound represented by formula (1B), the compound represented by formula (2B) and the compound represented by formula (3B) contained in the electrolyte is based on the mass of the electrolyte solution. The battery according to [11], which is 0.05% by mass or more and 0.5% by mass or less.
[13]
The battery according to any one of [9] to [12], wherein the negative electrode further includes a silane coupling agent or a third compound derived from a siloxane compound and a carbonate compound.
[14]
A battery module having a plurality of the batteries according to any one of [1] to [13].
[15]
The battery according to any one of [1] to [13];
A control unit for controlling the battery;
A battery pack having an exterior housing the battery.
[16]
[1] An electronic device comprising the battery according to any one of [13] and receiving power supply from the battery.
[17]
The battery according to any one of [1] to [13];
A conversion device that receives supply of electric power from the battery and converts it into driving force of a vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the battery.
[18]
[1] A power storage device that includes the battery according to any one of [13] and supplies electric power to an electronic device connected to the battery.
[19]
A power information control device that transmits and receives signals to and from other devices via a network,
The power storage device according to [18], wherein charge / discharge control of the battery is performed based on information received by the power information control device.
[20]
[1] A power system that receives supply of power from the battery according to any one of [13], or that supplies power to the battery from a power generation device or a power network.
[1]
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing an electrolyte solution containing a nonaqueous solvent, an electrolyte salt, and an additive;
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The non-aqueous solvent includes a chain sulfone compound,
The battery, wherein the additive comprises at least one of a silane coupling agent and a siloxane compound.
[2]
The battery according to [1], wherein the one compound is a silane coupling agent having a mercapto group.
[3]
The battery according to any one of [1] to [2], wherein the content of the chain sulfone compound is 0.1% by mass or more and 20% by mass or less with respect to the electrolytic solution.
[4]
The battery according to any one of [1] to [3], wherein the electrolyte salt includes at least one of lithium bis (fluoro) sulfonylimide and lithium bis (trifluoromethylsulfonyl) imide.
[5]
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing a non-aqueous solvent and an electrolyte solution containing an electrolyte salt,
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The battery includes a first compound derived from a silane coupling agent or a siloxane compound and a chain sulfone compound.
[6]
The battery according to [5], wherein the silane coupling agent is a silane coupling agent having a mercapto group.
[7]
The battery according to any one of [5] to [6], further comprising a second compound derived from a chain sulfone compound.
[8]
The battery according to any one of [5] to [7], wherein the first compound includes at least one disulfide compound represented by the formula (1).

(In the formula, n is an integer of 1 to 8. R1, R2, R3 and R4 are each independently a halogen group, an alkyl group, a halogenated alkyl group, an alkoxy group or a siloxane group.)
[9]
The content of the disulfide compound represented by the formula (1) contained in the electrolyte is 0.05% by mass or more and 0.5% by mass or less with respect to the mass of the electrolytic solution [8]. battery.
[10]
The battery according to any one of [7] to [8], wherein the second compound includes at least one sulfonyl compound represented by the formula (2).

(In the formula, R5 is a halogen group, an alkyl group, a halogenated alkyl group or an alkoxy group. R6 is H or Li.)
[11]
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing an electrolyte solution containing a nonaqueous solvent, an electrolyte salt, and an additive;
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The non-aqueous solvent includes a carbonate compound,
The battery, wherein the additive comprises at least one of a silane coupling agent and a siloxane compound.
[12]
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing a non-aqueous solvent and an electrolyte solution containing an electrolyte salt,
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The negative electrode is a battery including a silane coupling agent or a third compound derived from a siloxane compound and a carbonate compound.
[13]
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing an electrolyte solution containing a nonaqueous solvent, an electrolyte salt, and an additive;
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The non-aqueous solvent includes a cyclic carboxylic acid ester compound,
The electrolyte salt includes a fluorine-containing lithium salt containing at least fluorine,
The battery, wherein the additive comprises at least one of a silane coupling agent and a siloxane compound.
[14]
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing a non-aqueous solvent and an electrolyte solution containing an electrolyte salt,
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The negative electrode is a fourth compound derived from a silane coupling agent or a siloxane compound, and
A battery comprising at least one compound of a fifth compound derived from a silane coupling agent or a siloxane compound and a cyclic carboxylic acid ester compound.
[15]
A battery module having a plurality of the batteries according to any one of [1] to [14].
[16]
The battery according to any one of [1] to [14];
A control unit for controlling the battery;
A battery pack having an exterior housing the battery.
[17]
[1] An electronic device comprising the battery according to any one of [14] and receiving power supply from the battery.
[18]
The battery according to any one of [1] to [14];
A conversion device that receives supply of electric power from the battery and converts it into driving force of a vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the battery.
[19]
[1] A power storage device including the battery according to any one of [14] and supplying electric power to an electronic device connected to the battery.
[20]
[1] A power system that receives power from the battery according to any one of [14], or that supplies power to the battery from a power generation device or a power network.

1-1 ... nonaqueous electrolyte battery, 1-1A ... battery body, 1-2 ... nonaqueous electrolyte battery, 1-2A ... battery body, 3-1 ... positive electrode lead, 3 -2 ... Positive electrode lead, 4-1 ... Negative electrode lead, 4-2 ... Negative electrode lead, 11 ... Battery can, 12, 13 ... Insulating plate, 14 ... Battery cover, 15 ... Safety valve mechanism, 15A ... Disc plate, 16 ... Heat sensitive resistance element, 17 ... Gasket, 20 ... Winding electrode body, 21 ... Positive electrode, 21A ... Positive electrode current collector Body, 21B ... positive electrode active material layer, 22 ... negative electrode, 22A ... negative electrode current collector, 22B ... negative electrode active material layer, 23 ... separator, 24 ... center pin, 25. .. Positive electrode lead, 26... Negative electrode lead, 30... Winding electrode body, 31... Positive electrode lead, 32. ... Positive electrode, 33A ... Positive electrode current collector, 33B ... Positive electrode active material layer, 34 ... Negative electrode, 34A ... Negative electrode current collector, 34B ... Negative electrode active material layer, 35 ... Separator 36 ... electrolyte 37 ... protective tape 40 ... exterior member 41 ... adhesion film 60 ... exterior member 61 ... adhesion film 70 ... laminated electrode Body 71, positive electrode lead 72, negative electrode lead 73, positive electrode, 74, negative electrode, 75, separator, 76, fixing member, 100, battery unit, 110. ..Bracket, 111 ... chamfered portion, 112 ... outer peripheral wall, 113 ... rib portion, 120 ... bus bar, 120-1 ... bus bar, 120-1 ... bus bar, 130-1 ..Double-sided tape, 130-2 ... Double-sided tape, 1 0 ... module case, 151 ... rubber sheet, 160 ... battery module, 211 ... power supply, 212 ... positive electrode lead, 213 ... negative electrode lead, 214, 215 ... tab, 216 ... Circuit board, 217 ... Lead wire with connector, 218, 219 ... Adhesive tape, 220 ... Label, 221 ... Control part, 222 ... Switch part, 224 ... Temperature Detection unit, 225... Positive electrode terminal, 227... Negative electrode terminal, 231... Insulating sheet, 301... Assembled battery, 301 a. -Diode, 303a ... Discharge control switch, 303b ... Diode, 304 ... Switch part, 307 ... Current detection resistor, 308 ... Temperature detection element, 310 ... Control unit, 311 ... Voltage detection unit, 313 ... Current measurement unit, 314 ... Switch control unit, 317 ... Memory, 318 ... Temperature detection unit, 321 ... Positive electrode terminal, 322 ... Negative electrode terminal, 400 ... Power storage system, 401 ... Housing, 402 ... Centralized power system, 402a ... Thermal power generation, 402b ... Nuclear power generation, 402c ... Hydroelectric power generation, 403 ... Power storage device, 404 ... Power generation device, 405 ... Power consumption device, 405a ... Refrigerator, 405b ... Air conditioner, 405c ... TV, 405d ... Bus, 406 ... Electric Vehicle, 406a ... Electric vehicle, 406b ... Hybrid car, 406c ... Electric motorcycle, 407 ... Smart meter, 408 ... Power hub, 409 ... Power network, 410 ... Control device, 411 ... sensor, 412 ... information network, 413 ... server, 500 ... hybrid vehicle, 501 ... engine, 502 ... generator, 503 ... electric power driving force conversion Device, 504a ... Drive wheel, 504b ... Drive wheel, 505a ... Wheel, 505b ... Wheel, 508 ... Battery, 509 ... Vehicle control device, 510 ... Sensor, 511 ..Charging port

Claims

A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing an electrolyte solution containing a nonaqueous solvent, an electrolyte salt, and an additive;
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The non-aqueous solvent includes a chain sulfone compound,
The battery, wherein the additive comprises at least one of a silane coupling agent and a siloxane compound.
The battery according to claim 1, wherein the one compound is a silane coupling agent having a mercapto group.
The battery according to claim 1, wherein the content of the chain sulfone compound is 0.1% by mass or more and 20% by mass or less with respect to the electrolytic solution.
The battery according to claim 1, wherein the electrolyte salt contains at least one of lithium bis (fluoro) sulfonylimide and lithium bis (trifluoromethylsulfonyl) imide.
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing a non-aqueous solvent and an electrolyte solution containing an electrolyte salt,
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The battery includes a first compound derived from a silane coupling agent or a siloxane compound and a chain sulfone compound.
The battery according to claim 5, wherein the silane coupling agent is a silane coupling agent having a mercapto group.
The battery according to claim 5, further comprising a second compound derived from a chain sulfone compound.
The battery according to claim 5, wherein the first compound includes at least one disulfide compound represented by the formula (1).

(In the formula, n is an integer of 1 to 8. R1, R2, R3 and R4 are each independently a halogen group, an alkyl group, a halogenated alkyl group, an alkoxy group or a siloxane group.)
The content of the disulfide compound represented by the formula (1) contained in the electrolyte is 0.05% by mass or more and 0.5% by mass or less with respect to the mass of the electrolytic solution. battery.
The battery according to claim 7, wherein the second compound includes at least one sulfonyl compound represented by the formula (2).

(In the formula, R5 is a halogen group, an alkyl group, a halogenated alkyl group or an alkoxy group. R6 is H or Li.)
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing an electrolyte solution containing a nonaqueous solvent, an electrolyte salt, and an additive;
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The non-aqueous solvent includes a carbonate compound,
The battery, wherein the additive comprises at least one of a silane coupling agent and a siloxane compound.
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing a non-aqueous solvent and an electrolyte solution containing an electrolyte salt,
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The negative electrode is a battery including a silane coupling agent or a third compound derived from a siloxane compound and a carbonate compound.
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing an electrolyte solution containing a nonaqueous solvent, an electrolyte salt, and an additive;
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The non-aqueous solvent includes a cyclic carboxylic acid ester compound,
The electrolyte salt includes a fluorine-containing lithium salt containing at least fluorine,
The battery, wherein the additive comprises at least one of a silane coupling agent and a siloxane compound.
A positive electrode including a positive electrode active material;
A negative electrode containing a negative electrode active material;
An electrolyte containing a non-aqueous solvent and an electrolyte solution containing an electrolyte salt,
The negative electrode active material includes a titanium-containing inorganic oxide containing at least titanium and oxygen as constituent elements,
The negative electrode is a fourth compound derived from a silane coupling agent or a siloxane compound, and
A battery comprising at least one compound of a fifth compound derived from a silane coupling agent or a siloxane compound and a cyclic carboxylic acid ester compound.
A battery module having a plurality of the batteries according to claim 1.
A battery according to claim 1;
A control unit for controlling the battery;
A battery pack having an exterior housing the battery.
An electronic device having the battery according to claim 1 and receiving supply of electric power from the battery.
A battery according to claim 1;
A conversion device that receives supply of electric power from the battery and converts it into driving force of a vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the battery.
A power storage device that has the battery according to claim 1 and supplies electric power to an electronic device connected to the battery.
A power system that receives power from the battery according to claim 1 or that supplies power to the battery from a power generation device or a power network.