JP2010262801A - Secondary battery, and electrolyte - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a secondary battery capable of obtaining superior cycle characteristics and preservation characteristics. <P>SOLUTION: The electrolyte solution contains two kinds or more of solvents and one kind of it is a halogenated cyclic compound. This halogenated cyclic compound is a cyclic compound in which a portion having a straight-chain carbon chain with the carbon number 3 as a basic skeleton (-C(R1)(R2)-C(R3)(R4)-C(R5)(R6)-) and a portion containing unsaturated carbon bond (-X-C(=Z)-Y-) are coupled. At least one of R1, R2, R5 and R6 is a halogen group or a halogenated alkyl group, and at least one of R3 and R4 is a hydrogen group or an alkyl group. Since chemical stability of the electrolyte solution is improved, decomposition reaction of the electrolyte solution upon charge and discharge is suppressed. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an electrolyte containing a solvent and an electrolyte salt, and a secondary battery using the same.

  In recent years, portable electronic devices such as a video camera, a digital still camera, a mobile phone, and a laptop computer have been widely used, and there is a strong demand for miniaturization, weight reduction, and long life. Accordingly, as a power source, development of a battery, in particular, a secondary battery that is small and lightweight and capable of obtaining a high energy density is in progress.

  Among these, lithium ion secondary batteries that use the insertion and release of lithium ions as charge / discharge reactions and lithium metal secondary batteries that use precipitation and dissolution of lithium metal are highly expected. This is because an energy density higher than that of a lead battery or a nickel cadmium battery can be obtained.

  The secondary battery includes an electrolyte together with a positive electrode and a negative electrode. The positive electrode has a positive electrode active material layer on the positive electrode current collector, and the negative electrode has a negative electrode active material layer on the negative electrode current collector. The electrolyte is obtained by dissolving an electrolyte salt or the like in a solvent.

  Various studies have been made on the solvent of the electrolyte that functions as a medium for the charge / discharge reaction because it greatly affects the performance of the secondary battery. Specifically, non-halogenated cyclic carbonates, partially halogenated cyclic carbonates or fully halogenated cyclic carbonates are used to improve cycle characteristics (see, for example, Patent Documents 1 to 5).

JP 2003-243035 A JP-A-11-260402 JP 2002-175948 A JP 05-034781 A U.S. Pat. No. 3,455,954

  In recent years, portable electronic devices have become more sophisticated and multifunctional, and their power consumption tends to increase. Therefore, charging and discharging of secondary batteries are frequently repeated, and their cycle characteristics and storage characteristics are likely to deteriorate. Is in the situation. For this reason, further improvement is desired for the cycle characteristics and storage characteristics of the secondary battery.

  The present invention has been made in view of such problems, and an object thereof is to provide an electrolyte capable of obtaining excellent cycle characteristics and storage characteristics, and a secondary battery using the electrolyte.

  The electrolyte of the present invention contains an electrolyte salt and two or more kinds of solvents, and one of the solvents is a halogenated cyclic compound represented by the formula (1). The secondary battery of the present invention includes a positive electrode, a negative electrode, and an electrolyte, and the electrolyte has the above-described composition.

（Ｒ１〜Ｒ６は水素基、ハロゲン基、アルキル基あるいはハロゲン化アルキル基であり、それらのうちの少なくとも１つはハロゲン基あるいはハロゲン化アルキル基である。ただし、Ｒ１、Ｒ２、Ｒ５およびＲ６のうちの少なくとも１つはハロゲン基あるいはハロゲン化アルキル基であり、Ｒ３およびＲ４のうちの少なくとも１つは水素基あるいはアルキル基である。Ｘ、ＹおよびＺはオキソ基あるいはチオ基である。）

(R1 to R6 are a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group. However, of R1, R2, R5 and R6, And at least one of R3 and R4 is a hydrogen group or an alkyl group, and X, Y, and Z are an oxo group or a thio group.)

  According to the electrolyte of the present invention, two or more kinds of solvents are contained, and one of the solvents is the halogenated cyclic compound represented by the formula (1). Stability is improved. Therefore, according to the secondary battery using the electrolyte of the present invention, since the decomposition reaction of the electrolyte is suppressed at the time of charge / discharge while sufficiently progressing the charge / discharge reaction, excellent cycle characteristics and storage characteristics are obtained. be able to.

It is sectional drawing showing the structure of the 1st secondary battery provided with the electrolyte which concerns on one embodiment of this invention. It is sectional drawing showing the structure of a winding electrode body. It is sectional drawing which represents the structure of a negative electrode typically. It is sectional drawing which represents typically the other structure of a negative electrode. It is the SEM photograph showing the cross-section of a negative electrode, and its schematic diagram. It is the SEM photograph showing the other cross-section of a negative electrode, and its schematic diagram. It is a disassembled perspective view showing the structure of a 3rd secondary battery. It is sectional drawing showing the structure of a winding electrode body. It is a figure showing the analysis result of SnCoC containing material by XPS.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The order of explanation is as follows.

1. Electrolyte Electrochemical device using electrolyte (secondary battery)
2-1. First secondary battery (lithium ion secondary battery: cylindrical type)
2-2. Second secondary battery (lithium metal secondary battery: cylindrical type)
2-3. Third secondary battery (lithium ion secondary battery: Laminate film type)

<1. Electrolyte>
The electrolyte according to an embodiment of the present invention is used for an electrochemical device such as a secondary battery, for example, and is obtained by dissolving an electrolyte salt in two or more kinds of solvents. However, the electrolyte may contain other materials such as various additives in addition to the solvent and the electrolyte salt.

[solvent]
One of the solvents is a halogenated cyclic compound represented by the formula (1) (hereinafter simply referred to as “halogenated cyclic compound”). The reason why the solvent contains a halogenated cyclic compound is that the chemical stability of the electrolyte is improved, so that the decomposition reaction of the electrolyte is suppressed during the electrode reaction. The type of halogenated cyclic compound contained in the solvent may be one type or two or more types. R1 to R6 may be the same type of group or different types of groups. R1 to R6 may be the same group or different groups. The halogenated cyclic compound also includes optical isomers.

（Ｒ１〜Ｒ６は水素基、ハロゲン基、アルキル基あるいはハロゲン化アルキル基であり、それらのうちの少なくとも１つはハロゲン基あるいはハロゲン化アルキル基である。ただし、Ｒ１、Ｒ２、Ｒ５およびＲ６のうちの少なくとも１つはハロゲン基あるいはハロゲン化アルキル基であり、Ｒ３およびＲ４のうちの少なくとも１つは水素基あるいはアルキル基である。Ｘ、ＹおよびＺはオキソ基あるいはチオ基である。）

(R1 to R6 are a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group. However, of R1, R2, R5 and R6, And at least one of R3 and R4 is a hydrogen group or an alkyl group, and X, Y, and Z are an oxo group or a thio group.)

  This halogenated cyclic compound is a moiety (-C (R1) (R2) -C (R3) (R4) -C (R5) (R6) having a straight carbon chain having 3 carbon atoms as a basic skeleton). -) And a cyclic compound in which an unsaturated carbon bond-containing moiety (-XC (= Z) -Y-) is linked. In this case, at least one of R1, R2, R5 and R6 is a halogen group or a halogenated alkyl group, and at least one of R3 and R4 is a hydrogen group or an alkyl group.

  The kind of the halogen group is not particularly limited, but among them, fluorine is preferable. This is because the chemical stability of the electrolyte is further improved as compared with the case of chlorine or the like.

  The halogenated alkyl group is a group in which at least a part of hydrogen in the alkyl group is substituted with halogen. The type of the halogen is not particularly limited, but among them, fluorine is preferable for the same reason as the above-described type of the halogen group.

  The number of carbon atoms of the alkyl group or halogenated alkyl group is not particularly limited, but is preferably as small as possible, and more preferably 3 or less. This is because the solubility and compatibility of the halogenated cyclic compound are improved.

  X, Y and Z may be any combination as long as each is a combination selected from an oxo group or a thio group. Specifically, when Z is an oxo group, —X—C (═Z) —Y— represents —O—C (═O) —O—, —O—C (═O) —S—. , -S-C (= O) -O- or -S-C (= O) -S-. When Z is a thio group, —X—C (═Z) —Y— represents —O—C (═S) —O—, —O—C (═S) —S—, — S-C (= S) -O- or -S-C (= S) -S-.

  Especially, it is preferable that a halogenated cyclic compound is what is represented by Formula (2). The halogenated cyclic compound represented by the formula (2) is a cyclic carbonate having —O—C (═O) —O— as —X—C (═Z) —Y—. This is because they are easily available and have excellent solubility and compatibility. Moreover, it is because the chemical stability of electrolyte is fully improved.

（Ｒ７〜Ｒ１２は水素基、ハロゲン基、アルキル基あるいはハロゲン化アルキル基であり、それらのうちの少なくとも１つはハロゲン基あるいはハロゲン化アルキル基である。ただし、Ｒ７、Ｒ８、Ｒ１１およびＲ１２のうちの少なくとも１つはハロゲン基あるいはハロゲン化アルキル基であり、Ｒ９およびＲ１０のうちの少なくとも１つは水素基あるいはアルキル基である。）

(R7 to R12 are a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group. However, of R7, R8, R11 and R12, At least one of is a halogen group or a halogenated alkyl group, and at least one of R9 and R10 is a hydrogen group or an alkyl group.)

  Specific examples of the halogenated cyclic compound represented by Formula (2) include those represented by Formula (2-1) to Formula (2-52). This is because the chemical stability of the electrolyte is sufficiently improved. Among these, those shown in Formula (2-1), Formula (2-2), or Formula (2-4) are preferable. This is because it can be easily obtained and can be stably mixed with various non-aqueous solvents.

  As described above, the halogenated cyclic compound is not limited to those having —O—C (═O) —O— as —X—C (═Z) —Y—. ) -S- and the like. Here, taking the example shown in Formula (2-1) as an example, the halogenated cyclic compound may be represented by Formula (2-53) to Formula (2-59).

  The halogenated cyclic compound also includes optical isomers as described above. Here, taking the example shown in Formula (2-4) as an example, the halogenated cyclic compound may be represented by either Formula (2-4A) or Formula (2-4B).

  Of course, specific examples of the halogenated cyclic compound may have the structure shown in the formula (1), the formula (2-1) to the formula (2-59), the formula (2-4A), and the formula (2). -4B).

  The content of the halogenated cyclic compound in the solvent is not particularly limited. In this case, the content of the halogenated cyclic compound may be optimized according to specific conditions when the electrolyte is used in an electrochemical device. As such specific conditions, for example, when an electrolyte is used in a secondary battery as an electrochemical device, the type of the negative electrode active material in the negative electrode can be used.

  The remaining type of the solvent is one or more of other non-aqueous solvents such as organic solvents (excluding those corresponding to the halogenated cyclic compound). The reason why the solvent includes not only the halogenated cyclic compound but also other non-aqueous solvents is that the electrode reaction can sufficiently proceed through the electrolyte.

  The other non-aqueous solvent is preferably at least one of cyclic carbonate, chain carbonate, lactone, and acetate. This is because the compatibility with the halogenated cyclic compound is excellent and the electrode reaction can proceed smoothly. The cyclic carbonate is, for example, ethylene carbonate, propylene carbonate or butylene carbonate. Examples of the chain carbonate ester include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and methyl propyl carbonate. The lactone is γ-butyrolactone or γ-valerolactone. Examples of the acetate ester include methyl acetate, ethyl acetate, and propyl acetate.

  Among these, at least one of a cyclic carbonate and a chain carbonate is preferable. In this case, a combination of a cyclic carbonate having a high viscosity (high dielectric constant) solvent (for example, a relative dielectric constant ε ≧ 30) and a chain carbonate having a low viscosity solvent (for example, viscosity ≦ 1 mPa · s) is more preferable. preferable. This is because the dissociation property of the electrolyte salt and the ion mobility are improved.

  Other nonaqueous solvents may be the following various organic solvents. 1,2-dimethoxyethane or tetrahydrofuran. 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane or 1,4-dioxane. Methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethyl acetate or ethyl trimethyl acetate. Acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, N, N-dimethylformamide, N-methylpyrrolidinone or N-methyloxazolidinone. N, N'-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, trimethyl phosphate or dimethyl sulfoxide. Of course, these may be arbitrarily combined with the cyclic carbonates described above.

  The content of the other non-aqueous solvent in the solvent is not particularly limited. For example, when a cyclic carbonate and a chain carbonate are used as the other non-aqueous solvent, the content of the cyclic carbonate in the non-aqueous solvent is 5% by weight or more and 95% by weight or less. The content of is 5 wt% or more and 95 wt% or less.

  In particular, the solvent preferably contains at least one of unsaturated carbon-bonded cyclic carbonates represented by formulas (3) to (5). This is because a stable protective film is formed on the surface of the electrode during the electrode reaction, so that the decomposition reaction of the electrolyte is suppressed. The “unsaturated carbon bond cyclic ester carbonate” is a cyclic ester carbonate having one or two or more unsaturated carbon bonds. The content of the unsaturated carbon bond cyclic carbonate in the solvent is, for example, 0.01 wt% or more and 10 wt% or less. The kind of unsaturated carbon bond cyclic ester carbonate is not limited to those described below, and other types may be used.

（Ｒ２１およびＲ２２は水素基あるいはアルキル基である。）

(R21 and R22 are a hydrogen group or an alkyl group.)

（Ｒ２３〜Ｒ２６は水素基、アルキル基、ビニル基あるいはアリル基であり、それらのうちの少なくとも１つはビニル基あるいはアリル基である。）

(R23 to R26 are a hydrogen group, an alkyl group, a vinyl group, or an allyl group, and at least one of them is a vinyl group or an allyl group.)

（Ｒ２７はアルキレン基である。）

(R27 is an alkylene group.)

  The unsaturated carbon bond cyclic ester carbonate shown in Formula (3) is a vinylene carbonate compound. The following are mentioned as an example of this vinylene carbonate type compound. Vinylene carbonate, methyl vinylene carbonate or ethyl vinylene carbonate. 4,5-dimethyl-1,3-dioxol-2-one, 4,5-diethyl-1,3-dioxol-2-one, 4-fluoro-1,3-dioxol-2-one or 4-trifluoro Methyl-1,3-dioxol-2-one. Among these, vinylene carbonate is preferable. This is because it can be easily obtained and a high effect can be obtained.

  The unsaturated carbon bond cyclic carbonate represented by the formula (4) is a vinyl ethylene carbonate compound. The following are mentioned as an example of this vinyl carbonate ethylene-type compound. Vinylethylene carbonate, 4-methyl-4-vinyl-1,3-dioxolan-2-one or 4-ethyl-4-vinyl-1,3-dioxolan-2-one. 4-n-propyl-4-vinyl-1,3-dioxolan-2-one, 5-methyl-4-vinyl-1,3-dioxolan-2-one, 4,4-divinyl-1,3-dioxolane- 2-one or 4,5-divinyl-1,3-dioxolan-2-one. Of these, vinyl ethylene carbonate is preferred. This is because it can be easily obtained and a high effect can be obtained. Of course, as R13 to R16, all may be vinyl groups, all may be allyl groups, or vinyl groups and allyl groups may be mixed.

  The unsaturated carbon bond cyclic carbonate represented by the formula (5) is a methylene ethylene carbonate compound. The following are mentioned as an example of this methylene ethylene carbonate type compound. 4-methylene-1,3-dioxolan-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one or 4,4-diethyl-5-methylene-1,3-dioxolane- 2-one. As this methylene ethylene carbonate compound, there may be one having two methylene groups in addition to one having one methylene group (compound shown in Formula (5)).

  In addition, as unsaturated carbon bond cyclic carbonate ester, the catechol carbonate (catechol carbonate) etc. which have a benzene ring other than what was shown to Formula (3)-Formula (5) may be sufficient.

  Moreover, it is preferable that the solvent contains at least 1 sort (s) of the halogenated chain carbonate represented by Formula (6), and the halogenated cyclic carbonate represented by Formula (7). This is because a stable protective film is formed on the surface of the electrode during the electrode reaction, so that the decomposition reaction of the electrolyte is suppressed. The “halogenated chain carbonate ester” is a chain carbonate ester containing halogen as a constituent element, and the “halogenated cyclic carbonate ester” is a cyclic carbonate ester containing halogen as a constituent element. R31 to R36 may be the same group or different groups. The same applies to R37 to R40. The content of the halogenated chain carbonate and the halogenated cyclic carbonate in the solvent is, for example, 0.01 wt% or more and 50 wt% or less. The kind of the halogenated chain carbonate ester or the halogenated cyclic carbonate ester is not limited to those described below, and other types may be used.

（Ｒ３１〜Ｒ３６は水素基、ハロゲン基、アルキル基あるいはハロゲン化アルキル基であり、それらのうちの少なくとも１つはハロゲン基あるいはハロゲン化アルキル基である。）

(R31 to R36 are a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group.)

（Ｒ３７〜Ｒ３０は水素基、ハロゲン基、アルキル基あるいはハロゲン化アルキル基であり、それらのうちの少なくとも１つはハロゲン基あるいはハロゲン化アルキル基である。）

(R37 to R30 are a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group.)

  In the halogenated chain carbonic acid ester or the halogenated cyclic carbonic acid ester, the type of halogen is not particularly limited, but among them, fluorine, chlorine or bromine is preferable, and fluorine is more preferable. This is because an effect higher than that of other halogens can be obtained. However, the number of halogens is preferably two rather than one, and may be three or more. This is because the ability to form a protective film increases, and a stronger and more stable protective film is formed, so that the decomposition reaction of the electrolyte is further suppressed.

  Examples of the halogenated chain carbonate include fluoromethyl methyl carbonate, bis (fluoromethyl) carbonate, and difluoromethyl methyl carbonate. Moreover, what is represented by Formula (7-1)-Formula (7-21) is mentioned as an example of halogenated cyclic carbonate. This halogenated cyclic carbonate includes geometric isomers. Among them, examples of the halogenated cyclic carbonate include 4-fluoro-1,3-dioxolan-2-one represented by Formula (7-1) or 4,5-difluoro-1, represented by Formula (7-3). 3-dioxolan-2-one is preferred and the latter is more preferred. In particular, in 4,5-difluoro-1,3-dioxolan-2-one, the trans isomer is preferable to the cis isomer. This is because it can be easily obtained and a high effect can be obtained.

  Moreover, it is preferable that the solvent contains sultone (cyclic sulfonate ester). This is because the chemical stability of the electrolytic solution is further improved. Examples of this sultone include propane sultone and propene sultone. The content of sultone in the solvent is, for example, 0.5% by weight or more and 5% by weight or less. However, the type of sultone is not necessarily limited to the above.

  Furthermore, it is preferable that the solvent contains an acid anhydride. This is because the chemical stability of the electrolytic solution is further improved. Examples of the acid anhydride include carboxylic acid anhydride, disulfonic acid anhydride, and anhydride of carboxylic acid and sulfonic acid. Examples of the carboxylic acid anhydride include succinic anhydride, glutaric anhydride, and maleic anhydride. Examples of the disulfonic anhydride include ethane disulfonic anhydride and propane disulfonic anhydride. Examples of the anhydride of carboxylic acid and sulfonic acid include anhydrous sulfobenzoic acid, anhydrous sulfopropionic acid, and anhydrous sulfobutyric acid. The content of the acid anhydride in the solvent is, for example, 0.5% by weight or more and 5% by weight or less. However, the type of acid anhydride is not necessarily limited to the above.

[Electrolyte salt]
The electrolyte salt includes, for example, any one or more of light metal salts such as lithium salts. However, the electrolyte salt may contain other salts other than the light metal salt, for example.

The following are mentioned as an example of lithium salt. Lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate or lithium hexafluoroarsenate. Lithium tetraphenylborate (LiB (C ₆ H ₅ ) ₄ ), lithium methanesulfonate (LiCH ₃ SO ₃ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ) or lithium tetrachloroaluminate (LiAlCl ₄ ) . It is dilithium hexafluorosilicate (Li ₂ SiF ₆ ), lithium chloride (LiCl) or lithium bromide (LiBr). Lithium monofluorophosphate (LiPFO ₃ ) or lithium difluorophosphate (LiPF ₂ O ₂ ). This is because excellent characteristics can be obtained in an electrochemical device using an electrolyte. However, the type of the electrolyte salt is not limited to the above, and other types may be used.

  Among these, at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, and lithium hexafluoroarsenate is preferable, and lithium hexafluorophosphate is more preferable. This is because a higher effect can be obtained because the internal resistance is lowered.

  In particular, the electrolyte salt preferably contains at least one of the compounds represented by the formulas (8) to (10). This is because a higher effect can be obtained. R51 and R53 may be the same group or different groups. The same applies to R61 to R63, R71 and R72. However, the type of electrolyte salt is not limited to that described below, and other types may be used.

（Ｘ５１は長周期型周期表における１族元素あるいは２族元素、またはアルミニウムである。Ｍ５１は遷移金属元素、または長周期型周期表における１３族元素、１４族元素あるいは１５族元素である。Ｒ５１はハロゲン基である。Ｙ５１は−（Ｏ＝）Ｃ−Ｒ５２−Ｃ（＝Ｏ）−、−（Ｏ＝）Ｃ−Ｃ（Ｒ５３）₂ −あるいは−（Ｏ＝）Ｃ−Ｃ（＝Ｏ）−である。ただし、Ｒ５２はアルキレン基、ハロゲン化アルキレン基、アリーレン基あるいはハロゲン化アリーレン基である。Ｒ５３はアルキル基、ハロゲン化アルキル基、アリール基あるいはハロゲン化アリール基である。なお、ａ５は１以上４以下の整数であり、ｂ５は０、２あるいは４であり、ｃ５、ｄ５、ｍ５およびｎ５は１以上３以下の整数である。）

(X51 is a group 1 element or group 2 element in the long-period periodic table, or aluminum. M51 is a transition metal element, or a group 13, element or group 15 element in the long-period periodic table. R51 Y51 is — (O═) C—R52—C (═O) —, — (O═) C—C (R53) ₂ — or — (O═) C—C (═O) Where R52 is an alkylene group, a halogenated alkylene group, an arylene group or a halogenated arylene group, R53 is an alkyl group, a halogenated alkyl group, an aryl group or a halogenated aryl group, and a5 is An integer of 1 or more and 4 or less, b5 is 0, 2 or 4, and c5, d5, m5 and n5 are integers of 1 or more and 3 or less.

（Ｘ６１は長周期型周期表における１族元素あるいは２族元素である。Ｍ６１は遷移金属元素、または長周期型周期表における１３族元素、１４族元素あるいは１５族元素である。Ｙ６１は−（Ｏ＝）Ｃ−（Ｃ（Ｒ６１）₂ ）_b6−Ｃ（＝Ｏ）−、−（Ｒ６３）₂ Ｃ−（Ｃ（Ｒ６２）₂ ）_c6−Ｃ（＝Ｏ）−、−（Ｒ６３）₂ Ｃ−（Ｃ（Ｒ６２）₂ ）_c6−Ｃ（Ｒ６３）₂ −、−（Ｒ６３）₂ Ｃ−（Ｃ（Ｒ６２）₂ ）_c6−Ｓ（＝Ｏ）₂ −、−（Ｏ＝）₂ Ｓ−（Ｃ（Ｒ６２）₂ ）_d6−Ｓ（＝Ｏ）₂ −あるいは−（Ｏ＝）Ｃ−（Ｃ（Ｒ６２）₂ ）_d6−Ｓ（＝Ｏ）₂ −である。ただし、Ｒ６１およびＲ６３は水素基、アルキル基、ハロゲン基あるいはハロゲン化アルキル基であり、それぞれのうちの少なくとも１つはハロゲン基あるいはハロゲン化アルキル基である。Ｒ６２は水素基、アルキル基、ハロゲン基あるいはハロゲン化アルキル基である。なお、ａ６、ｅ６およびｎ６は１あるいは２であり、ｂ６およびｄ６は１以上４以下の整数であり、ｃ６は０以上４以下の整数であり、ｆ６およびｍ６は１以上３以下の整数である。）

(X61 is a group 1 element or group 2 element in the long-period periodic table. M61 is a transition metal element, or a group 13, element, or group 15 element in the long-period periodic table. Y61 is − ( O =) C- (C (R61 ) 2) b6 -C (= O) -, - (R63) 2 C- (C (R62) 2) c6 -C (= O) -, - (R63) 2 C — (C (R62) ₂ ) _c6 —C (R63) ₂ —, — (R63) ₂ C— (C (R62) ₂ ) _c6 —S (═O) ₂ —, — (O═) ₂ S— ( C (R62) ₂ ) _d6- S (= O) _{2- or-} (O =) C- (C (R62) ₂ ) _d6- S (= O) _2- , where R61 and R63 are hydrogen groups. , An alkyl group, a halogen group, or a halogenated alkyl group, and at least one of each is a halogen group or a halogenated alkyl group. R62 is a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group, wherein a6, e6 and n6 are 1 or 2, b6 and d6 are integers of 1 or more and 4 or less, c6 is an integer of 0 or more and 4 or less, and f6 and m6 are integers of 1 or more and 3 or less.)

（Ｘ７１は長周期型周期表における１族元素あるいは２族元素である。Ｍ７１は遷移金属元素、または長周期型周期表における１３族元素、１４族元素あるいは１５族元素である。Ｒｆはフッ素化アルキル基あるいはフッ素化アリール基であり、いずれの炭素数も１〜１０である。Ｙ７１は−（Ｏ＝）Ｃ−（Ｃ（Ｒ７１）₂ ）_d7−Ｃ（＝Ｏ）−、−（Ｒ７２）₂ Ｃ−（Ｃ（Ｒ７１）₂ ）_d7−Ｃ（＝Ｏ）−、−（Ｒ７２）₂ Ｃ−（Ｃ（Ｒ７１）₂ ）_d7−Ｃ（Ｒ７２）₂ −、−（Ｒ７２）₂ Ｃ−（Ｃ（Ｒ７１）₂ ）_d7−Ｓ（＝Ｏ）₂ −、−（Ｏ＝）₂ Ｓ−（Ｃ（Ｒ７１）₂ ）_e7−Ｓ（＝Ｏ）₂ −あるいは−（Ｏ＝）Ｃ−（Ｃ（Ｒ７１）₂ ）_e7−Ｓ（＝Ｏ）₂ −である。ただし、Ｒ７１は水素基、アルキル基、ハロゲン基あるいはハロゲン化アルキル基である。Ｒ７２は水素基、アルキル基、ハロゲン基あるいはハロゲン化アルキル基であり、そのうちの少なくとも１つはハロゲン基あるいはハロゲン化アルキル基である。なお、ａ７、ｆ７およびｎ７は１あるいは２であり、ｂ７、ｃ７およびｅ７は１以上４以下の整数であり、ｄ７は０以上４以下の整数であり、ｇ７およびｍ７は１以上３以下の整数である。）

(X71 is a group 1 element or a group 2 element in the long-period type periodic table. M71 is a transition metal element, or a group 13, element, or a group 15 element in the long-period type periodic table. Rf is fluorinated. An alkyl group or a fluorinated aryl group, each having 1 to 10 carbon atoms Y71 is — (O═) C— (C (R71) ₂ ) _d7 —C (═O) —, — (R72); ₂ C— (C (R71) ₂ ) _d7 —C (═O) —, — (R72) ₂ C— (C (R71) ₂ ) _d7 —C (R72) ₂ —, — (R72) ₂ C— ( _{C (R71) 2) d7 -S} (= O) 2 -, - (O =) 2 S- (C (R71) 2) e7 -S (= O) 2 - or - (O =) C- (C _{(R71) 2) e7 -S (} = O) 2 -. is, however, R71 is a hydrogen group, an alkyl group, a halogen group, or a halogen Kaa R72 is a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group, at least one of which is a halogen group or a halogenated alkyl group, wherein a7, f7 and n7 are 1 or 2 B7, c7 and e7 are integers of 1 or more and 4 or less, d7 is an integer of 0 or more and 4 or less, and g7 and m7 are integers of 1 or more and 3 or less.

  Group 1 elements are hydrogen, lithium, sodium, potassium, rubidium, cesium, and francium. Group 2 elements are beryllium, magnesium, calcium, strontium, barium and radium. Group 13 elements are boron, aluminum, gallium, indium and thallium. Group 14 elements are carbon, silicon, germanium, tin and lead. Group 15 elements are nitrogen, phosphorus, arsenic, antimony and bismuth.

  Examples of the compound represented by the formula (8) include those represented by the formula (8-1) to the formula (8-6). Examples of the compound represented by the formula (9) include those represented by the formula (9-1) to the formula (9-8). An example of the compound represented by the formula (10) includes a compound represented by the formula (10-1).

  Moreover, it is preferable that electrolyte salt contains at least 1 sort (s) of the compounds represented by Formula (11)-Formula (13). This is because a higher effect can be obtained. Note that m and n may be the same value or different values. The same applies to p, q and r. However, the type of electrolyte salt is not limited to that described below, and other types may be used.

_{LiN (C m F 2m + 1} SO 2) (C n F 2n + 1 SO 2) ... (11)
(M and n are integers of 1 or more.)

（Ｒ８１は炭素数が２以上４以下の直鎖状あるいは分岐状のパーフルオロアルキレン基である。）

(R81 is a linear or branched perfluoroalkylene group having 2 to 4 carbon atoms.)

LiC (C _p F _{2p + 1} SO ₂ ) (C _q F _{2q + 1} SO ₂ ) (C _r F _{2r + 1} SO ₂ ) (13)
(P, q and r are integers of 1 or more.)

The compound represented by the formula (11) is a chain imide compound. The following are mentioned as an example of this compound. Bis (trifluoromethanesulfonyl) imide lithium (LiN (CF ₃ SO ₂ ) ₂ ) or bis (pentafluoroethanesulfonyl) imide lithium (LiN (C ₂ F ₅ SO ₂ ) ₂ ). (Trifluoromethanesulfonyl) (pentafluoroethanesulfonyl) imidolithium (LiN (CF ₃ SO ₂ ) (C ₂ F ₅ SO ₂ )). (Trifluoromethanesulfonyl) (heptafluoropropanesulfonyl) imidolithium (LiN (CF ₃ SO ₂ ) (C ₃ F ₇ SO ₂ )). (Trifluoromethanesulfonyl) (nonafluorobutanesulfonyl) imidolithium (LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ )).

  The compound shown in Formula (12) is a cyclic imide compound. Examples of this compound include those represented by formula (12-1) to formula (12-4).

The compound represented by the formula (13) is a chain methide compound. Examples of this compound include lithium tris (trifluoromethanesulfonyl) methide (LiC (CF ₃ SO ₂ ) ₃ ).

  The content of the electrolyte salt is preferably 0.3 mol / kg or more and 3.0 mol / kg or less with respect to the solvent. This is because high ionic conductivity is obtained.

  According to this electrolyte, two or more kinds of solvents are contained, one of which is a halogenated cyclic compound represented by the formula (1). In this case, as compared with the case where the halogenated cyclic compound is not included, the case where the compound having another structure different from the formula (1) is included, or the case where only the halogenated cyclic compound is included, Chemical stability is improved without inhibiting the progress of the electrode reaction. Examples of the compound having another structure include those represented by the formula (13). Therefore, since the decomposition reaction of the electrolyte during the electrode reaction is suppressed while the electrode reaction proceeds sufficiently, it can contribute to the performance improvement of the electrochemical device. More specifically, when the electrolyte is used in a secondary battery, excellent cycle characteristics and storage characteristics can be obtained.

  In particular, if the halogenated cyclic compound has a structure represented by the formula (2), a higher effect can be obtained. Further, if the remaining type of the solvent is at least one of cyclic carbonate, chain carbonate, lactone and acetate, higher effects can be obtained.

  Furthermore, if the solvent contains at least one of unsaturated carbon bond cyclic carbonate, halogenated chain carbonate, halogenated cyclic carbonate, sultone and acid anhydride, higher effects can be obtained. . Further, the electrolyte salt is at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, and compounds represented by the formulas (8) to (13). If it contains, a higher effect can be acquired.

<2. Electrochemical Device Using Electrolyte (Secondary Battery)>
Next, usage examples of the above-described electrolyte will be described. Here, when a secondary battery is given as an example of an electrochemical device, the above-described electrolyte is used for a secondary battery as follows.

<2-1. First secondary battery>
1 and 2 show a cross-sectional configuration of the first secondary battery. In FIG. 2, a part of the wound electrode body 20 shown in FIG. 1 is enlarged. The secondary battery described here is, for example, a lithium ion secondary battery in which the capacity of the negative electrode is expressed by insertion and extraction of lithium ions that are electrode reactants.

[Overall structure of secondary battery]
In the secondary battery, a wound electrode body 20 and a pair of insulating plates 12 and 13 are mainly housed in a substantially hollow cylindrical battery can 11. A battery structure using such a 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, the surface of the battery can 11 may be plated with nickel (Ni) or the like. 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 thermal resistance element (Positive Temperature Coefficient: PTC element) 16 are caulked through a gasket 17 at the open end of the battery can 11. Thereby, 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 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.

  The wound electrode body 20 is obtained by laminating and winding a positive electrode 21 and a negative electrode 22 via a separator 23. For example, 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]
The positive electrode 21 is, for example, one in which a positive electrode active material layer 21B is provided on both surfaces of a positive electrode current collector 21A. However, the positive electrode active material layer 21B may be provided only on one surface of the positive electrode current collector 21A.

  The positive electrode current collector 21A is made of, for example, aluminum, nickel, stainless steel, or the like.

  The positive electrode active material layer 21B includes one or more positive electrode materials capable of inserting and extracting lithium ions as a positive electrode active material, and a positive electrode binder or a positive electrode as necessary. Other materials such as a conductive agent may be included.

As the positive electrode material, a lithium-containing compound is preferable. This is because a high energy density can be obtained. Examples of the lithium-containing compound include a composite oxide containing lithium (Li) and a transition metal element as constituent elements, and a phosphate compound containing lithium and a transition metal element as constituent elements. Especially, what contains at least 1 sort (s) of cobalt (Co), nickel, manganese (Mn), and iron as a transition metal element is preferable. This is because a higher voltage can be obtained. The chemical formula is represented by, for example, Li _x M1O ₂ or Li _y M2PO ₄ . In the formula, M1 and M2 represent one or more transition metal elements. Moreover, the values of x and y vary depending on the charge / discharge state, and are generally 0.05 ≦ x ≦ 1.10 and 0.05 ≦ y ≦ 1.10.

Examples of the composite oxide containing lithium and a transition metal element include lithium cobalt composite oxide (Li _x CoO ₂ ), lithium nickel composite oxide (Li _x NiO ₂ ), or lithium represented by formula (14). Examples include nickel-based composite oxides. Examples of the phosphate compound containing lithium and a transition metal element include a lithium iron phosphate compound (LiFePO ₄ ) or a lithium iron manganese phosphate compound (LiFe _1-u Mn _u PO ₄ (u <1)). Is mentioned. This is because high battery capacity is obtained and excellent cycle characteristics are also obtained.

LiNi _1-x M _x O ₂ (14)
(M is cobalt, manganese, iron, aluminum, vanadium (V), tin, magnesium (Mg), titanium (Ti), strontium (Sr), calcium (Ca), zirconium (Zr), molybdenum (Mo), technetium ( Tc), ruthenium (Ru), tantalum (Ta), tungsten (W), rhenium (Re), ytterbium (Y), copper (Cu), zinc (Zn), barium (Ba), boron (B), chromium ( Cr), silicon, gallium (Ga), phosphorus (P), antimony (Sb), and niobium (Nb), where x is 0.005 <x <0.5.

  In addition, examples of the positive electrode material include oxides, disulfides, chalcogenides, and conductive polymers. Examples of the oxide include titanium oxide, vanadium oxide, and manganese dioxide. Examples of the disulfide include titanium disulfide and molybdenum sulfide. An example of the chalcogenide is niobium selenide. Examples of the conductive polymer include sulfur, polyaniline, and polythiophene.

  Of course, the positive electrode material may be other than the above. Further, two or more kinds of the series of positive electrode materials described above may be mixed in any combination.

  Examples of the positive electrode binder include synthetic rubbers such as styrene butadiene rubber, fluorine rubber, and ethylene propylene diene, and polymer materials such as polyvinylidene fluoride. These may be single and multiple types may be mixed.

  Examples of the positive electrode conductive agent include carbon materials such as graphite, carbon black, acetylene black, and ketjen black. These may be single and multiple types may be mixed. The positive electrode conductive agent may be a metal material or a conductive polymer as long as it is a conductive material.

[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. However, the negative electrode active material layer 22B may be provided only on one surface of the negative electrode current collector 22A.

  The negative electrode current collector 22A is made of, for example, copper, nickel, stainless steel, or the like. The surface of the negative electrode current collector 22A is preferably roughened. This is because the so-called anchor effect improves the adhesion of the negative electrode active material layer 22B to the negative electrode current collector 22A. In this case, the surface of the negative electrode current collector 22A only needs to be roughened at least in a region facing the negative electrode active material layer 22B. Examples of the roughening method include a method of forming fine particles by electrolytic treatment. This electrolytic treatment is a method of providing irregularities by forming fine particles on the surface of the anode current collector 22A by an electrolytic method in an electrolytic bath. The copper foil produced by the electrolytic method is generally called “electrolytic copper foil”.

  The negative electrode active material layer 22B includes one or more negative electrode materials capable of inserting and extracting lithium ions as a negative electrode active material, and a negative electrode binder or a negative electrode as necessary. Other materials such as a conductive agent may be included. Note that details regarding the negative electrode binder and the negative electrode conductive agent are the same as, for example, the positive electrode binder and the positive electrode conductive agent, respectively. In the negative electrode active material layer 22B, for example, it is preferable that the chargeable capacity of the negative electrode material is larger than the discharge capacity of the positive electrode 21 in order to prevent unintentional deposition of lithium metal during charging and discharging.

  Examples of the negative electrode material include a carbon material. This is because the crystal structure changes very little during insertion and extraction of lithium ions, so that a high energy density and excellent cycle characteristics can be obtained, and it also functions as a negative electrode conductive agent. Examples of the carbon material include graphitizable carbon, non-graphitizable carbon having a (002) plane spacing of 0.37 nm or more, and graphite having a (002) plane spacing of 0.34 nm or less. is there. More specifically, there are pyrolytic carbons, cokes, glassy carbon fibers, organic polymer compound fired bodies, activated carbon or carbon blacks. Of these, the cokes include pitch coke, needle coke, petroleum coke, and the like. The organic polymer compound fired body is obtained by firing and carbonizing a phenol resin, a furan resin, or the like at an appropriate temperature. The shape of the carbon material may be any of fibrous, spherical, granular or scale-like.

  Moreover, as a negative electrode material, the material (metallic material) which contains at least 1 sort (s) of a metallic element and a semimetallic element as a structural element is mentioned, for example. This is because a high energy density can be obtained. Such a material may be a single element, an alloy or a compound of a metal element or a metalloid element, or may be two or more of them, or may have at least a part of one or more of those phases. . The “alloy” in the present invention includes an alloy containing one or more metal elements and one or more metalloid elements in addition to an alloy composed of two or more metal elements. Further, the “alloy” may contain a nonmetallic element. The structure includes a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or those in which two or more of them coexist.

  The metal element or metalloid element described above is, for example, a metal element or metalloid element capable of forming an alloy with lithium, and specifically, is at least one of the following elements. Magnesium, boron, aluminum, gallium, indium (In), silicon, germanium (Ge), tin, or lead (Pb). Bismuth (Bi), cadmium (Cd), silver (Ag), zinc, hafnium (Hf), zirconium, yttrium, palladium (Pd) or platinum (Pt). Among these, at least one of silicon and tin is preferable. This is because a high energy density can be obtained because of its excellent ability to occlude and release lithium ions.

  The material containing at least one of silicon and tin may be, for example, a simple substance, an alloy or a compound of silicon or tin, or two or more of them, or at least one of those phases or two or more phases. You may have in a part.

  Examples of silicon alloys include those containing at least one of the following elements as constituent elements other than silicon. Tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony or chromium. Examples of silicon compounds include those containing oxygen or carbon as constituent elements other than silicon. The silicon compound may contain, for example, any one or more of the elements described for the silicon alloy as a constituent element other than silicon.

Examples of silicon alloys or compounds include the following. SiB ₄ , SiB ₆ , Mg ₂ Si, Ni ₂ Si, TiSi ₂ , MoSi ₂ , CoSi ₂ , NiSi ₂ , CaSi ₂ , CrSi ₂ or Cu ₅ Si. FeSi ₂ , MnSi ₂ , NbSi ₂ , TaSi ₂ , VSi ₂ , WSi ₂ , ZnSi ₂ , SiC, Si ₃ N ₄ , Si ₂ N ₂ O, SiO _v (0 <v ≦ 2), SnO _w (0 <w ≦ 2) or LiSiO.

Examples of the tin alloy include those containing at least one of the following elements as constituent elements other than tin. Silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony or chromium. Examples of tin compounds include those containing oxygen or carbon. In addition, the compound of tin may contain any 1 type (s) or 2 or more types of the element demonstrated about the alloy of tin as structural elements other than tin, for example. Examples of tin alloys or compounds include SnSiO ₃ , LiSnO, Mg ₂ Sn, and the like.

  In particular, as a material containing silicon (silicon-containing material), for example, a simple substance of silicon is preferable. This is because a high battery capacity and excellent cycle characteristics can be obtained. Note that “single substance” is a simple substance (which may contain a small amount of impurities) in a general sense, and does not necessarily mean 100% purity.

  Moreover, as a material containing tin (tin-containing material), for example, a material containing tin as the first constituent element and further containing the second and third constituent elements is preferable. The second constituent element is, for example, at least one of the following elements. Cobalt, iron, magnesium, titanium, vanadium, chromium, manganese, nickel, copper, zinc, gallium or zirconium. Niobium, molybdenum, silver, indium, cerium (Ce), hafnium, tantalum, tungsten, bismuth or silicon. The third constituent element is, for example, at least one of boron, carbon, aluminum, and phosphorus. This is because by having the second and third constituent elements, a high battery capacity and excellent cycle characteristics can be obtained.

  Among these, a material containing Sn, cobalt, and carbon (SnCoC-containing material) is preferable. As the composition of this SnCoC-containing material, for example, the carbon content is 9.9 mass% to 29.7 mass%, and the content ratio of tin and cobalt (Co / (Sn + Co)) is 20 mass% to 70 mass%. It is below mass%. This is because a high energy density can be obtained in such a composition range.

  This SnCoC-containing material has a phase containing tin, cobalt and carbon, and the phase is preferably low crystalline or amorphous. This phase is a reaction phase capable of reacting with lithium, and excellent characteristics can be obtained by the presence of the reaction phase. The half width of the diffraction peak obtained by X-ray diffraction of this phase is 1.0 ° or more at a diffraction angle 2θ when CuKα ray is used as the specific X-ray and the drawing speed is 1 ° / min. It is preferable. This is because lithium ions are occluded and released more smoothly, and the reactivity with the electrolyte and the like is reduced. Note that the SnCoC-containing material may contain a phase containing a simple substance or a part of each constituent element in addition to the low crystalline or amorphous phase.

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

  In the SnCoC-containing material, it is preferable that at least a part of carbon that is a constituent element is bonded to a metal element or a metalloid element that is another constituent element. This is because aggregation or crystallization of tin or the like is suppressed. The bonding state of elements can be confirmed by, for example, X-ray photoelectron spectroscopy (XPS). In a commercially available apparatus, for example, Al—Kα ray or Mg—Kα ray is used as the soft X-ray. When at least a part of carbon is bonded to a metal element or a metalloid element, the peak of the synthetic wave of carbon 1s orbital (C1s) appears in a region lower than 284.5 eV. It is assumed that the energy calibration is performed so that the peak of 4f orbit (Au4f) of gold atom is obtained at 84.0 eV. At this time, since the surface contamination carbon usually exists on the surface of the substance, the C1s peak of the surface contamination carbon is set to 284.8 eV, which is used as the energy standard. In the XPS measurement, the waveform of the C1s peak is obtained in a form including the surface contamination carbon peak and the carbon peak in the SnCoC-containing material. For example, the analysis is performed using commercially available software. To separate. 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).

  Note that the SnCoC-containing material may further contain other constituent elements as necessary. Examples of such other constituent elements include at least one of silicon, iron, nickel, chromium, indium, niobium, germanium, titanium, molybdenum, aluminum, phosphorus, gallium, and bismuth.

  In addition to this SnCoC-containing material, a material containing tin, cobalt, iron and carbon (SnCoFeC-containing material) is also preferable. The composition of the SnCoFeC-containing material can be arbitrarily set. For example, the composition when the content of iron is set to be small is as follows. The carbon content is 9.9 mass% or more and 29.7 mass% or less, the iron content is 0.3 mass% or more and 5.9 mass% or less, and the content ratio of tin and cobalt (Co / (Sn + Co)) ) Is 30% by mass or more and 70% by mass or less. For example, the composition in the case where the content of iron is set to be large is as follows. The carbon content is 11.9% by mass or more and 29.7% by mass or less. Further, the content ratio of tin, cobalt and iron ((Co + Fe) / (Sn + Co + Fe)) is 26.4 mass% to 48.5 mass%, and the content ratio of cobalt and iron (Co / (Co + Fe)). Is 9.9 mass% or more and 79.5 mass% or less. This is because a high energy density can be obtained in such a composition range. The physical properties and the like (half width, etc.) of this SnCoFeC-containing material are the same as those of the above-described SnCoC-containing material.

  Moreover, as another negative electrode material, a metal oxide or a high molecular compound is mentioned, for example. Examples of the metal oxide include iron oxide, ruthenium oxide, and molybdenum oxide. Examples of the polymer compound include polyacetylene, polyaniline, and polypyrrole.

  Of course, the negative electrode material may be other than the above. A series of negative electrode active materials may be mixed in any combination of two or more.

  The negative electrode active material layer 22B is formed by, for example, a coating method, a gas phase method, a liquid phase method, a thermal spraying method, a firing method (sintering method), or two or more methods thereof. The application method is, for example, a method in which a particulate negative electrode active material is mixed with a binder and then dispersed in a solvent and applied. Examples of the vapor phase method include a physical deposition method or a chemical deposition method. Specifically, there are a vacuum deposition method, a sputtering method, an ion plating method, a laser ablation method, a thermal chemical vapor deposition (CVD) method, a plasma chemical vapor deposition method, and the like. Examples of the liquid phase method include an electrolytic plating method and an electroless plating method. The thermal spraying method is a method of spraying the negative electrode active material in a molten state or a semi-molten state. The baking method is, for example, a method in which heat treatment is performed at a temperature higher than the melting point of a binder or the like after being applied in the same procedure as the application method. A known method can be used for the firing method. As an example, an atmosphere firing method, a reaction firing method, a hot press firing method, or the like can be given.

  The negative electrode active material is, for example, a plurality of particles. In this case, the negative electrode active material layer 22B includes a plurality of particulate negative electrode active materials (hereinafter simply referred to as “negative electrode active material particles”). It is formed by. However, the negative electrode active material particles may be formed by a method other than the vapor phase method.

  When the negative electrode active material particles are formed by a deposition method such as a gas phase method, the negative electrode active material particles may have a single-layer structure formed through a single deposition step, It may have a multilayer structure formed through a plurality of deposition steps. However, when using a vapor deposition method with high heat during deposition, the negative electrode active material particles preferably have a multilayer structure. Since the deposition process of the negative electrode material is performed in a plurality of times (the negative electrode material is sequentially formed and deposited thinly), the negative electrode current collector 22A is exposed to higher heat than when the deposition process is performed once. This is because the time to be saved is shortened. As a result, the negative electrode current collector 22A is less susceptible to thermal damage.

  For example, the negative electrode active material particles are preferably grown from the surface of the negative electrode current collector 22A in the thickness direction of the negative electrode active material layer 22B and connected to the surface of the negative electrode current collector 22A at the root. . This is because the expansion and contraction of the negative electrode active material layer 22B are suppressed during charging and discharging. The negative electrode active material particles are formed by a vapor phase method, a liquid phase method, a thermal spraying method, a firing method, or the like, and are preferably alloyed at least at a part of the interface with the negative electrode current collector 22A. In this case, the constituent element of the negative electrode current collector 22A may be diffused into the negative electrode active material particles at the interface between them, or the constituent element of the negative electrode active material particles may be diffused into the negative electrode current collector 22A. Alternatively, both constituent elements may be diffused.

  In particular, the negative electrode active material layer 22B includes an oxide-containing film that covers the surface of the negative electrode active material particles (a region that will be in contact with the electrolyte if no oxide-containing film is provided), if necessary. Preferably it is. This is because the oxide-containing film functions as a protective film against the electrolyte, so that the decomposition reaction of the electrolyte is suppressed during charging and discharging. Thereby, cycle characteristics and storage characteristics are improved. The oxide-containing film may cover the entire surface of the negative electrode active material particles, or may cover only a part of the surface, but it is preferable to cover the entire surface. This is because the decomposition reaction of the electrolyte is further suppressed.

  The oxide-containing film includes, for example, at least one of a silicon oxide, a germanium oxide, and a tin oxide, and preferably includes a silicon oxide. This is because the entire surface of the negative electrode active material particles can be easily covered and an excellent protective action can be obtained. Of course, the oxide-containing film may contain an oxide other than the above.

  The oxide-containing film is formed by, for example, a gas phase method or a liquid phase method, and among these, it is preferably formed by a liquid phase method. This is because the surface of the negative electrode active material particles can be easily covered over a wide range. Examples of the liquid phase method include a liquid phase precipitation method, a sol-gel method, a coating method, or a dip coating method. Among these, the liquid phase precipitation method, the sol-gel method, or the dip coating method is preferable, and the liquid phase precipitation method is more preferable. This is because a higher effect can be obtained. Note that the oxide-containing film may be formed by a single formation method among the above-described series of formation methods, or may be formed by two or more types of formation methods.

  Further, the negative electrode active material layer 22B has a metal material containing a metal element that does not alloy with lithium as a constituent element in the gap inside the negative electrode active material layer 22B as necessary (hereinafter simply referred to as “metal material”). It is preferable that it contains. This is because a plurality of negative electrode active material particles are bound via the metal material, and expansion and contraction of the negative electrode active material layer 22B are suppressed. Thereby, cycle characteristics and storage characteristics are improved. The details of the “gap inside the negative electrode active material layer 22B” will be described later (see FIGS. 5 and 6).

  Examples of the metal element described above include at least one of iron, cobalt, nickel, zinc, and copper. Of these, cobalt is preferable. This is because the metal material can easily enter the gap in the negative electrode active material layer 22B and an excellent binding action can be obtained. Of course, the metal element may be a metal element other than the above. However, the “metal material” referred to here is not limited to a simple substance but is a broad concept including an alloy or a metal compound.

  The metal material is formed by, for example, a gas phase method or a liquid phase method, and it is preferable that the metal material is formed by a liquid phase method. This is because the metal material easily enters the gap in the negative electrode active material layer 22B. Examples of the liquid phase method include an electrolytic plating method and an electroless plating method, among which the electrolytic plating method is preferable. This is because the metal material is more likely to enter the gaps and the formation time thereof can be shortened. This metal material may be formed by a single forming method in the series of forming methods described above, or may be formed by two or more forming methods.

  Note that the negative electrode active material layer 22B may include only one of the oxide-containing film and the metal material, or may include both. However, in order to improve the cycle characteristics and the like, it is preferable to include both. In the case of including only one of them, it is preferable to include an oxide-containing film in order to further improve the cycle characteristics and the like. In the case where both the oxide-containing film and the metal material are included, whichever may be formed first, in order to improve the cycle characteristics and the like, it is preferable to form the oxide-containing film first.

  Here, the detailed configuration of the negative electrode 22 will be described with reference to FIGS.

  First, the case where the negative electrode active material layer 22B includes an oxide-containing film together with a plurality of negative electrode active material particles will be described. 3 and 4 schematically show a cross-sectional structure of the negative electrode 22. Here, the case where the negative electrode active material particles have a single layer structure is shown.

  In the case shown in FIG. 3, for example, when a negative electrode material is deposited on the negative electrode current collector 22A by a vapor phase method such as a vapor deposition method, a plurality of negative electrode active material particles 221 are formed on the negative electrode current collector 22A. It is formed. In this case, when the surface of the negative electrode current collector 22A is roughened and a plurality of protrusions (for example, fine particles formed by electrolytic treatment) are present on the surface, the negative electrode active material particles 221 are arranged together with the protrusions described above. Grows in the thickness direction. For this reason, the plurality of negative electrode active material particles 221 are arranged on the surface of the negative electrode current collector 22A and are connected to the surface of the negative electrode current collector 22A at the root. After that, for example, when the oxide-containing film 222 is formed on the surface of the negative electrode active material particles 221 by a liquid phase method such as a liquid phase deposition method, the oxide-containing film 222 is applied to the surface of the negative electrode active material particles 221. Cover almost entirely. In this case, a wide range from the top of the negative electrode active material particle 221 to the root is covered. Such a wide covering state is a characteristic obtained when the oxide-containing film 222 is formed by a liquid phase method. That is, when the oxide-containing film 222 is formed by using the liquid phase method, the covering action extends not only to the top of the negative electrode active material particles 221 but also to the root, and thus the base is covered with the oxide-containing film 222.

  On the other hand, in the case shown in FIG. 4, for example, after the plurality of negative electrode active material particles 221 are formed by the vapor phase method, the oxide-containing film 223 is similarly formed by the vapor phase method. The oxide-containing film 223 covers only the tops of the negative electrode active material particles 221. Such a narrow covering state is a characteristic obtained when the oxide-containing film 223 is formed by a vapor phase method. That is, when the oxide-containing film 223 is formed using the vapor phase method, the covering action does not reach the root of the negative electrode active material particles 221, but the base is not covered with the oxide-containing film 223.

  3 illustrates the case where the negative electrode active material layer 22B is formed by a vapor phase method, but the negative electrode active material layer 22B may be formed by another forming method such as a coating method or a sintering method. The same. Also in these cases, the oxide-containing film 222 is formed so as to cover almost the entire surface of the plurality of negative electrode active material particles.

  Next, the case where the negative electrode active material layer 22B includes a metal material together with a plurality of negative electrode active material particles will be described. 5 and 6 show an enlarged cross-sectional structure of the negative electrode 22. 5 and 6, (A) is a scanning electron microscope (SEM) photograph (secondary electron image), and (B) is a schematic picture of the SEM image shown in (A). Here, a case where a plurality of negative electrode active material particles 221 have a multilayer structure is shown.

  As shown in FIG. 5, when the negative electrode active material particles 221 have a multilayer structure, a plurality of gaps 224 are generated inside the negative electrode active material layer 22B due to the arrangement structure, the multilayer structure, and the surface structure. ing. The gap 224 mainly includes two types of gaps 224A and 224B classified according to the cause of occurrence. The gap 224 </ b> A is generated between adjacent negative electrode active material particles 221, and the gap 224 </ b> B is generated between layers of the negative electrode active material particles 221.

  Note that a void 225 may be formed on the exposed surface (outermost surface) of the negative electrode active material particles 221. The voids 225 are generated between the protrusions because fine whisker-like protrusions (not shown) are formed on the surface of the negative electrode active material particles 221. The void 225 may be generated over the entire exposed surface of the negative electrode active material particles 221 or may be generated only in part. However, since the above-described whisker-like protrusions are generated on the surface every time the negative electrode active material particles 221 are formed, the void 225 is generated not only on the exposed surface of the negative electrode active material particles 221 but also between the layers. There is.

  As shown in FIG. 6, the negative electrode active material layer 22B has a metal material 226 in the gaps 224A and 224B. In this case, the metal material 226 may be provided in only one of the gaps 224A and 224B, but it is preferable that the metal material 226 is provided in both of them. This is because a higher effect can be obtained.

  The metal material 226 enters the gap 224A between the adjacent negative electrode active material particles 221. Specifically, when the negative electrode active material particles 221 are formed by a vapor phase method or the like, as described above, the negative electrode active material particles 221 grow for each protrusion existing on the surface of the negative electrode current collector 22A. A gap 224 </ b> A is generated between the adjacent negative electrode active material particles 221. Since the gap 224A causes a decrease in the binding property of the negative electrode active material layer 22B, a metal material 226 is embedded in the gap 224A in order to improve the binding property. In this case, a part of the gap 224A only needs to be filled, but the larger the filling amount, the better. This is because the binding property of the negative electrode active material layer 22B is further improved. The filling amount of the metal material 226 is preferably 20% or more, more preferably 40% or more, and further preferably 80% or more.

  In addition, the metal material 226 enters the gap 224 </ b> B in the negative electrode active material particles 221. Specifically, when the negative electrode active material particles 221 have a multilayer structure, a gap 224B is generated between the layers. Like the gap 224A, the gap 224B causes a decrease in the binding property of the negative electrode active material layer 22B. Therefore, in order to improve the binding property, the metal material 226 is embedded in the gap 224B. In this case, it is sufficient that a part of the gap 224B is filled, but a larger filling amount is preferable. This is because the binding property of the negative electrode active material layer 22B is further improved.

  Note that the negative electrode active material layer 22B is provided in order to prevent negative whisker-like protrusions (not shown) generated on the exposed surface of the uppermost negative electrode active material particles 221 from adversely affecting the performance of the secondary battery. A metal material 226 may be provided in the gap 225. Specifically, when the negative electrode active material particles 221 are formed by a vapor phase method or the like, fine whisker-like protrusions are formed on the surface thereof, and voids 225 are generated between the protrusions. The voids 225 increase the surface area of the negative electrode active material particles 221 and increase the amount of irreversible film formed on the surface of the negative electrode active material particles 221, which may cause a reduction in the progress of the charge / discharge reaction. . Therefore, a metal material 226 is embedded in the gap 225 in order to suppress a decrease in the progress of the charge / discharge reaction. In this case, it is sufficient that a part of the gap 225 is buried, but the larger the amount of filling, the better. This is because the progress of the charge / discharge reaction can be further suppressed. In FIG. 6, the fact that the metal material 226 is scattered on the surface of the uppermost negative electrode active material particle 221 indicates that the above-described fine protrusions are present at the spot. Of course, the metal material 226 does not necessarily have to be scattered on the surface of the negative electrode active material particle 221, and may cover the entire surface.

  In particular, the metal material 226 that has entered the gap 224B also functions to fill the gap 225 in each layer. Specifically, when the negative electrode material is deposited a plurality of times, a fine protrusion is generated on the surface of the negative electrode active material particle 221 for each deposition. For this reason, the metal material 226 is not only embedded in the gap 224B in each layer, but also embedded in the gap 225 in each layer.

  5 and 6, the case where the negative electrode active material particles 221 have a multilayer structure and both the gaps 224A and 224B exist in the negative electrode active material layer 22B has been described. For this reason, the negative electrode active material layer 22B has the metal material 226 in the gaps 224A and 224B. On the other hand, when the negative electrode active material particle 221 has a single layer structure and only the gap 224A exists in the negative electrode active material layer 22B, the negative electrode active material layer 22B has the metal material 226 only in the gap 224A. It will have. Of course, since the gap 225 is generated in both cases, the gap 225 has the metal material 226 in either case.

[Separator]
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 a synthetic resin such as polytetrafluoroethylene, polypropylene, or polyethylene, or a porous film made of ceramic, and two or more kinds of these porous films are laminated. It may be done.

[Electrolyte]
The separator 23 is impregnated with the above-described electrolyte as a liquid electrolyte (electrolytic solution). The content of the halogenated cyclic compound in the solvent is preferably determined according to, for example, the type of the negative electrode active material. Specifically, when the negative electrode active material contains a carbon material, it is preferably 0.01 wt% or more and 10 wt%, and when the negative electrode active material contains a metal material, 0.01 wt% The content is preferably 50% by weight or less. This is because the chemical stability of the electrolytic solution is improved, so that the decomposition reaction of the electrolytic solution is suppressed during charging and discharging.

[Operation of secondary battery]
In this secondary battery, at the time of charging, for example, lithium ions are released from the positive electrode 21 and inserted in the negative electrode 22 through the electrolytic solution impregnated in the separator 23. On the other hand, at the time of discharging, for example, lithium ions are released from the negative electrode 22 and inserted in the positive electrode 21 through the electrolytic solution impregnated in the separator 23.

[Method for producing secondary battery]
This secondary battery is manufactured by the following procedure, for example.

  First, the positive electrode 21 is produced. First, a positive electrode active material and, if necessary, a positive electrode binder and a positive electrode conductive agent are mixed to form a positive electrode mixture, and 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 and then dried to form the positive electrode active material layer 21B. Finally, the positive electrode active material layer 21B is compression-molded using a roll press or the like while being heated as necessary. In this case, the compression molding may be repeated a plurality of times.

  Next, the negative electrode 22 is produced by the same procedure as that of the positive electrode 21 described above. In this case, a negative electrode mixture obtained by mixing a negative electrode active material and, if necessary, a negative electrode binder and a negative electrode conductive agent is dispersed in an organic solvent to obtain a paste-like negative electrode mixture slurry. After that, the negative electrode mixture slurry is uniformly applied to both surfaces of the negative electrode current collector 22A to form the negative electrode active material layer 22B, and then the negative electrode active material layer 22B is compression molded.

  Note that the negative electrode 22 may be manufactured by a procedure different from that of the positive electrode 21. In this case, first, a negative electrode material is deposited on both surfaces of the negative electrode current collector 22A using a vapor phase method such as a vapor deposition method to form a plurality of negative electrode active material particles. After that, if necessary, an oxide-containing film is formed using a liquid phase method such as a liquid phase deposition method, or a metal material is formed using a liquid phase method such as an electrolytic plating method, or both are formed. Thus, the negative electrode active material layer 22B is formed.

  Finally, a secondary battery is assembled using the electrolytic solution together with the positive electrode 21 and the negative electrode 22. 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 accommodated in the battery can 11 while being sandwiched between the pair of insulating plates 12 and 13. In this case, the tip of the positive electrode lead 25 is attached to the safety valve mechanism 15 by welding or the like, and the tip of the negative electrode lead 26 is attached to the battery can 11 by welding or the like. Subsequently, an electrolytic solution is injected into the battery can 11 and impregnated in the separator 23. Finally, the battery lid 14, the safety valve mechanism 15, and the heat sensitive resistance element 16 are caulked to the opening end of the battery can 11 through the gasket 17. Thereby, the secondary battery shown in FIGS. 1 and 2 is completed.

  According to the first secondary battery, when the capacity of the negative electrode 22 is expressed by occlusion and release of lithium ions, the above-described electrolyte (electrolytic solution) is provided, so that the electrolytic solution is decomposed during charging and discharging. The reaction is suppressed. Therefore, excellent cycle characteristics and storage characteristics can be obtained.

  In particular, when a metal material (such as a simple substance of silicon or a SnCoC-containing material) that is advantageous for increasing the capacity is used as the negative electrode active material of the negative electrode 22, excellent cycle characteristics and storage characteristics can be obtained. It is possible to obtain a higher effect than when it is present.

<2-2. Second secondary battery>
The second secondary battery is a lithium metal secondary battery in which the capacity of the negative electrode is expressed by precipitation and dissolution of lithium metal. This secondary battery has the same configuration as the first secondary battery except that the negative electrode active material layer 22B is made of lithium metal, and is manufactured by the same procedure.

  This secondary battery uses lithium metal as a negative electrode active material, and can thereby obtain a high energy density. The negative electrode active material layer 22B may already exist from the time of assembly, but may not be present at the time of assembly, and may be composed of lithium metal deposited during charging. Further, the negative electrode current collector 22A may be omitted by using the negative electrode active material layer 22B as a current collector.

  In this secondary battery, at the time of charging, for example, lithium ions are released from the positive electrode 21 and deposited as lithium metal on the surface of the negative electrode current collector 22 </ b> A through the electrolytic solution impregnated in the separator 23. On the other hand, at the time of discharge, for example, lithium metal is eluted as lithium ions from the negative electrode active material layer 22 </ b> B and inserted into the positive electrode 21 through the electrolytic solution impregnated in the separator 23.

  According to the second secondary battery, when the capacity of the negative electrode 22 is expressed by precipitation and dissolution of lithium metal, the above-described electrolyte (electrolytic solution) is provided. Therefore, excellent cycle characteristics and storage characteristics can be obtained by the same action as the first secondary battery. Other effects relating to the secondary battery are the same as those of the first secondary battery.

<2-3. Third secondary battery>
FIG. 7 illustrates an exploded perspective configuration of the third secondary battery, and FIG. 8 illustrates an enlarged cross section taken along line VIII-VIII of the spirally wound electrode body 30 illustrated in FIG.

  This secondary battery is, for example, a lithium ion secondary battery as in the case of the first secondary battery, and is mainly a winding in which the positive electrode lead 31 and the negative electrode lead 32 are attached inside the film-shaped exterior member 40. The rotating electrode body 30 is accommodated. A battery structure using such an exterior member 40 is called a laminate film type.

  For example, 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 toward the outside. However, the installation position of the positive electrode lead 31 and the negative electrode lead 32 with respect to the spirally wound electrode body 30, the lead-out direction thereof, and the like are not particularly limited. The positive electrode lead 31 is made of, for example, aluminum, and the negative electrode lead 32 is made of, for example, copper, nickel, stainless steel, or the like. These materials have, for example, a thin plate shape or a mesh shape.

  The exterior member 40 is, for example, a laminate film in which a fusion layer, a metal layer, and a surface protective layer are laminated in this order. In this case, for example, the outer edges of the fusion layers of the two films are bonded together by an adhesive or the like so that the fusion layer faces the wound electrode body 30. The fusion layer is, for example, a polymer film such as polyethylene or polypropylene. The metal layer is, for example, a metal foil such as an aluminum foil. The surface protective layer is, for example, a polymer film such as nylon or polyethylene terephthalate.

  Among these, as the exterior member 40, an aluminum laminated film in which a polyethylene film, an aluminum foil, and a nylon film are laminated in this order is preferable. However, the exterior member 40 may be a laminated film having another laminated structure instead of the above-described aluminum laminated film, or may be a polymer film such as polypropylene or a metal film.

  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. Examples of such a material include polyolefin resins such as polyethylene, polypropylene, modified polyethylene, and modified polypropylene.

  The wound electrode body 30 is obtained by laminating and winding a positive electrode 33 and a negative electrode 34 via a separator 35 and an electrolyte layer 36, and an outermost peripheral portion thereof is protected by a protective tape 37. In the positive electrode 33, for example, a positive electrode active material layer 33B is provided on both surfaces of a positive electrode current collector 33A. The configurations of the positive electrode current collector 33A and the positive electrode active material layer 33B are the same as those of the positive electrode current collector 21A and the positive electrode active material layer 21B in the first secondary battery, respectively. In the negative electrode 34, for example, a negative electrode active material layer 34B is provided on both surfaces of a negative electrode current collector 34A. The configurations of the negative electrode current collector 34A and the negative electrode active material layer 34B are the same as the configurations of the negative electrode current collector 22A and the negative electrode active material layer 22B in the first secondary battery, respectively.

  The configuration of the separator 35 is the same as the configuration of the separator 23 in the first secondary battery.

  The electrolyte layer 36 is one in which an electrolytic solution is held by a polymer compound, and may contain other materials such as various additives as necessary. The electrolyte layer 36 is 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 leakage of the electrolyte is prevented.

  Examples of the polymer compound include at least one of the following polymer materials. Polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, polysiloxane, or polyvinyl fluoride. Polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene or polycarbonate. It is a copolymer of vinylidene fluoride and hexafluoropyrene. These may be single and multiple types may be mixed. Among these, polyvinylidene fluoride or a copolymer of vinylidene fluoride and hexafluoropyrene is preferable. This is because it is electrochemically stable.

  The composition of the electrolytic solution is the same as the composition of the electrolytic solution in the first secondary battery. However, in the electrolyte layer 36 which is a gel electrolyte, the solvent of the electrolytic solution is a wide concept including not only a liquid solvent but also a material having ion conductivity capable of dissociating the electrolyte salt. Therefore, when using a polymer compound having ion conductivity, the polymer compound is also included in the solvent.

  In place of the gel electrolyte layer 36 in which the electrolytic solution is held by the polymer compound, the electrolytic solution may be used as it is. In this case, the separator 35 is impregnated with the electrolytic solution.

  In this secondary battery, at the time of charging, for example, lithium ions are released from the positive electrode 33 and inserted in the negative electrode 34 through the electrolyte layer 36. On the other hand, at the time of discharging, for example, lithium ions are released from the negative electrode 34 and inserted in the positive electrode 53 through the electrolyte layer 36.

  The secondary battery provided with the gel electrolyte layer 36 is manufactured by, for example, the following three types of procedures.

  In the first manufacturing method, first, the positive electrode 33 and the negative electrode 34 are manufactured by the same procedure as that of the positive electrode 21 and the negative electrode 22 in the first secondary battery. Specifically, the positive electrode active material layer 33B is formed on both surfaces of the positive electrode current collector 33A to produce the positive electrode 33, and 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. To do. Then, after preparing the precursor solution containing electrolyte solution, a high molecular compound, and a solvent and apply | coating to the positive electrode 33 and the negative electrode 34, the solvent is volatilized and the gel electrolyte layer 36 is formed. Subsequently, the positive electrode lead 31 is attached to the positive electrode current collector 33A by welding or the like, and the negative electrode lead 32 is attached to the negative electrode current collector 34A by welding or the like. Subsequently, the positive electrode 33 and the negative electrode 34 on which the electrolyte layer 36 is formed are stacked and wound via the separator 35, and then a protective tape 37 is adhered to the outermost peripheral portion to produce the wound electrode body 30. . Finally, after sandwiching the wound electrode body 30 between the two film-shaped exterior members 40, the outer edges of the exterior member 40 are bonded to each other by heat fusion or the like, and the wound electrode body 30 is enclosed. To do. 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 secondary battery shown in FIGS. 7 and 8 is completed.

  In the second manufacturing method, first, 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-shaped exterior members 40, the remaining outer peripheral edge except for the outer peripheral edge on one side is adhered by heat fusion or the like, thereby forming a bag-shaped exterior 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 fusion or the like. Finally, the monomer is thermally polymerized to obtain a polymer compound, and the gel electrolyte layer 36 is formed. Thereby, the secondary battery is completed.

  In the third manufacturing method, a wound body is formed by forming a wound body in the same manner as in the second manufacturing method described above except that the separator 35 coated with the polymer compound on both sides is used first. 40 is housed inside. Examples of the polymer compound applied to the separator 35 include a polymer (such as a homopolymer, a copolymer, or a multi-component copolymer) containing vinylidene fluoride as a component. Specifically, polyvinylidene fluoride, a binary copolymer containing vinylidene fluoride and hexafluoropropylene as components, and a ternary copolymer containing vinylidene fluoride, hexafluoropropylene and chlorotrifluoroethylene as components. Such as coalescence. In addition, the high molecular compound may contain the other 1 type, or 2 or more types of high molecular compound with the polymer which uses the above-mentioned vinylidene fluoride as a component. Subsequently, after the electrolytic solution is prepared and injected into the exterior member 40, the opening of the exterior member 40 is sealed by heat fusion or the like. Finally, the exterior member 40 is heated while applying a load to bring the separator 35 into close contact with the positive electrode 33 and the negative electrode 34 via the polymer compound. As a result, the electrolytic solution is impregnated into the polymer compound, and the polymer compound is gelled to form the electrolyte layer 36, thereby completing the secondary battery.

  In the third manufacturing method, battery swelling is suppressed more than in the first manufacturing method. Further, in the third manufacturing method, almost no monomer or solvent, which is a raw material of the polymer compound, remains in the electrolyte layer 36 and the formation process of the polymer compound is better controlled than in the second manufacturing method. . For this reason, sufficient adhesion is obtained between the positive electrode 33, the negative electrode 34 and the separator 35 and the electrolyte layer 36.

  According to the third secondary battery, when the capacity of the negative electrode 34 is expressed by insertion and extraction of lithium ions, the electrolyte layer 36 includes the above-described electrolyte (electrolytic solution). Therefore, excellent cycle characteristics and storage characteristics can be obtained by the same action as the first secondary battery. Other effects relating to the secondary battery are the same as those of the first secondary battery. Note that the third secondary battery is not limited to having the same configuration as the first secondary battery, and may have the same configuration as the second secondary battery.

  Specific examples of the present invention will be described in detail.

(Experimental Examples 1-1 to 1-20)
The laminate film type lithium ion secondary battery shown in FIGS. 7 and 8 was produced by the following procedure.

First, the positive electrode 33 was produced. First, lithium carbonate (Li ₂ CO ₃ ) and cobalt carbonate (CoCO ₃ ) were mixed at a molar ratio of 0.5: 1, and then calcined in air at 900 ° C. for 5 hours to obtain a lithium cobalt composite oxide ( LiCoO ₂ ) was obtained. Subsequently, 91 parts by mass of lithium cobalt composite oxide as a positive electrode active material, 6 parts by mass of graphite as a positive electrode conductive agent, and 3 parts by mass of polyvinylidene fluoride as a positive electrode binder were mixed to obtain a positive electrode mixture. Subsequently, the positive electrode mixture was dispersed in N-methyl-2-pyrrolidone to obtain a paste-like positive electrode mixture slurry. Subsequently, the positive electrode mixture slurry was uniformly applied to both surfaces of the positive electrode current collector 33A using a coating apparatus, and then dried to form the positive electrode active material layer 33B. As the positive electrode current collector 33A, a strip-shaped aluminum foil (thickness = 20 μm) was used. Finally, the positive electrode active material layer 33B was compression molded using a roll press.

  Next, the negative electrode 34 was produced. First, 90 parts by mass of artificial graphite as a negative electrode active material and 10 parts by mass of polyvinylidene fluoride as a negative electrode binder were mixed to obtain a negative electrode mixture. Subsequently, the negative electrode mixture was dispersed in N-methyl-2-pyrrolidone to obtain a paste-like negative electrode mixture slurry. Subsequently, the negative electrode mixture slurry was uniformly applied to both surfaces of the negative electrode current collector 34A using a coating apparatus and then dried to form a negative electrode active material layer 34B. As the negative electrode current collector 34A, a strip-shaped electrolytic copper foil (thickness = 15 μm) was used. Finally, the negative electrode active material layer 34B was compression molded using a roll press.

Next, an electrolytic solution that is a liquid electrolyte was prepared. First, after mixing ethylene carbonate (EC) and diethyl carbonate (DEC) as a solvent, a halogenated cyclic compound was added as another solvent. In this case, the mixing ratio of EC and DEC was set to EC: DEC = 50: 50 by weight, and the type and content of the halogenated cyclic compound were set as shown in Table 1. After that, lithium hexafluorophosphate (LiPF ₆ ) was dissolved as an electrolyte salt in the mixed solvent. In this case, the content of the electrolyte salt was 1 mol / kg with respect to the mixed solvent.

  Finally, a secondary battery was assembled using the electrolytic solution together with the positive electrode 33 and the negative electrode 34. First, the positive electrode lead 31 made of aluminum was welded to one end of the positive electrode current collector 33A, and the negative electrode lead 32 made of nickel was welded to one end of the negative electrode current collector 34A. Subsequently, after laminating the positive electrode 33, the separator 35, the negative electrode 34, and the separator 35 in this order and then winding them in the longitudinal direction, fixing the winding end portion with a protective tape 37 made of an adhesive tape, A wound body that is a precursor of the wound electrode body 30 was formed. As the separator 35, a three-layer structure (thickness = 23 μm) in which a film mainly composed of porous polyethylene was sandwiched between films mainly composed of porous polypropylene. Subsequently, after sandwiching the wound body between the exterior members 40, the outer edge portions except for one side were heat-sealed, and the wound body was housed inside the bag-shaped exterior member 40. As the exterior member 40, a laminate having a three-layer structure in which a nylon film (thickness = 30 μm), an aluminum foil (thickness = 40 μm), and an unstretched polypropylene film (thickness = 30 μm) are laminated from the outside. A film (total thickness = 100 μm) was used. Subsequently, an electrolytic solution was injected from the opening of the exterior member 40 and impregnated in the separator 35, thereby manufacturing the wound electrode body 30. Finally, the laminated film type secondary battery was completed by thermally sealing and sealing the opening of the exterior member 40 in a vacuum atmosphere. In the production of this secondary battery, the thickness of the positive electrode active material layer 33B was adjusted so that lithium metal did not deposit on the negative electrode 34 during full charge.

(Experimental Examples 1-21 to 1-23)
As shown in Table 1, Experimental Examples 1-1 to 1-20 except that the halogenated cyclic compound was not used, the compound shown in Formula (13) was used, or only the halogenated cyclic compound was used. The same procedure was followed.

  For the secondary batteries of Examples 1-1 to 1-23, the cycle characteristics and the storage characteristics were examined. The results shown in Table 1 were obtained.

  When examining the cycle characteristics, first, charging and discharging were performed for 2 cycles in an atmosphere at 23 ° C., and the discharge capacity at the second cycle was measured. Subsequently, the battery was repeatedly charged and discharged in the same atmosphere until the total number of cycles reached 300 cycles, and the discharge capacity at the 300th cycle was measured. Finally, the cycle retention ratio (%) = (discharge capacity at the 300th cycle / discharge capacity at the second cycle) × 100 was calculated. At the time of charging, constant current constant voltage charging was performed up to an upper limit voltage of 4.2 V with a current of 0.2C. At the time of discharge, constant current discharge was performed with a current of 0.2 C to a final voltage of 2.7 V. This “0.2 C” is a current value at which the theoretical capacity can be discharged in 5 hours.

  When examining the storage characteristics, first, charging and discharging were performed for 2 cycles in an atmosphere at 23 ° C., and the discharge capacity before storage was measured. Subsequently, the battery was stored again in a constant temperature bath at 80 ° C. for 10 days while being charged again, and then discharged in an atmosphere at 23 ° C., and the discharge capacity after storage was measured. Finally, storage retention ratio (%) = (discharge capacity after storage / discharge capacity before storage) × 100 was calculated. The charge / discharge conditions are the same as in the case of examining the cycle characteristics.

  The procedure and conditions for examining the cycle characteristics and storage characteristics described above are the same in the following.

  In a secondary battery using a carbon material (artificial graphite) as a negative electrode active material, when two or more kinds of solvents including a halogenated cyclic compound were used, a high cycle retention rate and storage retention rate were obtained. In this case, better results were obtained when the content of the halogenated cyclic compound was 0.01 wt% or more and 10 wt% or less. When only the halogenated cyclic compound was used, the charge / discharge reaction hardly proceeded, and therefore the cycle maintenance ratio and the storage maintenance ratio could not be calculated. From these facts, in the secondary battery of the present invention, when artificial graphite is used as the negative electrode active material, the electrolyte solution contains other non-aqueous solvent together with the halogenated cyclic compound. Storage characteristics are obtained.

(Experimental examples 2-1 to 2-22)
As shown in Table 2, the same procedure as in Experimental Examples 1-4, 1-6, and 1-21 was performed except that the composition of the mixed solvent in the electrolytic solution was changed. In this case, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) or propylene carbonate (PC) was used. Methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA) or γ-butyrolactone (GBL) was used. Vinylene carbonate (VC), bis (fluoromethyl) carbonate (DFDMC), 4-fluoro-1,3-dioxolan-2-one (FEC) or trans-4,5-difluoro-1,3-dioxolan-2-one (DFEC) was used. Propene sultone (PRS), sulfobenzoic anhydride (SBAH) or sulfopropionic anhydride (SPAH) was used. The mixing ratio of EC, PC, and DEC was EC: PC: DEC = 10: 20: 70 by weight. The contents of VC and DFEC were 2% by weight, the contents of DFDMC and FEC were 5% by weight, and the contents of PRS, SBAH and SPAH were 1% by weight. When the cycle characteristics and the storage characteristics of the secondary batteries of Examples 2-1 to 2-22 were examined, the results shown in Table 2 were obtained.

  Even when the composition of the mixed solvent was changed, the same results as in Table 1 were obtained. In particular, when VC or the like is added, the cycle maintenance ratio and the storage maintenance ratio may increase. Therefore, in the secondary battery of the present invention using artificial graphite as the negative electrode active material, excellent cycle characteristics and storage characteristics can be obtained even if the composition of the mixed solvent is changed.

(Experimental examples 3-1 to 3-4)
As shown in Table 3, the same procedure as in Experimental Example 1-4 was performed except that the type of electrolyte salt in the electrolytic solution was changed. In this case, lithium tetrafluoroborate (LiBF ₄ ) or (4,4,4-trifluorobutyric acid oxalate) lithium borate (LiTFOB) shown in Formula (8-8) was used. Bis (trifluoromethanesulfonyl) imidolithium (LiN (CF ₃ SO ₂ ) ₂ : LiTFSI) or lithium difluorophosphate (LiPF ₂ O ₂ ) was used. Further, the content of LiPF ₆ was 0.9 mol / kg with respect to the mixed solvent, and the content of LiBF _{4 and the} like was 0.1 mol / kg with respect to the mixed solvent. When the cycle characteristics and storage characteristics of the secondary batteries of Examples 3-1 to 3-4 were examined, the results shown in Table 3 were obtained.

  Even when the type of the electrolyte salt was changed, the same results as in Table 1 were obtained. Therefore, in the secondary battery of the present invention using artificial graphite as the negative electrode active material, excellent cycle characteristics and storage characteristics can be obtained even if the type of the electrolyte salt is changed.

(Experimental examples 4-1 to 4-27)
The same procedure as in Experimental Examples 1-1 to 1-23 was performed except that the negative electrode 34 was produced using silicon as the negative electrode active material and the content of the halogenated cyclic compound was changed as shown in Table 4. Passed. In the case of producing the negative electrode 34, silicon was deposited on the surface of the negative electrode current collector 34A using a vapor deposition method (electron beam vapor deposition method) to form a negative electrode active material layer 34B including a plurality of negative electrode active material particles. . In this case, the deposition process was repeated 10 times so that the total thickness of the negative electrode active material layer 22B was 6 μm. When the cycle characteristics and the storage characteristics of the secondary batteries of Examples 4-1 to 4-27 were examined, the results shown in Table 4 were obtained.

  In the secondary battery using a metal material (silicon) as the negative electrode active material, the same results as in Table 1 were obtained. That is, when two or more kinds of solvents containing a halogenated cyclic compound were used, a high cycle retention rate and storage retention rate were obtained. From these facts, in the secondary battery of the present invention, when silicon is used as the negative electrode active material, the solvent of the electrolytic solution contains other non-aqueous solvent together with the halogenated cyclic compound. Characteristics are obtained.

(Experimental examples 5-1 to 5-22)
As shown in Table 5, the same procedure as in Experimental Examples 2-1 to 2-22 was performed except that silicon was used as the negative electrode active material in the same manner as in Experimental Examples 4-1 to 4-27. When the cycle characteristics and the storage characteristics of the secondary batteries of Examples 5-1 to 5-22 were examined, the results shown in Table 5 were obtained.

  Even when the composition of the mixed solvent was changed, the same results as in Table 4 were obtained. For these reasons, in the secondary battery of the present invention using silicon as the negative electrode active material, excellent cycle characteristics and storage characteristics can be obtained even if the composition of the mixed solvent is changed.

(Experimental examples 6-1 to 6-4)
As shown in Table 6, the same procedure as in Experimental Examples 3-1 to 3-4 was performed except that silicon was used as the negative electrode active material in the same manner as in Experimental Examples 4-1 to 4-27. When the cycle characteristics and storage characteristics of the secondary batteries of Examples 6-1 to 6-4 were examined, the results shown in Table 6 were obtained.

  Even when the type of the electrolyte salt was changed, the same results as in Table 4 were obtained. For these reasons, in the secondary battery of the present invention using silicon as the negative electrode active material, excellent cycle characteristics and storage characteristics can be obtained even if the type of the electrolyte salt is changed.

(Experimental examples 7-1 to 7-4)
A procedure similar to that of Experimental Examples 4-4, 5-11, 4-25, and 5-21 was performed except that the negative electrode 34 was produced using a SnCoC-containing material as the negative electrode active material.

  In producing the negative electrode 34, first, cobalt powder and tin powder were alloyed to form cobalt-tin alloy powder, and then carbon powder was added and dry mixed. Subsequently, 10 g of the above mixture was set together with about 400 g of steel balls having a diameter of 9 mm in a reaction vessel of a planetary ball mill manufactured by Ito Seisakusho. Subsequently, after replacing the inside of the reaction vessel with an argon atmosphere, an operation for 10 minutes and a pause for 10 minutes at a rotation speed of 250 revolutions per minute were repeated until the total operation time reached 20 hours. Subsequently, after the reaction vessel was cooled to room temperature and the SnCoC-containing material was taken out, the coarse powder was removed through a 280 mesh sieve.

  When the composition of the obtained SnCoC-containing material was analyzed, the content of tin was 49.5% by mass, the content of cobalt was 29.7% by mass, the content of carbon was 19.8% by mass, the content of tin and cobalt The ratio (Co / (Sn + Co)) was 37.5% by mass. At this time, the tin and cobalt contents were measured by inductively coupled plasma (ICP) emission analysis, and the carbon content was measured by a carbon / sulfur analyzer. Further, when the SnCoC-containing material was analyzed by the X-ray diffraction method, a diffraction peak having a half width in the range of 2θ = 20 ° to 50 ° was observed. Further, when the SnCoC-containing material was analyzed by XPS, a peak P1 was obtained as shown in FIG. When this peak P1 was analyzed, a peak P2 of surface contamination carbon and a peak P3 of C1s in the SnCoC-containing material on the lower energy side (region lower than 284.5 eV) were obtained. From this result, it was confirmed that carbon in the SnCoC-containing material was bonded to other elements.

  After obtaining the SnCoC-containing material, 80 parts by mass of the SnCoC-containing material as the negative electrode active material, 8 parts by mass of polyvinylidene fluoride as the negative electrode binder, 11 parts by mass of graphite and 1 part by mass of acetylene black as the negative electrode conductive agent Thus, a negative electrode mixture was obtained. Subsequently, the negative electrode mixture was dispersed in N-methyl-2-pyrrolidone to obtain a paste-like negative electrode mixture slurry. Finally, the negative electrode mixture slurry is uniformly applied to both surfaces of the negative electrode current collector 22A using a coating apparatus and then dried to form the negative electrode active material layer 34B, and then the film is compressed using a roll press. Molded.

  When the cycle characteristics, storage characteristics, and initial charge / discharge characteristics of the secondary batteries of Experimental Examples 7-1 to 7-4 were examined, the results shown in Table 7 were obtained.

  In the secondary battery using a metal-based material (SnCoC-containing material) as the negative electrode active material, the same results as in Table 4 were obtained. That is, when two or more kinds of solvents containing a halogenated cyclic compound were used, a high cycle retention rate and storage retention rate were obtained. Therefore, in the secondary battery of the present invention, when the SnCoC-containing material is used as the negative electrode active material, excellent cycle characteristics are obtained because the solvent of the electrolytic solution contains other non-aqueous solvent together with the halogenated cyclic compound. And storage properties are obtained.

(Experimental examples 8-1 to 8-10)
As shown in Table 8, Experimental Examples 4-4, 5-11, 5-12, 4-25, 5-21, and 51-2, except that the oxide-containing film and / or the metal material were formed. The same procedure as in 5-22 was performed.

In the case of forming the oxide-containing film, first, a plurality of negative electrode active material particles were formed by the same procedure as that of 4-1 to 4-27. Thereafter, a silicon oxide (SiO ₂ ) was deposited on the surface of the negative electrode active material particles by using a liquid phase deposition method. In this case, the negative electrode current collector 34A on which the negative electrode active material particles are formed is immersed in a solution obtained by dissolving boron as an anion scavenger in hydrofluoric acid for 3 hours, and the surface of the negative electrode active material particles After depositing silicon oxide, it was washed with water and dried under reduced pressure.

In the case of forming a metal material, an electrolytic plating method was used to energize while supplying air to the plating bath, and a cobalt (Co) plating film was grown in the gaps between the negative electrode active material particles. In this case, a cobalt plating solution manufactured by Japan High-Purity Chemical Co., Ltd. was used as the plating solution, the current density was 2 A / dm ^{2 to} 5 A / dm ² , and the plating rate was 10 nm / second.

  When the cycle characteristics of the secondary batteries of Examples 8-1 to 8-10 were examined, the results shown in Table 8 were obtained.

  Even when the oxide-containing film and the metal material were formed, the same results as in Table 4 were obtained. In particular, when both the oxide-containing film and the metal material were formed, the cycle maintenance ratio and the storage maintenance ratio were higher than when only one of them was formed. Further, when only the oxide-containing film was formed, the cycle maintenance ratio and the storage maintenance ratio were higher than when only the metal material was formed. For these reasons, in the secondary battery of the present invention, if the oxide-containing film and the metal material are formed, the cycle characteristics and the storage characteristics are further improved.

  From the results shown in Tables 1 to 8, in the secondary battery of the present invention, the electrolytic solution contains two or more solvents, and one of them is a halogenated cyclic compound represented by the formula (1). Therefore, excellent cycle characteristics and storage characteristics can be obtained without depending on the type of the negative electrode active material, the composition of the mixed solvent, the type of the electrolyte salt, or the presence or absence of the oxide-containing film and the metal material.

  In this case, when the metal material (silicon or SnCoC-containing material) is used as compared with the case where the carbon material (artificial graphite) is used as the negative electrode active material, the increase rate of the cycle maintenance rate and the storage maintenance rate is increased. It was. Therefore, a higher effect can be obtained in the latter case than in the former case. This result shows that the use of a metal material that is advantageous for increasing the capacity as the negative electrode active material makes the electrolyte solution more easily decomposed than when a carbon material is used. it is conceivable that.

  The present invention has been described with reference to the embodiments and examples. However, the present invention is not limited to the embodiments described in the above embodiments and examples, and various modifications can be made. For example, the use application of the dicarbonyl compound of the present invention is not necessarily limited to the secondary battery, but may be other electrochemical devices. Other applications include, for example, capacitors.

  In the above-described embodiments and examples, the lithium ion secondary battery or the lithium metal secondary battery has been described as the type of the secondary battery, but is not necessarily limited thereto. The secondary battery of the present invention also includes a secondary battery in which the capacity of the negative electrode includes a capacity due to insertion and extraction of lithium ions and a capacity due to precipitation and dissolution of lithium metal, and is represented by the sum of these capacities. , As well as applicable. In this case, a negative electrode material capable of inserting and extracting lithium ions is used as the negative electrode active material, and the chargeable capacity of the negative electrode material is set to be smaller than the discharge capacity of the positive electrode. .

  In the above-described embodiments and examples, the case where the battery structure is a cylindrical type or a laminate film type and the case where the battery element has a winding structure have been described as examples, but the present invention is not necessarily limited thereto. . The secondary battery of the present invention can be similarly applied to a case where it has another battery structure such as a square shape, a coin shape or a button shape, and a case where the battery element has another structure such as a laminated structure.

  In the above-described embodiments and examples, the case where lithium is used as the element of the electrode reactant is described, but the present invention is not necessarily limited thereto. The element of the electrode reactant may be, for example, another group 1 element such as sodium (Na) or potassium (K), a group 2 element such as magnesium or calcium, or another light metal such as aluminum. Since the effect of the present invention should be obtained without depending on the element type of the electrode reactant, the same effect can be obtained even if the type is changed.

  In the above-described embodiments and examples, the appropriate range derived from the results of the examples is described for the content of the halogenated cyclic compound, but the description is that the content is outside the above-described range. The possibility of becoming is not completely denied. In other words, the appropriate range described above is a particularly preferable range for obtaining the effects of the present invention. Therefore, as long as the effects of the present invention can be obtained, the content may slightly deviate from the above ranges.

  In the above-described embodiments and examples, the structure of the halogenated cyclic compound is described with reference to the general formula (1). However, the structure may be out of the formula (1). It is not a complete denial. That is, since formula (1) represents a particularly preferable structure for obtaining the effects of the present invention, the structure of the halogenated cyclic compound can be represented by formula (1) as long as the functions and effects of the present invention can be obtained. You may deviate somewhat from 1). More specifically, the halogenated cyclic compound may be a derivative in which one or two or more substituents are introduced into the structure shown in Formula (1).

  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 ... Adhesive film, 221 ... Negative electrode active material particle, 222 ... Oxide Containing film, 224 (224A, 224B) ... gap, 225 ... gap, 226 ... metal material.

Claims (17)

A positive electrode and a negative electrode, and an electrolyte containing an electrolyte salt and two or more solvents,
One type of the solvent is a secondary battery, which is a halogenated cyclic compound represented by the formula (1).

(R1 to R6 are a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group. However, of R1, R2, R5 and R6, And at least one of R 3 and R 4 is a hydrogen group or an alkyl group, and X, Y, and Z are an oxo group (—O—) or a thio group ( -S-).) The secondary battery according to claim 1, wherein the halogenated cyclic compound is represented by Formula (2).

(R7 to R12 are a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group. However, of R7, R8, R11 and R12, At least one of is a halogen group or a halogenated alkyl group, and at least one of R9 and R10 is a hydrogen group or an alkyl group.) The secondary battery according to claim 2, wherein the halogenated cyclic compound is represented by Formula (2-1) to Formula (2-52).

  The secondary battery according to claim 3, wherein the halogenated cyclic compound is represented by the formula (2-1), the formula (2-2), or the formula (2-4).   The secondary battery according to claim 1, wherein the remaining type of the solvent is at least one of a cyclic carbonate, a chain carbonate, a lactone, and an acetate.   The cyclic carbonate is ethylene carbonate, propylene carbonate or butylene carbonate, the chain carbonate is dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate or methylpropyl carbonate, and the lactone is γ-butyrolactone or γ- The secondary battery according to claim 5, wherein the secondary battery is valerolactone, and the acetate is methyl acetate, ethyl acetate, or propyl acetate.   The negative electrode can store and release a carbon material, lithium metal (Li), or an electrode reactant as a negative electrode active material, and includes at least one of a metal element and a metalloid element as a constituent element The secondary battery according to claim 1, comprising a material.   The secondary battery according to claim 1, wherein the negative electrode contains a material containing at least one of silicon (Si) and tin (Sn) as a constituent element as a negative electrode active material. The material containing at least one of silicon and tin as a constituent element is a simple substance of silicon or a SnCoC-containing material containing tin, cobalt (Co), and carbon (C) as constituent elements,
In the SnCoC-containing material, the carbon content is 9.9 mass% to 29.7 mass%, the ratio of tin and cobalt (Co / (Sn + Co)) is 20 mass% to 70 mass%, and X The secondary battery according to claim 7, wherein a half-value width of a diffraction peak obtained by line diffraction is 1.0 ° or more.   The secondary battery according to claim 1, wherein the negative electrode contains a carbon material as a negative electrode active material, and the content of the halogenated cyclic compound in the solvent is 0.01 wt% or more and 10 wt% or less.   The negative electrode contains a material containing at least one of silicon and tin as a constituent element as a negative electrode active material, and the content of the halogenated cyclic compound in the solvent is 0.01 wt% or more and 50 wt% or less. The secondary battery according to claim 1. The solvent is an unsaturated carbon-bonded cyclic ester carbonate represented by formula (3) to formula (5), a halogenated chain ester carbonate represented by formula (6), or a halogenation represented by formula (7). The secondary battery according to claim 1, comprising at least one of cyclic carbonate, sultone, and acid anhydride.

(R21 and R22 are a hydrogen group or an alkyl group.)

(R23 to R26 are a hydrogen group, an alkyl group, a vinyl group, or an allyl group, and at least one of them is a vinyl group or an allyl group.)

(R27 is an alkylene group.)

(R31 to R36 are a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group.)

(R37 to R40 are a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group.)   The unsaturated carbon-bonded cyclic carbonate is vinylene carbonate, vinyl ethylene carbonate or methylene ethylene carbonate, and the halogenated chain carbonate is fluoromethyl methyl carbonate, bis (fluoromethyl) carbonate or difluoromethyl methyl carbonate, The secondary battery according to claim 12, wherein the halogenated cyclic carbonate is 4-fluoro-1,3-dioxolan-2-one or 4,5-difluoro-1,3-dioxolan-2-one. The electrolyte salt includes lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium perchlorate (LiClO ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), and a formula ( The secondary battery according to claim 1, comprising at least one of compounds represented by 8) to formula (13).

(X51 is a group 1 element or group 2 element in the long-period periodic table, or aluminum (Al). M51 is a transition metal element, or a group 13 element, group 14 element, or group 15 element in the long-period periodic table. is .R51 is a halogen group .Y51 - (O =) C- R52-C (= O) -, - (O =) C-C (R53) 2 - or - (O =) C-C ( ═O) —, wherein R 52 is an alkylene group, a halogenated alkylene group, an arylene group or a halogenated arylene group, and R 53 is an alkyl group, a halogenated alkyl group, an aryl group or a halogenated aryl group. A5 is an integer of 1 to 4, b5 is 0, 2 or 4, and c5, d5, m5 and n5 are integers of 1 to 3.

(X61 is a group 1 element or group 2 element in the long-period periodic table. M61 is a transition metal element, or a group 13, element, or group 15 element in the long-period periodic table. Y61 is − ( O =) C- (C (R61 ) 2) b6 -C (= O) -, - (R63) 2 C- (C (R62) 2) c6 -C (= O) -, - (R63) 2 C — (C (R62) ₂ ) _c6 —C (R63) ₂ —, — (R63) ₂ C— (C (R62) ₂ ) _c6 —S (═O) ₂ —, — (O═) ₂ S— ( C (R62) ₂ ) _d6- S (= O) _{2- or-} (O =) C- (C (R62) ₂ ) _d6- S (= O) _2- , where R61 and R63 are hydrogen groups. , An alkyl group, a halogen group, or a halogenated alkyl group, and at least one of each is a halogen group or a halogenated alkyl group. R62 is a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group, wherein a6, e6 and n6 are 1 or 2, b6 and d6 are integers of 1 or more and 4 or less, c6 is an integer of 0 or more and 4 or less, and f6 and m6 are integers of 1 or more and 3 or less.)

(X71 is a group 1 element or a group 2 element in the long-period type periodic table. M71 is a transition metal element, or a group 13, element, or a group 15 element in the long-period type periodic table. Rf is fluorinated. An alkyl group or a fluorinated aryl group, each having 1 to 10 carbon atoms, Y71 is — (O═) C— (C (R71) ₂ ) _d7 —C (═O) —, — (R72); ) ₂ C- (C (R71) ₂ ) _d7 -C (= O)-,-(R72) ₂ C- (C (R71) ₂ ) _d7 -C (R72) ₂ -,-(R72) ₂ C- _{(C (R71) 2) d7} -S (= O) 2 -, - (O =) 2 S- (C (R71) 2) e7 -S (= O) 2 - or - (O =) C- ( _{C (R71) 2) e7 -S} (= O) 2 -. is, however, R71 is a hydrogen group, an alkyl group, a halogen group, or a halogen R72 is a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group, at least one of which is a halogen group or a halogenated alkyl group, wherein a7, f7 and n7 are 1 or 2 and b7, c7 and e7 are integers of 1 or more and 4 or less, d7 is an integer of 0 or more and 4 or less, and g7 and m7 are integers of 1 or more and 3 or less.
_{LiN (C m F 2m + 1} SO 2) (C n F 2n + 1 SO 2) ... (11)
(M and n are integers of 1 or more.)

(R81 is a linear or branched perfluoroalkylene group having 2 to 4 carbon atoms.)
LiC (C _p F _{2p + 1} SO ₂ ) (C _q F _{2q + 1} SO ₂ ) (C _r F _{2r + 1} SO ₂ ) (13)
(P, q and r are integers of 1 or more.)   The secondary battery according to claim 1, wherein the positive electrode and the negative electrode are capable of inserting and extracting lithium ions as electrode reactants. Including an electrolyte salt and two or more solvents,
1 type of the said solvent is an electrolyte which is a halogenated cyclic compound represented by Formula (1).

(R1 to R6 are a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group. However, of R1, R2, R5 and R6, And at least one of R3 and R4 is a hydrogen group or an alkyl group, and X, Y, and Z are an oxo group or a thio group.)   The electrolyte according to claim 16, which is used for a secondary battery.

Images