JP4957944B2 - Secondary battery - Google Patents

Description

The present invention relates to a secondary battery using an electrolytic solution containing a cyclic carbonate derivative having a halogen atom.

  In recent years, many portable electronic devices such as a camera-integrated VTR (video tape recorder), a digital still camera, a mobile phone, a portable information terminal, or a notebook computer have appeared, and their size and weight have been reduced. Accordingly, as a portable power source for electronic devices, research and development for improving the energy density of batteries, particularly secondary batteries, are being actively promoted. Among these, lithium ion secondary batteries using a carbon material for the negative electrode, a composite material of lithium (Li) and a transition metal for the positive electrode, and a carbonate ester for the electrolyte are compared with conventional lead batteries and nickel cadmium batteries. Since a large energy density can be obtained, it is widely used.

Recently, with the improvement in performance of portable electronic devices, further improvement in capacity has been demanded, and it is considered to use tin (Sn) or silicon (Si) instead of carbon material as the negative electrode active material. Has been. This is because the theoretical capacity of tin is 994 mAh / g and the theoretical capacity of silicon is 4199 mAh / g, which is much larger than the theoretical capacity of graphite, 372 mAh / g, and an improvement in capacity can be expected. In particular, it has been reported that a negative electrode in which a thin film of tin or silicon is formed on a current collector can maintain a relatively large discharge capacity without pulverization of the negative electrode active material even by insertion and extraction of lithium ( For example, see Patent Document 1).
International Publication No. WO01 / 031724 Pamphlet

  However, tin or silicon that occludes lithium has high activity, and the cyclic carbonates or chain carbonates that are conventionally used in the electrolyte solution are decomposed, and lithium is inactivated. There was a problem of being. Therefore, by using a cyclic carbonate derivative having a halogen atom such as 4-fluoro-1,3-dioxolan-2-one or 4-chloro-1,3-dioxolan-2-one in the electrolytic solution, It has been studied to suppress the decomposition reaction of the electrolytic solution and improve the charge / discharge efficiency. However, the effect of suppressing the decomposition reaction of the electrolytic solution is not sufficient, and further improvement in charge / discharge efficiency has been desired.

This invention is made | formed in view of this problem, The objective is to provide the secondary battery which can improve charging / discharging efficiency.

A first secondary battery according to the present invention is provided with an electrolyte together with a positive electrode and a negative electrode, and the negative electrode can occlude and release an electrode reactant, and tin (Sn) and A material containing at least one of silicon (Si) , and the electrolytic solution includes a cyclic carbonate derivative having a halogen atom and at least one selected from the group consisting of compounds represented by chemical formula 1, chemical formula 2 or chemical formula 3 1 type is included.

（式中、Ａ１は、ＣＨ（Ｒ３）またはＮＨを表し、Ｒ３は水素（Ｈ）、ハロゲン、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。Ｒ１およびＲ２は、水素、ハロゲン、ＮＨ₂ 、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。）

(In the formula, A1 represents CH (R3) or NH, and R3 represents hydrogen (H), halogen, an alkyl group having 4 or less carbon atoms , or at least part of hydrogen of an alkyl group having 4 or less carbon atoms. R1 and R2 represent a group substituted with halogen, wherein hydrogen, halogen, NH ₂ , an alkyl group having 4 or less carbon atoms , or a group in which at least a part of hydrogen of an alkyl group having 4 or less carbon atoms is substituted with halogen Represents.)

（式中、Ａ２は、ＣＨ（Ｒ５）またはＮＨを表し、Ｒ５は水素、ハロゲン、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。Ｒ４は、水素、ハロゲン、ＮＨ₂ 、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。）

(In the formula, A2 represents CH (R5) or NH, and R5 represents hydrogen, halogen, an alkyl group having 4 or less carbon atoms , or at least part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen. R4 represents hydrogen, halogen, NH ₂ , an alkyl group having 4 or less carbon atoms , or a group obtained by substituting at least part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen.)

（式中、Ａ３は、ＣＨ（Ｒ６）またはＮＨを表し、Ｒ６は水素、ハロゲン、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。）

(In the formula, A3 represents CH (R6) or NH, and R6 represents hydrogen, halogen, an alkyl group having 4 or less carbon atoms , or at least a part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen. Represents the selected group.)

A second secondary battery according to the present invention includes an electrolyte solution together with a positive electrode and a negative electrode, and the negative electrode can occlude and release electrode reactants, and includes tin and silicon as constituent elements. The compound shown in Chemical Formula 4, Chemical Formula 5 or Chemical Formula 6 is chelate-bonded to at least a part of the negative electrode, and the electrolytic solution is a cyclic carbonate having a halogen atom. Derivatives are included.

（式中、Ａ１は、ＣＨ（Ｒ３）またはＮＨを表し、Ｒ３は水素（Ｈ）、ハロゲン、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。Ｒ１およびＲ２は、水素、ハロゲン、ＮＨ₂ 、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。）

(In the formula, A1 represents CH (R3) or NH, and R3 represents hydrogen (H), halogen, an alkyl group having 4 or less carbon atoms , or at least part of hydrogen of an alkyl group having 4 or less carbon atoms. R1 and R2 represent a group substituted with halogen, wherein hydrogen, halogen, NH ₂ , an alkyl group having 4 or less carbon atoms , or a group in which at least a part of hydrogen of an alkyl group having 4 or less carbon atoms is substituted with halogen Represents.)

（式中、Ａ２は、ＣＨ（Ｒ５）またはＮＨを表し、Ｒ５は水素、ハロゲン、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。Ｒ４は、水素、ハロゲン、ＮＨ₂ 、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。）

(In the formula, A2 represents CH (R5) or NH, and R5 represents hydrogen, halogen, an alkyl group having 4 or less carbon atoms , or at least part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen. R4 represents hydrogen, halogen, NH ₂ , an alkyl group having 4 or less carbon atoms , or a group obtained by substituting at least part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen.)

（式中、Ａ３は、ＣＨ（Ｒ６）またはＮＨを表し、Ｒ６は水素、ハロゲン、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。）

(In the formula, A3 represents CH (R6) or NH, and R6 represents hydrogen, halogen, an alkyl group having 4 or less carbon atoms , or at least a part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen. Represents the selected group.)

According to the first secondary battery of the present invention, since the electrolytic solution contains a cyclic carbonate derivative having a halogen atom and the compound shown in Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3, The activity can be reduced, and the decomposition reaction of the electrolytic solution in the negative electrode can be suppressed. Thus, excellent charge / discharge efficiency can be obtained.

According to the second secondary battery of the present invention, the electrolytic solution contains a cyclic carbonate derivative having a halogen atom, and at least a part of the negative electrode contains a compound represented by Chemical Formula 4, Chemical Formula 5 or Chemical Formula 6: Since it has a chelate-bonded structure, the activity of the negative electrode surface can be reduced, and the decomposition reaction of the electrolytic solution in the negative electrode can be suppressed. Thus, excellent charge / discharge efficiency can be obtained.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

(First embodiment)
FIG. 1 shows a cross-sectional configuration of a secondary battery according to an embodiment of the present invention. This secondary battery is a so-called cylindrical type, and a wound electrode body 20 in which a belt-like positive electrode 21 and a negative electrode 22 are wound through a separator 23 inside a substantially hollow cylindrical battery can 11. have. The battery can 11 is made of, for example, iron (Fe) plated with nickel (Ni), and has one end closed and the other end open. Inside the battery can 11, a pair of insulating plates 12, 13 are arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 20.

  At the open end of the battery can 11, a battery lid 14, a safety valve mechanism 15 provided inside the battery lid 14 and a heat sensitive resistance element (Positive Temperature Coefficient; PTC element) 16 are interposed via a gasket 17. It is attached by caulking, and the inside of the battery can 11 is sealed. The battery lid 14 is made of, for example, the same material as the battery can 11. The safety valve mechanism 15 is electrically connected to the battery lid 14 via the heat sensitive resistance element 16, and the disk plate 15A is reversed when the internal pressure of the battery exceeds a certain level due to an internal short circuit or external heating. Thus, the electrical connection between the battery lid 14 and the wound electrode body 20 is cut off. When the temperature rises, the heat sensitive resistance element 16 limits the current by increasing the resistance value and prevents abnormal heat generation due to a large current. The gasket 17 is made of, for example, an insulating material, and asphalt is applied to the surface.

  For example, a center pin 24 is inserted in the center of the wound electrode body 20. A positive electrode lead 25 made of aluminum or the like is connected to the positive electrode 21 of the spirally wound electrode body 20, 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 electrically connected to the battery lid 14 by being welded to the safety valve mechanism 15, and the negative electrode lead 26 is welded to and electrically connected to the battery can 11.

  FIG. 2 shows an enlarged part of the spirally wound electrode body 20 shown in FIG. The positive electrode 21 includes, for example, a positive electrode current collector 21A having a pair of opposed surfaces, and a positive electrode active material layer 21B provided on both surfaces of the positive electrode current collector 21A. The positive electrode current collector 21A is made of a metal material such as aluminum, nickel, or stainless steel, for example. The positive electrode active material layer 21B includes, for example, one or more of positive electrode materials capable of inserting and extracting lithium as a positive electrode active material, and a conductive material such as a carbon material and polyfluoride as necessary. A binder such as vinylidene may be included.

As a cathode material capable of inserting and extracting lithium, for example, lithium cobalt oxide, lithium nickel oxide or solid solutions _{thereof, (Li (Ni x Co y} Mn z) O 2)) (x, y, and z The values are 0 <x <1, 0 <y <1, 0 ≦ z <1, x + y + z = 1), or manganese spinel (LiMn ₂ O ₄ ) or its solid solution (Li (Mn _2−v Ni _v )) A lithium composite oxide such as O ₄ ) (value of v is v <2) or a phosphate compound having an olivine structure such as lithium iron phosphate (LiFePO ₄ ) is preferable. This is because a high energy density can be obtained. Examples of the positive electrode material capable of inserting and extracting lithium include oxides such as titanium oxide, vanadium oxide and manganese dioxide, disulfides such as iron disulfide, titanium disulfide and molybdenum disulfide, and sulfur. And conductive polymers such as polyaniline and polythiophene.

  The negative electrode 22 has, for example, a structure in which a negative electrode active material layer 22B is provided on both surfaces of a negative electrode current collector 22A having a pair of opposed surfaces. The anode current collector 22A is made of, for example, a metal material such as copper (Cu), nickel, or stainless steel.

  The negative electrode active material layer 22B includes, for example, any one or more of negative electrode materials capable of inserting and extracting lithium as a negative electrode active material.

  Examples of the negative electrode material capable of inserting and extracting lithium include a material containing tin or silicon as a constituent element. This is because tin and silicon have a large ability to occlude and release lithium, and a high energy density can be obtained.

  As such a negative electrode material, specifically, a simple substance, an alloy, or a compound of tin, a simple substance, an alloy, or a compound of silicon, or a material having one or more phases thereof at least in part. Is mentioned. In the present invention, alloys include those containing one or more metal elements and one or more metalloid elements in addition to those composed of two or more metal elements. Moreover, the nonmetallic element may be included. There are structures in which a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or two or more of them coexist.

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

  Examples of the tin compound or silicon compound include those containing oxygen (O) or carbon (C), and may contain the second constituent element described above in addition to tin or silicon.

  Among these, as this negative electrode material, tin, cobalt, and carbon are included as constituent elements, the carbon content is 9.9 mass% or more and 29.7 mass% or less, and the total of tin and cobalt is A CoSnC-containing material having a cobalt ratio Co / (Sn + Co) of 30% by mass to 70% by mass is preferable. This is because a high energy density can be obtained in such a composition range, and excellent cycle characteristics can be obtained.

  This CoSnC-containing material may further contain other constituent elements as necessary. As other constituent elements, for example, silicon, iron, nickel, chromium, indium, niobium (Nb), germanium, titanium, molybdenum (Mo), aluminum, phosphorus, gallium (Ga) or bismuth are preferable, and two or more kinds are included. May be included. This is because the capacity or cycle characteristics can be further improved.

  This CoSnC-containing material has a phase containing tin, cobalt, and carbon, and this phase preferably has a low crystallinity or an amorphous structure. In this CoSnC-containing material, it is preferable that at least a part of carbon as a constituent element is bonded to a metal element or a semimetal element as another constituent element. The decrease in cycle characteristics is thought to be due to the aggregation or crystallization of tin or the like, but this is because such aggregation or crystallization can be suppressed by combining carbon with other elements. .

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

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

  As a negative electrode material capable of inserting and extracting lithium, for example, a material containing another metal element or other metalloid element capable of forming an alloy with lithium as a constituent element can also be used. Such metal elements or metalloid elements include magnesium (Mg), boron (B), aluminum, gallium, indium, germanium, lead (Pb), bismuth, cadmium (Cd), silver, zinc, hafnium (Hf). , Zirconium (Zr), yttrium (Y), palladium (Pd), or platinum (Pt).

  As a negative electrode material capable of inserting and extracting lithium, in addition to these negative electrode materials, other negative electrode materials may be mixed and used. Examples of other negative electrode materials include carbon materials such as graphite, non-graphitizable carbon, and graphitizable carbon. Such a carbon material has very little change in crystal structure due to insertion and extraction of lithium, and when used with the above-described negative electrode material, a high energy density and excellent cycle characteristics can be obtained. It is also preferable because it functions as a conductive material.

  At least a part of the surface of the negative electrode material capable of inserting and extracting lithium is chelate-bonded with, for example, one or more of the compounds shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9. . Specifically, for example, a chelate bond is formed with a silicon atom or a tin atom of the negative electrode material, and the chemical formula 10 (1), (2), chemical formula 11 (1), (2), or chemical formula 12 (1), (2) is obtained. The structure shown is formed. Thereby, the activity of the surface of the negative electrode material can be reduced, and the decomposition reaction of the electrolytic solution can be suppressed.

式中、Ａ１は、ＣＨ（Ｒ３）またはＮＨを表し、Ｒ３は水素（Ｈ）、ハロゲン、アルキル基、またはアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。Ｒ１およびＲ２は、水素、ハロゲン、ＮＨ₂ 、アルキル基、またはアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。Ｒ１，Ｒ２およびＲ３は、互いに同一でも異なっていてもよい。また、Ｒ１およびＲ２は、水素、ハロゲン、ＮＨ₂ 、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基が好ましく、Ｒ３は、水素、ハロゲン、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基が好ましい。

In the formula, A1 represents CH (R3) or NH, and R3 represents hydrogen (H), a halogen, an alkyl group, or a group obtained by substituting at least a part of hydrogen of an alkyl group with a halogen. R1 and R2 represent hydrogen, halogen, NH ₂ , an alkyl group, or a group obtained by substituting at least part of hydrogen of an alkyl group with halogen. R1, R2 and R3 may be the same or different from each other. R1 and R2 are preferably hydrogen, halogen, NH ₂ , an alkyl group having 4 or less carbon atoms, or a group in which at least part of hydrogen of an alkyl group having 4 or less carbon atoms is substituted with halogen, and R3 is Hydrogen, halogen, an alkyl group having 4 or less carbon atoms, or a group obtained by substituting at least a part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen is preferable.

式中、Ａ２は、ＣＨ（Ｒ５）またはＮＨを表し、Ｒ５は水素、ハロゲン、アルキル基、またはアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。Ｒ４は、水素、ハロゲン、ＮＨ₂ 、アルキル基、またはアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。Ｒ４およびＲ５は、互いに同一でも異なっていてもよい。また、Ｒ４は、水素、ハロゲン、ＮＨ₂ 、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基が好ましく、Ｒ５は、水素、ハロゲン、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基が好ましい。

In the formula, A2 represents CH (R5) or NH, and R5 represents hydrogen, halogen, an alkyl group, or a group obtained by substituting at least part of hydrogen of an alkyl group with halogen. R4 represents hydrogen, halogen, NH ₂ , an alkyl group, or a group in which at least part of hydrogen of the alkyl group is substituted with halogen. R4 and R5 may be the same or different from each other. R4 is preferably hydrogen, halogen, NH ₂ , an alkyl group having 4 or less carbon atoms, or a group in which at least a part of hydrogen of the alkyl group having 4 or less carbon atoms is substituted with halogen, and R5 is hydrogen, Halogen, an alkyl group having 4 or less carbon atoms, or a group obtained by substituting at least a part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen is preferable.

式中、Ａ３は、ＣＨ（Ｒ６）またはＮＨを表し、Ｒ６は水素、ハロゲン、アルキル基、またはアルキル基の少なくとも一部の水素をハロゲンで置換した基を表す。また、Ｒ６は、水素、ハロゲン、炭素数が４以下のアルキル基、または炭素数が４以下のアルキル基の少なくとも一部の水素をハロゲンで置換した基が好ましい。

In the formula, A3 represents CH (R6) or NH, and R6 represents hydrogen, halogen, an alkyl group, or a group obtained by substituting at least part of hydrogen of an alkyl group with halogen. R6 is preferably hydrogen, halogen, an alkyl group having 4 or less carbon atoms, or a group obtained by substituting at least part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen.

式中、Ａ１，Ｒ１およびＲ２は化７と同様である。

In the formula, A1, R1 and R2 are the same as in Chemical formula 7.

式中、Ａ２およびＲ４は化８と同様である。

In the formula, A2 and R4 are the same as those in Chemical formula 8.

式中、Ａ３は化９と同様である。

In the formula, A3 is the same as in formula 9.

  The separator 23 separates the positive electrode 21 and the negative electrode 22 and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes. The separator 23 is made of, for example, a porous film made of synthetic resin made of polytetrafluoroethylene, polypropylene, polyethylene or the like, or a multi-hard film made of ceramic, and these two or more kinds of porous films are laminated. It may be made the structure.

  For example, the separator 23 is impregnated with an electrolytic solution that is a liquid electrolyte. The electrolytic solution contains, for example, a solvent and an electrolyte salt dissolved in the solvent.

  The solvent contains a high dielectric constant solvent having a relative dielectric constant of 30 or more. This is because the number of lithium ions can be increased.

  The high dielectric constant solvent contains a cyclic carbonate derivative having a halogen atom. This is because a good film can be formed on the negative electrode 22 and the decomposition reaction of the electrolytic solution can be suppressed. Examples of such cyclic carbonate derivatives include fluorinated ethylene carbonates such as 4-fluoro-1,3-dioxolan-2-one shown in Chemical formula 13 (1), or Chemical formula 13 (2). Ethylene difluoride carbonate such as 4-methyl-5-fluoro-1,3-dioxolan-2-one or 4,5-difluoro-1,3-dioxolan-2-one shown in Chemical formula 13 (3), Or chlorine such as 4-trifluoromethyl-1,3-dioxolan-2-one represented by Chemical Formula 13 (4) or 4-chloro-1,3-dioxolan-2-one represented by Chemical Formula 13 (5) And ethylene carbonate. Of these, 4-fluoro-1,3-dioxolan-2-one or 4-chloro-1,3-dioxolan-2-one is preferred, and 4-fluoro-1,3-dioxolan-2-one is particularly desirable. This is because a higher effect can be obtained. One kind of cyclic carbonate derivative may be used alone, or a plurality of kinds may be mixed and used.

  In addition to these cyclic carbonate derivatives, other high dielectric constant solvents may be mixed and used as the high dielectric constant solvent. Other high dielectric constant solvents include, for example, cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate or vinyl ethylene carbonate, lactones such as γ-butyrolactone or γ-valerolactone, or N-methyl Examples include lactams such as 2-pyrrolidone, cyclic carbamates such as N-methyl-2-oxazolidinone, and sulfone compounds such as tetramethylene sulfone. As other high dielectric constant solvents, one kind may be used alone, or a plurality of kinds may be mixed and used.

  Moreover, it is preferable to mix and use a low-viscosity solvent having a viscosity of 1 mPa · s or less as the high dielectric constant solvent. This is because high ion conductivity can be obtained. Examples of the low-viscosity solvent include chain carbonate esters such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, or methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethyl acetate or A chain carboxylic acid ester such as ethyl trimethylacetate, or a chain amide such as N, N-dimethylacetamide, a chain carbamic acid ester such as methyl N, N-diethylcarbamate, ethyl N, N-diethylcarbamate, or Examples include ethers such as 1,2-dimethoxyethane, tetrahydrofuran, tetrahydropyran, and 1,3-dioxolane. One low viscosity solvent may be used alone, or a plurality of low viscosity solvents may be mixed and used.

As the electrolyte salt, e.g., lithium hexafluorophosphate (LiPF _6), lithium tetrafluoroborate (LiBF _4), lithium hexafluoroarsenate (LiAsF _6), lithium hexafluoro antimonate (LiSbF ₆₎ , Inorganic lithium salts such as lithium perchlorate (LiClO ₄ ), lithium tetrachloroaluminate (LiAlCl ₄ ), or lithium trifluoromethanesulfonate (CF ₃ SO ₃ Li), lithium bis (trifluoromethanesulfone) imide ((CF ₃ SO ₂ ) ₂ NLi), lithium bis (pentafluoroethanesulfone) imide ((C ₂ F ₅ SO ₂ ) ₂ NLi), lithium tris (trifluoromethanesulfone) methide ((CF ₃ SO ₂ ) ₃ CLi), etc. Examples thereof include lithium salts of perfluoroalkanesulfonic acid derivatives. One electrolyte salt may be used alone, or a plurality of electrolyte salts may be mixed and used.

  This electrolytic solution preferably contains the compound shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9. This is because, as described above, chelate bonding to the negative electrode material can reduce the activity of the surface of the negative electrode material and suppress the decomposition reaction of the electrolytic solution. One of the compounds shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9 may be used alone, or a plurality of types may be mixed and used.

  Specific examples of the compounds shown in Chemical formula 7, Chemical formula 8 or Chemical formula 9 include acetylacetone represented by chemical formula 14 (1), hexafluoroacetylacetone represented by chemical formula 14 (2), and chemical formula 14 (3). Diacetamide, bistrifluoroacetamide shown in Chemical formula 14 (4), malonyl chloride shown in Chemical formula 14 (5), bisformimide shown in Chemical formula 14 (6), biuret shown in Chemical formula 14 (7) There are dicyanamide shown in 14 (8), malononitrile shown in Chemical formula 14 (9), and cyanourea shown in Chemical formula 14 (10).

  The content of the compound shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9 is preferably 0.1% by mass or more and 5% by mass or less in the electrolytic solution. This is because a high effect can be obtained within this range.

  For example, the secondary battery can be manufactured as follows.

  First, for example, the positive electrode active material layer 21B is formed on the positive electrode current collector 21A to produce the positive electrode 21. The positive electrode active material layer 21B is prepared, for example, by mixing a positive electrode active material powder, a conductive material, and a binder to prepare a positive electrode mixture, and then using the positive electrode mixture in a solvent such as N-methyl-2-pyrrolidone. The positive electrode mixture slurry is dispersed to form a positive electrode mixture slurry, and the positive electrode mixture slurry is applied to the positive electrode current collector 21A, dried, and compression molded. Further, for example, in the same manner as the positive electrode 21, the negative electrode active material layer 22 </ b> B is formed on the negative electrode current collector 22 </ b> A to produce the negative electrode 22.

  Next, 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, the positive electrode 21 and the negative electrode 22 are wound through the separator 23, 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 welded to the battery can 11. The positive electrode 21 and the negative electrode 22 are sandwiched between a pair of insulating plates 12 and 13 and stored in the battery can 11. After that, an electrolytic solution is injected into the battery can 11 and impregnated in the separator 23, and the battery lid 14, the safety valve mechanism 15 and the heat sensitive resistance element 16 are caulked through the gasket 17 at the opening end of the battery can 11. To fix. At that time, for example, at least one of the compounds shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9 is added to the electrolytic solution, and at least a part thereof is chelate-bonded to the surface of the negative electrode 22. Thereby, the secondary battery shown in FIGS. 1 and 2 is completed.

  In the secondary battery, when charged, for example, lithium ions are extracted from the positive electrode 21 and inserted in the negative electrode 22 through the electrolytic solution. On the other hand, when discharging is performed, for example, lithium ions are extracted from the negative electrode 22 and inserted in the positive electrode 21 through the electrolytic solution. At that time, the electrolytic solution contains a cyclic carbonate derivative having a halogen atom, and the compound shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9 is chelate-bonded to at least a part of the negative electrode 22. Therefore, the activity of the surface of the negative electrode 22 is reduced, and the decomposition reaction of the electrolytic solution is suppressed.

  As described above, according to the present embodiment, the electrolyte solution includes a cyclic carbonate derivative having a halogen atom, and the negative electrode 22 has a structure in which the compound shown in Chemical Formula 7, Chemical Formula 8, or Chemical Formula 9 is chelate-bonded. Or because the electrolyte contains a cyclic carbonate derivative having a halogen atom and the compound shown in Chemical Formula 7, Chemical Formula 8, or Chemical Formula 9, the surface activity of the negative electrode 22 is reduced. And the decomposition reaction of the electrolytic solution in the negative electrode 22 can be suppressed. Thus, excellent charge / discharge efficiency can be obtained.

(Second Embodiment)
The secondary battery according to the second embodiment of the present invention has the same configuration and operation as the secondary battery according to the first embodiment, except that the configuration of the negative electrode is different. It can be manufactured in the same manner. Therefore, with reference to FIG. 1 and FIG. 2, the same code | symbol is attached | subjected to a corresponding component and description of the same part is abbreviate | omitted.

  The negative electrode 22 has a structure in which a negative electrode active material layer 22B is provided on both surfaces of a negative electrode current collector 22A, similarly to the secondary battery according to the first embodiment. The negative electrode active material layer 22B contains, for example, a material containing tin or silicon as a constituent element as a negative electrode active material. Specifically, for example, it contains a simple substance, an alloy, or a compound of tin, or a simple substance, an alloy, or a compound of silicon, and may contain two or more of them.

  The negative electrode active material layer 22B is formed by using, for example, a vapor phase method, a liquid phase method, a thermal spraying method, a firing method, or two or more of these methods. The electrical conductor 22A is preferably alloyed at least at a part of the interface. Specifically, it is preferable that the constituent element of the negative electrode current collector 22A is diffused in the negative electrode active material layer 22B, the constituent element of the negative electrode active material is diffused in the negative electrode current collector 22A, or they are mutually diffused at the interface. This is because breakage due to expansion / contraction of the negative electrode active material layer 22B due to charging / discharging can be suppressed, and electronic conductivity between the negative electrode active material layer 22B and the negative electrode current collector 22A can be improved. . The firing method is, for example, a method in which a particulate negative electrode active material is mixed with a binder, dispersed in a solvent, applied, and then heat treated at a temperature higher than the melting point of the binder. .

(Third embodiment)
FIG. 3 shows the configuration of the secondary battery according to the third embodiment. This secondary battery is a so-called laminate film type, and has a wound electrode body 30 to which a positive electrode lead 31 and a negative electrode lead 32 are attached accommodated in a film-shaped exterior member 40.

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

  The exterior member 40 is made of, for example, a rectangular aluminum laminated film in which a nylon film, an aluminum foil, and a polyethylene film are bonded together in this order. For example, the exterior member 40 is disposed so that the polyethylene film side and the wound electrode body 30 face each other, and the outer edge portions are in close contact with each other by fusion bonding or an adhesive. An adhesive 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, for example, a polyolefin resin such as polyethylene, polypropylene, modified polyethylene, or modified polypropylene.

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

  FIG. 4 shows a cross-sectional structure taken along line II of the spirally wound electrode body 30 shown in FIG. The electrode winding body 30 is obtained by stacking and winding a positive electrode 33 and a negative electrode 34 with a separator 35 and an electrolyte 36, and the outermost peripheral portion is protected by a protective tape 37.

  The positive electrode 33 has a structure in which a positive electrode active material layer 33B is provided on both surfaces of a positive electrode current collector 33A. The negative electrode 34 has a structure in which a negative electrode active material layer 34B is provided on both surfaces of a negative electrode current collector 34A, and the negative electrode active material layer 34B and the positive electrode active material layer 33B are arranged to face each other. The configuration of the positive electrode current collector 33A, the positive electrode active material layer 33B, the negative electrode current collector 34A, the negative electrode active material layer 34B, and the separator 35 is the same as that of the positive electrode current collector 21A in the secondary battery according to the first or second embodiment. The positive electrode active material layer 21B, the negative electrode current collector 22A, the negative electrode active material layer 22B, and the separator 23 are the same.

  The electrolyte 36 has a so-called gel shape including the electrolytic solution described in the first embodiment and a polymer compound serving as a holding body that holds the electrolytic solution. Examples of the polymer compound include, for example, an ether polymer compound such as polyethylene oxide or a crosslinked product containing polyethylene oxide, an ester polymer compound such as polymethacrylate, or an acrylate polymer compound, or polyvinylidene fluoride or vinylidene fluoride. Examples thereof include polymers of vinylidene fluoride such as a copolymer with hexafluoropropylene, and any one of these or a mixture of two or more thereof is used. In particular, from the viewpoint of redox stability, it is desirable to use a fluorine-based polymer compound such as a vinylidene fluoride polymer.

  The electrolyte 36 may be used as it is as a liquid electrolyte without holding the electrolytic solution in the polymer compound. In this case, the electrolytic solution is impregnated in the separator 35.

  For example, the secondary battery can be manufactured as follows.

  First, a precursor solution containing an electrolytic solution, a polymer compound, and a mixed solvent is applied to each of the positive electrode 33 and the negative electrode 34, and the mixed solvent is volatilized to form the electrolyte 36. Next, 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. Subsequently, the positive electrode 33 and the negative electrode 34 on which the electrolyte 36 is formed are laminated via a separator 35 to form a laminated body, and then the laminated body is wound in the longitudinal direction, and a protective tape 37 is adhered to the outermost peripheral portion. Thus, the wound electrode body 30 is formed. After that, for example, the wound electrode body 30 is sandwiched between the exterior members 40, and the outer edge portions of the exterior members 40 are sealed and sealed by thermal fusion or the like. At that 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 secondary battery shown in FIGS. 3 and 4 is obtained.

  Instead of winding the electrolyte 36 on the positive electrode 33 and the negative electrode 34, the positive electrode 33 and the negative electrode 34 are wound via the separator 35 and sandwiched between the exterior members 40. And an electrolyte composition containing a monomer of a polymer compound may be injected so that the monomer is polymerized inside the exterior member 40.

  Further, when an electrolytic solution is used as the electrolyte 36, the positive electrode 33 and the negative electrode 34 are wound as described above and sandwiched between the exterior members 40, and then the electrolytic solution is injected to seal the exterior member 40.

  The operation and effect of this secondary battery are the same as those of the secondary battery according to the first or second embodiment described above.

  Further, specific embodiments of the present invention will be described in detail.

(Examples 1-1 to 1-11)
The secondary battery shown in FIGS. First, 94 parts by mass of lithium cobalt composite oxide (LiCoO ₂ ) as a positive electrode active material, 3 parts by mass of graphite as a conductive material, and 3 parts by mass of polyvinylidene fluoride as a binder were mixed, and then N-methyl as a solvent. -2-Pyrrolidone was added to obtain a positive electrode mixture slurry. Next, the obtained positive electrode mixture slurry was uniformly applied to both surfaces of a positive electrode current collector 33A made of an aluminum foil having a thickness of 20 μm and dried to form a positive electrode active material layer 33B having a thickness of 70 μm. After that, the positive electrode current collector 33A on which the positive electrode active material layer 33B was formed was cut into a shape having a width of 50 mm and a length of 300 mm to produce the positive electrode 33.

  Further, silicon was used as the negative electrode active material, and a negative electrode active material layer 34B made of silicon having a thickness of 5 μm was formed on the negative electrode current collector 34A made of a copper foil having a thickness of 15 μm by a sputtering method. After that, the negative electrode current collector 34A on which the negative electrode active material layer 34B was formed was cut into a shape having a width of 50 mm and a length of 300 mm to produce the negative electrode 34.

  After producing the positive electrode 33 and the negative electrode 34, the positive electrode lead 31 made of aluminum is attached to the positive electrode 33, and the negative electrode lead 32 made of nickel is attached to the negative electrode 34, and the separator 35 made of a microporous polyethylene film having a thickness of 20 μm is interposed. The positive electrode 33 and the negative electrode 34 were laminated and wound to obtain a wound electrode body. Next, after sandwiching the wound electrode body between the exterior members 40 made of an aluminum laminate film, the outer edges of the exterior members 40 were bonded to form a bag shape with one side left. At that time, the positive electrode lead 31 and the negative electrode lead 32 are led out of the exterior member 40. Subsequently, 2 g of electrolyte solution was injected into the exterior member 40 from the open side and impregnated in the separator 35, and then the open side of the exterior member 40 was bonded by thermal fusion, and the secondary shown in FIGS. A battery was obtained.

  The electrolytic solution includes a cyclic carbonate derivative having a halogen atom as a high dielectric constant solvent, diethyl carbonate as a low viscosity solvent, lithium hexafluorophosphate as an electrolyte salt, and a cyclic carbonate derivative: diethyl carbonate: Lithium hexafluorophosphate = 42: 42: 16 was mixed at a mass ratio, and further added with additives. At that time, the content of the additive in the electrolytic solution was 1.0% by mass. The cyclic carbonate derivative is 4-chloro-1,3-dioxolan-2-one (ClEC) in Example 1-1, and 4-fluoro-1,3 in Examples 1-2 to 1-11. -Dioxolan-2-one (FEC). Further, as the additive, as the compound shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9, malonyl chloride shown in Chemical Formula 14 (5) was used in Examples 1-1 and 1-2, and in Example 1-3, Using acetylacetone shown in Chemical formula 14 (1), Example 1-4 using hexafluoroacetylacetone shown in Chemical formula 14 (2), and Example 1-5 using diacetamide shown in Chemical formula 14 (3) In Example 1-6, bistrifluoroacetamide shown in Chemical formula 14 (4) was used, in Example 1-7, bisformimide shown in Chemical formula 14 (6) was used, and in Example 1-8, Chemical formula 14 ( The biuret shown in 7) was used. In Example 1-9, the dicyanamide shown in Chemical formula 14 (8) was used. In Example 1-10, the malononitrile shown in Chemical formula 14 (9) was used. Then, cyanourine shown in Chemical formula 14 (10) It was used.

  As Comparative Example 1-1 with respect to Examples 1-1 to 1-11, except that ethylene carbonate was used in place of the cyclic carbonate derivative, the others were the same as those of Examples 1-1 to 1-11. A secondary battery was produced. At that time, the additive was malonyl chloride. Further, as Comparative Examples 1-2 to 1-4, secondary batteries were fabricated in the same manner as in Examples 1-1 to 1-11 except that the additive was not added. At that time, the high dielectric constant solvent was ethylene carbonate in Comparative Example 1-2, 4-chloro-1,3-dioxolan-2-one in Comparative Example 1-3, and 4-fluoro- in Comparative Example 1-4. It was 1,3-dioxolan-2-one.

  Furthermore, in Comparative Example 1-5, a secondary battery was fabricated in the same manner as in Examples 1-1 to 1-11, except that dimethyl malonate shown in Chemical formula 15 was used as an additive. At that time, the high dielectric constant solvent was 4-fluoro-1,3-dioxolan-2-one. Dimethyl malonate is not included in any of the compounds shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9.

  For the fabricated secondary batteries of Examples 1-1 to 1-11 and Comparative examples 1-1 to 1-5, in an environment of 23 ° C., the battery was charged with 900 mA and 4.2 V as the upper limit for 12 hours, and then suspended for 10 minutes. Then, the charging / discharging of discharging until reaching 2.5 V at 900 mA is repeated, and the discharge capacity maintenance ratio at the 50th cycle relative to the discharge capacity at the first cycle, that is, (discharge capacity at the 50th cycle / discharge capacity at the first cycle) ) × 100 (%). The results are shown in Table 1.

  As shown in Table 1, according to Example 1-1 or Examples 1-2 to 1-11 using the cyclic carbonate derivative and the compound shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9, In addition, the discharge capacity retention ratio was improved as compared with Comparative Example 1-3 or Comparative Example 1-4 in which the compound shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9 was not used. Moreover, the discharge capacity maintenance rate improved rather than the comparative example 1-1 which did not use a cyclic carbonate derivative. Further, in contrast to Comparative Example 1-2 in which the cyclic carbonate derivative and the compound shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9 were not used, chemical formula 7, chemical formula 8 or chemical formula 9 was used without using the cyclic carbonate derivative. In Comparative Example 1-1 using the compound shown in (2), the effect of improving the discharge capacity retention rate was hardly observed. In addition, in Comparative Example 1-5 using dimethyl malonate which is not included in the compound shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9, the discharge capacity retention rate was lower than that in Comparative Example 1-4 which did not contain this. .

  That is, it was found that the charge / discharge efficiency can be improved if the electrolytic solution contains the cyclic carbonate derivative and the compound shown in Chemical Formula 7, Chemical Formula 8, or Chemical Formula 9.

(Examples 2-1 to 2-11, 3-1 to 3-11)
In Examples 2-1 to 2-11, tin is used as the negative electrode active material, and the negative electrode active material layer 34B made of tin having a thickness of 5 μm is formed on the negative electrode current collector 34A made of copper foil having a thickness of 15 μm by vapor deposition. Except for the above, secondary batteries were fabricated in the same manner as in Examples 1-1 to 1-11.

  As Examples 3-1 to 3-11, a CoSnC-containing material powder containing indium and titanium is used as the negative electrode active material, 94 parts by mass of this CoSnC-containing material powder, and 3 mass of graphite which is a negative electrode active material and also a conductive material And 3 parts by weight of polyvinylidene fluoride as a binder are dispersed in N-methyl-2-pyrrolidone as a solvent, and then uniformly applied to a negative electrode current collector 34A made of a copper foil having a thickness of 15 μm and dried. A secondary battery was fabricated in the same manner as in Examples 1-1 to 1-11 except that the negative electrode active material layer 34B having a thickness of 70 μm was formed.

  At that time, the CoSnC-containing material powder was synthesized by mixing a tin-cobalt-indium-titanium alloy powder and a carbon powder and utilizing a mechanochemical reaction. When the composition of the obtained CoSnC-containing material was analyzed, the tin content was 48.0% by mass, the cobalt content was 23.0% by mass, the indium content was 5.0% by mass, The content was 2.0% by mass, the carbon content was 20.0% by mass, and the ratio Co / (Sn + Co) of cobalt to the total of tin and cobalt was 32% by mass. The carbon content was measured by a carbon / sulfur analyzer, and the contents of tin, cobalt, indium and titanium were measured by ICP (Inductively Coupled Plasma) emission analysis. Further, when X-ray diffraction was performed on the obtained CoSnC-containing material, a diffraction peak having a wide half-width with a diffraction angle 2θ of 1.0 ° or more was observed between diffraction angles 2θ = 20 ° to 50 °. It was. Further, when XPS was performed on the CoSnC-containing material, a peak P1 was obtained as shown in FIG. When the peak P1 was analyzed, a peak P2 of surface contamination carbon and a peak P3 of C1s in the CoSnC-containing material on the lower energy side than the peak P2 were obtained. This peak P3 was obtained in a region lower than 284.5 eV. That is, it was confirmed that carbon in the CoSnC-containing material was bonded to other elements.

  As Comparative Examples 2-1 to 2-5 and 3-1 to 3-5 for these Examples, other than using the same electrolytic solution as Comparative Examples 1-1-1 to 1-1-5, etc. Were fabricated in the same manner as in Examples 2-1 to 2-11 and 3-1 to 3-11.

  For the fabricated secondary batteries of Examples 2-1 to 2-11, 3-1 to 3-11 and Comparative Examples 2-1 to 2-5, 3-1 to 3-5, Examples 1-1 to The discharge capacity retention rate at the 50th cycle was determined in the same manner as in 1-11. The results are shown in Tables 2 and 3.

  As shown in Tables 2 and 3, the same results as in Examples 1-1 to 1-11 were obtained. That is, even if other negative electrode active materials are used, if the electrolytic solution contains the cyclic carbonate derivative and the compound shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9, the charge / discharge efficiency can be improved. I found out that

(Examples 4-1, 4-2, 5-1, 5-2, 6-1, 6-2)
A secondary battery was fabricated in the same manner as in Examples 1-2, 2-2, and 3-2 except that the content of malonyl chloride in the electrolytic solution was 0.1% by mass or 5.0% by mass. did. Regarding the fabricated secondary batteries of Examples 4-1, 4-2, 5-1, 5-2, 6-1, 6-2, the discharge capacity was maintained in the same manner as in Examples 1-1 to 1-11. The rate was examined. The results are shown in Tables 4, 5 and 6.

  As shown in Tables 4, 5 and 6, when the content of malonyl chloride in the electrolytic solution was 0.1% by mass or more and 5% by mass or less, a high discharge capacity retention rate was obtained. That is, it has been found that it is preferable that the content of the compound shown in Chemical Formula 7, Chemical Formula 8 or Chemical Formula 9 in the electrolytic solution is 0.1 mass% or more and 5 mass% or less.

  Although the present invention has been described with reference to the embodiments and examples, the present invention is not limited to the embodiments and examples, and various modifications can be made. For example, in the above-described embodiment and examples, the case where the electrolytic solution contains the compound shown in chemical formula 7, chemical formula 8 or chemical formula 9 has been described, but all of them are bonded to the negative electrode and are not left in the electrolytic solution. May be.

  In the above embodiments and examples, the case where an electrolytic solution is used as an electrolyte is described. In the above embodiment, a case where a gel electrolyte in which an electrolytic solution is held in a polymer compound is used is also described. Other electrolytes may be used. Other electrolytes include, for example, a mixture of an ion conductive inorganic compound such as ion conductive ceramics, ion conductive glass or ionic crystal and an electrolytic solution, or a mixture of another inorganic compound and an electrolytic solution. Or a mixture of these inorganic compounds and a gel electrolyte.

  Further, in the above embodiments and examples, a battery using lithium as an electrode reactant has been described. However, another alkali metal such as sodium (Na) or potassium (K), or an alkali such as magnesium or calcium (Ca) is used. The present invention can also be applied to the case of using an earth metal or another light metal such as aluminum.

  In addition, in the above embodiments or examples, a cylindrical or laminated film type secondary battery has been specifically described, but the present invention has other shapes such as a coin type, a button type, or a square type. The present invention can be similarly applied to secondary batteries having other structures or secondary batteries having other structures such as a stacked structure. Further, the present invention is not limited to the secondary battery, and can be similarly applied to other batteries such as a primary battery.

It is sectional drawing showing the structure of the secondary battery which concerns on one embodiment of this invention. It is sectional drawing which expands and represents a part of winding electrode body in the secondary battery shown in FIG. It is a disassembled perspective view showing the structure of the secondary battery which concerns on other embodiment of this invention. It is sectional drawing showing the structure along the II line of the winding electrode body shown in FIG. 1 shows an example of a peak obtained by X-ray photoelectron spectroscopy relating to a CoSnC-containing material produced in an example.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 11 ... Battery can, 12, 13 ... Insulation board, 14 ... Battery cover, 15 ... Safety valve mechanism, 15A ... Disc board, 16 ... Heat sensitive resistance element, 17 ... Gasket, 20, 30 ... Winding electrode body, 21, 33 ... Positive electrode, 21A, 33A ... Positive electrode current collector, 21B, 33B ... Positive electrode active material layer, 22, 34 ... Negative electrode, 22A, 34A ... Negative electrode current collector, 22B, 34B ... Negative electrode active material layer, 23, 35 ... Separator 24, center pin, 25, 31 ... positive electrode lead, 26, 32 ... negative electrode lead, 36 ... electrolyte, 37 ... protective tape, 40 ... exterior member, 41 ... adhesion film.

Claims (7)

Bei example a cathode, an anode,
The negative electrode is capable of occluding and releasing an electrode reactant, and contains a material containing at least one of tin (Sn) and silicon (Si) as a constituent element,
The electrolyte includes cyclic and carbonate derivative, of 1, and at least one selected from the group consisting of the compounds shown in Chemical formula 2 or Chemical Formula 3 having a halogen atom, a secondary battery.

(In the formula, A1 represents CH (R3) or NH, and R3 represents hydrogen (H), halogen, an alkyl group having 4 or less carbon atoms , or at least part of hydrogen of an alkyl group having 4 or less carbon atoms. R1 and R2 represent a group substituted with halogen, wherein hydrogen, halogen, NH ₂ , an alkyl group having 4 or less carbon atoms , or a group in which at least a part of hydrogen of an alkyl group having 4 or less carbon atoms is substituted with halogen Represents.)

(In the formula, A2 represents CH (R5) or NH, and R5 represents hydrogen, halogen, an alkyl group having 4 or less carbon atoms , or at least part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen. R4 represents hydrogen, halogen, NH ₂ , an alkyl group having 4 or less carbon atoms , or a group obtained by substituting at least part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen.)

(In the formula, A3 represents CH (R6) or NH, and R6 represents hydrogen, halogen, an alkyl group having 4 or less carbon atoms , or at least a part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen. Represents the selected group.) The compound shown in Chemical Formula 1 is at least one of acetylacetone, hexafluoroacetylacetone, diacetamide, bistrifluoroacetamide, malonyl chloride, bisformimide and biuret,
The compound shown in Chemical Formula 2 is cyanourea,
The secondary battery according to claim 1, wherein the compound represented by Chemical Formula 3 is at least one of dicyanamide and malononitrile. The content of the compound represented by Chemical Formula in the electrolytic solution 1, Formula 2 or Formula 3 is 5 wt% or less than 0.1 wt%, the secondary battery according to claim 1, wherein. The secondary of claim 1 , wherein the cyclic carbonate derivative comprises at least one of 4-fluoro-1,3-dioxolan-2-one and 4-chloro-1,3-dioxolan-2-one. battery. Bei example a cathode, an anode,
The negative electrode is capable of occluding and releasing an electrode reactant, and contains a material containing at least one of tin and silicon as a constituent element,
At least a part of the negative electrode is chelate-bonded with the compound shown in Chemical formula 4, Chemical formula 5 or Chemical formula 6,
The electrolyte solution is a secondary battery including a cyclic carbonate derivative having a halogen atom.

(In the formula, A1 represents CH (R3) or NH, and R3 represents hydrogen (H), halogen, an alkyl group having 4 or less carbon atoms , or at least part of hydrogen of an alkyl group having 4 or less carbon atoms. R1 and R2 represent a group substituted with halogen, wherein hydrogen, halogen, NH ₂ , an alkyl group having 4 or less carbon atoms , or a group in which at least a part of hydrogen of an alkyl group having 4 or less carbon atoms is substituted with halogen Represents.)

(In the formula, A2 represents CH (R5) or NH, and R5 represents hydrogen, halogen, an alkyl group having 4 or less carbon atoms , or at least part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen. R4 represents hydrogen, halogen, NH ₂ , an alkyl group having 4 or less carbon atoms , or a group obtained by substituting at least part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen.)

(In the formula, A3 represents CH (R6) or NH, and R6 represents hydrogen, halogen, an alkyl group having 4 or less carbon atoms , or at least a part of hydrogen of an alkyl group having 4 or less carbon atoms with halogen. Represents the selected group.) The compound shown in Chemical Formula 1 is at least one of acetylacetone, hexafluoroacetylacetone, diacetamide, bistrifluoroacetamide, malonyl chloride, bisformimide and biuret,
The compound shown in Chemical Formula 2 is cyanourea,
The secondary battery according to claim 5, wherein the compound represented by Chemical Formula 3 is at least one of dicyanamide and malononitrile. The secondary of claim 5 , wherein the cyclic carbonate derivative comprises at least one of 4-fluoro-1,3-dioxolan-2-one and 4-chloro-1,3-dioxolan-2-one. battery.

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