JP4951969B2 - Secondary battery - Google Patents

Description

  The present invention relates to a secondary battery.

  Non-aqueous electrolyte lithium ion or lithium secondary battery using carbon material or lithium metal for the negative electrode and lithium-containing composite oxide for the positive electrode can realize high energy density, so it can be used as a power source for mobile phones and laptop computers. Attention has been paid. In this secondary battery, it is generally known that a film called a surface film, a protective film, SEI or a film is formed on the surface of the electrode. Since this surface film has a great influence on charge / discharge efficiency, cycle life, and safety, it is known that control of the surface film is indispensable for improving the performance of the electrode. That is, when a carbon material is used as the negative electrode material, it is necessary to reduce the irreversible capacity, and in the lithium metal negative electrode, it is necessary to solve the problem of safety due to the decrease in charge / discharge efficiency and the generation of dendrite.

  Various techniques have been proposed as a technique for solving these problems. For example, when lithium metal is used as the negative electrode material, it has been proposed to suppress the formation of dendrite by providing a coating layer made of lithium fluoride or the like on the surface using a chemical reaction.

Patent Document 1 discloses a technique in which a lithium negative electrode is exposed to an electrolytic solution containing hydrofluoric acid, and the negative electrode is reacted with hydrofluoric acid to cover the surface with a lithium fluoride film. Hydrofluoric acid is produced by the reaction of LiPF ₆ and a small amount of water. On the other hand, a surface film of lithium hydroxide or lithium oxide is formed on the surface of the lithium negative electrode by natural oxidation in air. When these react, a surface film of lithium fluoride is formed on the negative electrode surface. However, this lithium fluoride film is formed by utilizing the reaction between the electrode interface and the liquid, and side reaction components are likely to be mixed into the surface film, and it may be difficult to obtain a uniform film. . Also, there may be cases where the surface film of lithium hydroxide or lithium oxide is not uniformly formed or there is a part where lithium is exposed. In these cases, a uniform thin film cannot be formed. In addition, there has been a safety problem due to the reaction of lithium with water or hydrogen fluoride. Moreover, when reaction is inadequate, unnecessary compound components other than a fluoride remain, and bad influences, such as causing the fall of ion conductivity, are considered. Furthermore, in the method of forming a fluoride layer using such a chemical reaction at the interface, the selection range of available fluorides and electrolytes is limited, and it is difficult to form a stable surface film with a high yield. There was a case.

  In Patent Document 2, a mixed gas of argon and hydrogen fluoride and an aluminum-lithium alloy are reacted to obtain a lithium fluoride surface film on the negative electrode surface. However, when a surface film is preliminarily present on the surface of the lithium metal, particularly when a plurality of types of compounds are present, the reaction tends to be non-uniform and it may be difficult to form a lithium fluoride film uniformly. It was. In this case, it is difficult to obtain a lithium secondary battery having sufficient cycle characteristics.

  Patent Document 3 discloses a technique for forming a surface film structure mainly composed of a substance having a rock salt type crystal structure on the surface of a lithium sheet having a uniform crystal structure, that is, a (100) crystal plane preferentially oriented. It is disclosed. By carrying out like this, it is said that uniform precipitation dissolution reaction, ie, charge / discharge of a battery, can be performed, dendrite precipitation of lithium metal can be suppressed, and the cycle life of the battery can be improved. It is stated that it is preferable to use lithium halide as the material used for the surface film, and it is preferable to use a solid solution of LiF and at least one selected from the group consisting of LiCl, LiBr and LiI. Yes. Specifically, in order to form a solid solution film with LiF and at least one selected from the group consisting of LiCl, LiBr, and LiI, the (100) crystal plane prepared by pressing (rolling) is preferentially oriented. A non-aqueous electrolyte battery by immersing the lithium sheet in the electrolyte containing at least one of chlorine molecules or chlorine ions, bromine molecules or bromine ions, iodine molecules or iodine ions and fluorine molecules or fluorine ions A negative electrode is created. In the case of this technology, a rolled lithium metal sheet is used, and since the lithium sheet is easily exposed to the atmosphere, a film derived from moisture and the like is easily formed on the surface, and the presence of active sites becomes uneven, which is the purpose. In some cases, it is difficult to produce a stable surface film. In this case, the effect of suppressing dentlite is not always sufficiently obtained.

  In addition, when a carbon material such as graphite or hard carbon capable of occluding and releasing lithium ions is used as the negative electrode, a technique for improving capacity and charge / discharge efficiency has been reported.

  In patent document 4, the negative electrode which coat | covered the carbon material with aluminum is proposed. Thereby, reductive decomposition on the carbon surface of solvent molecules solvated with lithium ions is suppressed, and deterioration of cycle life is suppressed. However, since aluminum reacts with a small amount of water, the capacity may decrease rapidly when the cycle is repeated.

  Patent Document 5 proposes a negative electrode in which a surface of a carbon material is covered with a thin film of a lithium ion conductive solid electrolyte. Thereby, it is said that the decomposition | disassembly of the solvent which arises when using a carbon material can be suppressed, and especially the lithium ion secondary battery which can use a propylene carbonate can be provided. However, cracks generated in the solid electrolyte due to changes in stress during insertion and desorption of lithium ions may lead to deterioration of characteristics. Further, due to non-uniformity such as crystal defects of the solid electrolyte, a uniform reaction cannot be obtained on the negative electrode surface, leading to deterioration of cycle life.

  Further, in Patent Document 6, the negative electrode is made of a material containing graphite, the main component is a cyclic carbonate and a chain carbonate as an electrolytic solution, and 0.1% by mass or more and 4% by mass or less of a cyclic monolith in the electrolytic solution. A secondary battery containing sulfonic acid ester 1,3-propane sultone and / or 1,4-butane sultone is disclosed. Here, 1,3-propane sultone or 1,4-butane sultone contributes to the formation of a passive film on the surface of the carbon material, and the active and highly crystallized carbon material such as natural graphite or artificial graphite is a passive film. It is considered that the coating has an effect of suppressing the decomposition of the electrolyte without impairing the normal reaction of the battery. In addition to the cyclic monosulfonic acid ester, Patent Documents 7 and 8 report that the same effect can be obtained by using a chain disulfonic acid ester. However, the cyclic monosulfonate of Patent Document 6 or the chain disulfonate of Patent Document 7 and Patent Document 8 mainly forms a film on the negative electrode. For example, a film may be formed on the positive electrode. It was sometimes difficult.

  Patent Documents 9 and 10 disclose a method for producing a cyclic sulfonic acid ester having two sulfonyl groups, and Non-Patent Documents 1 to 4 disclose a method for producing a chain disulfonic acid ester.

  In Patent Document 11, by adding an aromatic compound to the electrolytic solution solvent, the deterioration of the capacity when the secondary battery is repeatedly charged and discharged over a long period of time is suppressed by preventing oxidation of the electrolytic solution solvent. This is a technique for preventing the decomposition of the solvent by preferentially oxidatively decomposing the aromatic compound. However, when this additive is used, the positive electrode surface is not coated, so that the effect of improving the cycle characteristics may not be sufficient.

  Patent Document 12 describes a technique for improving cycle characteristics when a high-voltage positive electrode is used by adding a nitrogen-containing unsaturated cyclic compound to an electrolytic solution. However, although the nitrogen-containing unsaturated cyclic compound improves the charge / discharge efficiency of the negative electrode, it does not improve the charge / discharge efficiency of the positive electrode.

  In addition to the case where the above-described lithium metal or carbon material is used as a negative electrode, an example in which a solid solution of silicon and copper is used as an electrode for a secondary battery is reported in Patent Document 13, for example. According to this document, when an electrode using only silicon is occluded / released by alkali metal or the like, the volume expands / shrinks to about 4 times, and when this volume expansion increases, the active material becomes fine powder or a current collector Since the adhesion to the electrode is lost and the electrode surface is oxidized, the amount of occlusion of alkali metals, etc. is reduced by solidification with copper, etc., and the active material is pulverized and desorbed from the current collector It is said that volume expansion and contraction of the active material can be controlled so as not to occur.

  As a negative electrode active material, a method of using a metal or metalloid and a carbon material that occlude / release alkali metal such as lithium or alkaline earth metal and a carbon material has been studied. Patent Document 14 reports a negative electrode material composed of a metal or semimetal particle nucleus capable of forming a lithium alloy and a carbon layer covering the surface thereof.

A method of using an oxide and a carbon material that occlude / release alkali metal such as lithium or alkaline earth metal as a negative electrode active material has also been studied. Patent Document 15 includes oxide particles and carbonaceous material particles containing at least one element selected from Si, Sn, Ge, Al, Zn, Bi, and Mg, and the oxide particles are contained in the carbonaceous material particles. A negative electrode active material embedded in is reported.
JP-A-7-302617 JP-A-8-250108 Japanese Patent Laid-Open No. 11-288706 Japanese Patent Laid-Open No. 5-234583 JP-A-5-275077 JP 2000-3724 A JP 2000-133304 A US Pat. No. 6,436,582 Japanese Patent Publication No. 5-44946 U.S. Pat. No. 4,950,768 JP 2003-7334 A JP 2003-115324 A Japanese Patent Laid-Open No. 2002-0775350 JP 2000-215887 A JP 2000-243396 A J. et al. Am. Pham. Assoc. L26, 485-493, 1937 G. Schroeter, Lieb, Ann, Der Chemie, 418, 161-257, 1919 Biol. Aktiv. Soedin. Pp 64-69 (1968). Armyanskii Kimicheskii Zhurnal, 21, pp 393-396 (1968).

  The above prior art has the following common problems.

  The surface film generated on the electrode surface is deeply related to charge / discharge efficiency, cycle life, and safety depending on its properties, but there is no method for controlling the film for a long time. For example, when a surface film made of lithium halide or glassy oxide is formed on a layer made of lithium, the surface film can be obtained when it is used repeatedly, although a certain degree of dentite suppression effect can be obtained during initial use. As a result, the function as a protective film may be reduced. This is because the layer made of lithium changes its volume by inserting and extracting lithium, while the film made of lithium halide and the like located on the upper layer hardly changes in volume, so these layers and their interfaces The cause is considered to be internal stress. By generating such internal stress, it is considered that a part of the surface film made of lithium halide or the like is particularly damaged, and the dendrite suppressing function is lowered.

  When a carbon material such as graphite is used for the negative electrode, charges due to decomposition of solvent molecules or anions may appear as irreversible capacity components, leading to a reduction in the initial charge / discharge efficiency. Further, the composition, crystal state, stability, etc. of the film produced at this time have a great influence on the subsequent efficiency and cycle life. As described above, research has been conducted to improve the charge / discharge efficiency and cycle life by forming a film on the electrode for the secondary battery, but in general, sufficient battery characteristics have not been obtained yet. .

  Further, when silicon or the like is used as the negative electrode active material, there is a limit to effectively suppressing volume expansion and contraction even when a solid solution is formed with copper or the like, and further improvement has been desired.

  Here, using a metal, metalloid, or oxide that occludes / releases an alkali metal or alkaline earth metal such as lithium as the negative electrode active material means that only a carbon material such as amorphous carbon is used as the negative electrode active material. Since the capacity can be increased as compared with the conventional case, it is expected as a method for realizing a small and lightweight battery. However, the above-described metals, metalloids, or oxides have a large volume expansion / contraction associated with charge / discharge, and the resulting battery has insufficient cycle characteristics. In other words, cracks or the like may occur in the SEI formed on the surface due to the stress due to the expansion / contraction of the volume. When cracks or the like enter the SEI, the solvent of the electrolytic solution may enter the negative electrode active material and be decomposed to generate gas, or oxygen may enter and oxidative degradation of the negative electrode active material may occur. Carbon materials are expected to have improved conductivity and a cushioning effect against volume changes associated with charging / discharging of the above metals, metalloids, or oxides. Etc. cannot be prevented. Therefore, in a system using such a metal, metalloid, oxide or carbon material as a negative electrode active material, sufficient battery characteristics have not been obtained yet.

  The present invention has been made in view of the above problems, and as a negative electrode active material, a secondary material using a metal, a semimetal, an oxide, and a carbon material that occludes / releases an alkali metal or alkaline earth metal such as lithium. By adding a chain-like disulfonic acid ester to the battery electrolyte, a stable film is formed on the electrode surface to prevent decomposition of solvent molecules. Moreover, as a result, it aims at obtaining the secondary battery excellent in cycling characteristics and charging / discharging efficiency.

In order to solve the above problems, the present invention has the following configuration. That is, the present invention
In a secondary battery comprising at least a positive electrode, a negative electrode, and an electrolyte solution,
The negative electrode contains, as a negative electrode active material, a metal or a semimetal or oxide that absorbs and releases alkali metal or alkaline earth metal, and a carbon material, and
The electrolytic solution is a secondary battery including at least an aprotic solvent in which an electrolyte is dissolved and a compound represented by the following general formula (1).

(However, in the said General formula (1), R < ₁ > and R < ₄ > are respectively independently a hydrogen atom, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C1-C5. An alkoxy group, a substituted or unsubstituted fluoroalkyl group having 1 to 5 carbon atoms, a polyfluoroalkyl group having 1 to 5 carbon atoms, —SO ₂ X (X is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms) ), -SY (Y is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms), -COZ (Z is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms), and a halogen atom, R ₂ and R ₃ each independently represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted group. Or nothing Substituted phenoxy group, substituted or unsubstituted fluoroalkyl group having 1 to 5 carbon atoms, polyfluoroalkyl group having 1 to 5 carbon atoms, substituted or unsubstituted fluoroalkoxy group having 1 to 5 carbon atoms, 1 to carbon atoms 5 polyfluoroalkoxy group, hydroxyl group, halogen atom, -NX ¹ X ² (X ¹ and X ² are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms), and -NY ¹ CONY ² Y ³ (X ^{1 to} X ³ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms).

  In this specification, “polyfluoroalkylene group”, “polyfluoroalkyl group”, and “polyfluoroalkoxy group” are all hydrogen atoms bonded to carbon atoms of the corresponding alkylene group, alkyl group, and alkoxy group, respectively, by fluorine atoms. Represents a substituted group, and “fluoroalkylene group”, “fluoroalkyl group”, and “fluoroalkoxy group” are fluorine atoms in which part of hydrogen atoms bonded to carbon atoms of the corresponding alkylene group, alkyl group, and alkoxy group, respectively. Represents the one substituted by.

In the “substituted fluoroalkylene group”, “substituted fluoroalkyl group” and “substituted fluoroalkoxy group”, “substituted” means that at least one hydrogen atom bonded to a carbon atom is substituted with an atom or functional group other than fluorine. Represents that Examples of the atom or functional group other than fluorine include, for example, a halogen atom such as a chlorine atom, a bromine atom, and an iodine atom, a hydroxyl group, or an alkoxy group having 1 to 5 carbon atoms, or a group in which this is substituted with a halogen atom or a hydroxyl group. Or a group in which —SO ₂ — is introduced into these groups (for example, —OSO ₂ CH ₂ SO ₂ Cl) and the like. When this functional group contains a carbon atom, this carbon atom is not included in the number of “C1-5” in the description of “substituted or unsubstituted alkyl group having 1 to 5 carbon atoms” and the like. And

  According to the present invention, an alkaline metal such as lithium or an alkaline earth metal is occluded as a negative electrode active material by using an electrolyte solution for a secondary battery in which an aprotic solvent contains a chain disulfone compound according to the present invention.・ Even when using metal or metalloid or oxide and carbon materials that are released, the obtained secondary battery has excellent charge / discharge efficiency, good cycle characteristics, high capacity retention, and increased resistance during storage. An excellent lithium secondary battery capable of being suppressed can be obtained.

It is a schematic block diagram of the secondary battery which concerns on this invention. Metal or metalloid containing the element M ¹ is a schematic diagram showing a state of composite is coated with a carbon material. It is a schematic view showing a state in which the carbon material is coated with a metal or metalloid containing the element M ¹ is complexed. It is a schematic diagram which shows the state which the oxide coat | covered with the carbon material and has compounded. It is a schematic diagram which shows the state which the carbon material is coat | covered with the oxide and has compounded.

Explanation of symbols

11 Positive Electrode Current Collector 12 Layer Containing Positive Electrode Active Material 13 Layer Containing Negative Electrode Active Material 14 Negative Electrode Current Collector 15 Nonaqueous Electrolyte Solution 16 Porous Separator 2a, 3a Carbon Material 2b, 3b Metal containing Element M ¹ or Semi-metal 2c, 3c oxide

(Description of battery configuration according to the present invention)
FIG. 1 shows a schematic structure of an example of a battery according to the present invention. A positive electrode current collector 11, a layer 12 containing a positive electrode active material capable of inserting and extracting lithium ions, a layer 13 containing a negative electrode active material capable of inserting and extracting lithium ions, a negative electrode current collector 14 and electrolysis It is comprised from the liquid 15 and the separator 16 containing this. Here, the chain disulfonic acid compound (chain disulfonic acid ester) represented by the general formula (1) is included in the electrolytic solution 15.

(Current collector)
Aluminum, stainless steel, nickel, titanium, or an alloy thereof can be used as the positive electrode current collector 11, and copper, stainless steel, nickel, titanium, or an alloy thereof can be used as the negative electrode current collector 14. .

(Separator)
As the separator 16, a polyolefin such as polypropylene or polyethylene, or a porous film such as a fluororesin is preferably used.

(Positive electrode)
As the positive electrode active material, a commonly used lithium-containing composite oxide is used. Specifically, LiMO ₂ (M is selected from Mn, Fe, Co, and a part thereof is substituted with other cations such as Mg, Al, Ti, etc. Or a material such as LiMn ₂ O ₄ can be used. The selected positive electrode active material is dispersed and kneaded in a solvent such as N-methyl-2-pyrrolidone (NMP) together with a conductive material such as carbon black and a binder such as polyvinylidene fluoride (PVDF). The layer 12 which becomes a positive electrode can be obtained by a method such as coating on a substrate such as an aluminum foil.

(Negative electrode)
In the present invention, as the negative electrode active material contained in the negative electrode, a metal or semimetal, oxide, or carbon material that occludes / releases alkali metal such as lithium or alkaline earth metal is used.

It said metal or metalloid, element ^M 1 ^{(M 1} is Si, Sn, Al, Pb, Ag, element selected from Ge and Sb) the use of a metal or metalloid containing at least one more. The metal or metalloid, may be used an alkali metal or alkaline earth metal can be alloyed metal or metalloid, element M ¹ contained in the metal or metalloid is be one kind or two or more kinds good. When containing the element M ¹ 2 or more, these elements may comprise a metal or semi-metallic state respectively, may include a state of the alloy. Among these, it is preferable to use a metal or metalloid containing an element selected from Si, Sn and Al, and more preferable to use a metal or metalloid containing at least one of Si and Sn.

As the oxide, an oxide that can be alloyed with an alkali metal or an alkaline earth metal can be used. For example, the element M ² (M ² is Si, Sn, Al, Pb, Ag, Ge, Sb, B). , An element selected from P, W, and Ti). One or more elements other than oxygen contained in the oxide may be used. Two or more oxides can be used in combination. Among these, an oxide containing an element selected from Si, Sn, Al, Pb, Ag, Ge, and Sb is preferably used, and an oxide containing at least one of Si and Sn is more preferably used. The composition of the oxide may be stoichiometry or non-stoichiometry.

In addition, a metal or a semimetal and an oxide can be used in combination. In particular, a metal or a semimetal containing at least one or more of the element M ¹ (M ¹ is an element selected from Si, Sn, Al, Pb, Ag, Ge, and Sb), and the alkali metal or alkaline earth described above. It is preferable to use a metal and an oxide that can be alloyed in combination.

  As the carbon material, graphite, amorphous carbon, carbon nanotube, carbon nanohorn, fullerene, diamond-like carbon, soft carbon, hard carbon, or a mixture thereof can be used. The carbon material may be one type or two or more types. It is preferable to use at least one of graphite and amorphous carbon. The content of the carbon material relative to the whole negative electrode active material is preferably in the range of 5 to 95% by mass, more preferably in the range of 25 to 75% by mass, and in the range of 30 to 60% by mass. Further preferred. The carbon material is expected to exhibit an improved conductivity and a cushioning effect against a volume change associated with charging / discharging of the metal, metalloid, or oxide.

  The use of the above metal, metalloid, oxide, or carbon material as the negative electrode active material can increase the capacity compared to the case where only a carbon material such as amorphous carbon is used as the negative electrode active material. It is expected as a method to realize a small and lightweight battery. However, the metal, metalloid, or oxide as described above has a large volume expansion / contraction due to charge / discharge, and although the cushioning effect of the carbon material can be expected, the cycle characteristics of the obtained battery are still insufficient. Like the present invention, by using the additive of the general formula (1), which will be described later, even if a crack or the like is formed in the SEI formed on the surface due to the stress due to the expansion / contraction of the volume, the film is rapidly formed. It is thought that consumption of the solvent of the electrolytic solution is suppressed because it is formed. That is, this can prevent gas generation due to solvent decomposition. Further, since the supply of oxygen to the surface is blocked by the formation of the film, it is considered that deterioration due to oxidation of the active material is also suppressed. As a result, the battery of the present invention is considered to have good cycle characteristics even when the metal, metalloid, oxide, and carbon material as described above are used as the negative electrode active material.

In the present invention, the negative electrode active material contained in the negative electrode may contain an element X that does not alloy with an alkali metal or alkaline earth metal in addition to the element contained in the metal, metalloid, or oxide. These elements X are effective in suppressing volume change associated with charging / discharging of the negative electrode active material and improving conductivity, and even when the negative electrode active material having such a configuration is used, the same effects as described above can be obtained. Examples of the element X include elements selected from Fe, Ni, Cu, and Ti. These elements X may be present as long as they are not alloyed with an alkali metal or alkaline earth metal. However, for example, Ti element is not alloyed with alkali metal or alkaline earth metal in the state of metal, but may be alloyed with alkali metal or alkaline earth metal in the state of oxide. The Ti element in is not classified into this element X (for example, Ti element in the state of Li ₄ Ti ₅ O ₁₂ ). The element X contained in the negative electrode active material may be one type or two or more types. When the negative electrode active material contains two or more elements X, these elements may be included in the state of a metal or a metal compound, or may be included in the state of an alloy or an alloy compound. Further, it may be alloyed with the above metal, metalloid or oxide.

In the case of a negative electrode active material containing the above element M ¹ (M ¹ is an element selected from Si, Sn, Al, Pb, Ag, Ge and Sb) containing at least one metal or semimetal and the above element X, ratio of the element ^{M 1} and the element X, the element ^{M 1} in atomic ratio: element X = 19: 1 to 1: is preferably 9. When the amount of the element X is too large, the proportion of the metal or metalloid involved in charge / discharge decreases, so that the volume energy density and the weight energy density of the negative electrode tend to decrease. When the element X is too small, the element X There is a tendency that the effect of adding, that is, the suppression of volume change accompanying charging / discharging of the negative electrode active material and the effect of improving conductivity are reduced. More preferably, the atomic ratio is element M ¹ : element X = 14: 1 to 3: 7, and more preferably element M ¹ : element X = 9: 1 to 5: 5.

Said element and oxide containing ^{M 2,} when the negative electrode active material containing the above element X, the ratio of the element ^{M 2} and the element X, the element ^{M 2} in atomic ratio: element X = 19: 1 to 1: 9 is preferred. If the amount of element X is too large, the proportion of oxides involved in charge / discharge decreases, so the volume energy density and weight energy density of the negative electrode tend to decrease. If the amount of element X is too small, element X is added. As a result, there is a tendency that the effect of suppressing the volume change accompanying the charging / discharging of the negative electrode active material and the effect of improving the conductivity are reduced. More preferably, the atomic ratio is element M ² : element X = 14: 1 to 3: 7, and further preferably element M ² : element X = 9: 1 to 5: 5.

  In addition to the above, the negative electrode active material of the present invention can include materials that occlude and release alkali metals or alkaline earth metals such as lithium, such as lithium metals and lithium alloys.

  A negative electrode active material can be made into the form containing the particle | grains containing at least one of the said metal, a semimetal, or an oxide, and the said carbon material. The particles containing both the metal or metalloid or oxide and the carbon material, that is, the composite particle, the at least part of the periphery of the metal or metalloid or oxide particles is the carbon material. And composite particles obtained by coating at least part of the periphery of the carbon material particles with the metal, metalloid, or oxide. These particles may be further coated with a carbon film on the surface.

  The negative electrode active material as described above can also be formed by a vacuum film formation method or a pressure contact method. As the vacuum film forming method, a vacuum deposition method, a sputtering method, a CVD method, or the like can be used. As the pressure welding method, a mechano-fusion method, a mechanical milling method, or the like can be used.

  Then, for example, a negative electrode having a layer containing at least a part of the negative electrode active material as described above can be formed by a coating method or a vacuum film forming method. As the vacuum film forming method, a vacuum deposition method, a sputtering method, a CVD method, or the like can be used.

  The negative electrode of the secondary battery of the present invention has a layered structure having a layer containing the metal, metalloid or oxide as a main component and a layer containing the carbon material as a main component. preferable. Here, the “main component layer” is assumed that the main component occupies 50% by mass or more of the entire material constituting the layer. When the above layered structure is formed, it is preferable that each layer occupies 70% by mass or more of the main component.

For the negative electrode active material using a metal or metalloid and carbon material containing an element M ¹ above, is described below with more detail.

Metal or metalloid and carbon material containing an element M ¹ described above may simply be mixed, each in the form of particles. Or a metal or metalloid 2b containing the element M ¹ may be conjugated is coated with a carbon material 2a as shown in FIG. Or a carbon material 3a may be conjugated coated with a metal or metalloid 3b including the element M ^1, as shown in FIG. When complexed, and high conductivity, the expression of the cushion effect of the volume change due to charging and discharging of the metal or metalloid containing the element M ¹ can be expected.

Metal or particles composed of semi-metal, metal including the element M ¹ or metalloid and metal or metalloid and said element comprises particles, and the element M ¹ consists of the element X including the element M ¹ Particles composed of X and lithium metal or a lithium alloy can be produced by using a vacuum film formation method or a pressure contact method in addition to a normal production method.

  As a composite method, a vacuum film formation method such as a CVD method, a pressure contact method such as a mechanical milling method or a mechanofusion method, or a sol-gel method can be used.

If complexing coated by carbon material a metal or metalloid containing the element M ^1, for example by a CVD method, it is possible to coat the carbon material film on the metal or metalloid containing the element M ^1. Alternatively, the metal or semi-metal including the element M ¹ is coated with a carbonaceous material such as tar, and fired at about 1000 ° C. in an inert atmosphere, thereby the metal or semi-containing the element M ¹ Carbon particles can be applied to particles made of metal. Further, it is possible to coat the carbon material film on the metal or metalloid containing the element M ¹ by vacuum evaporation.

Further, even when using the pressure method such as mechanical milling and mechanofusion, the metal or metalloid containing the element M ¹ can be composited coated by the carbon material. For example, mixing a metal or semi-metal particles and the carbon material particles containing the element M ^1, by mechanical milling, to composite embedded a metal or metalloid particles containing the element M ¹ in the carbon material particles be able to. Further, after compounding the metal or metalloid containing a carbon material and the element M ¹ by mechanical milling, as described above, by a CVD method or a carbon material deposition may be performed a carbon material coating.

A carbon material, when the composite coated with a metal or metalloid containing the element M ^1, for example by a CVD method, a metal or semi-metal film containing an element M to the carbon material particles, thereby compounding Can do. Or, a metal or semi-metal film containing an element M ¹ to the carbon material particles by sol-gel method, can be conjugated.

As an anode active material, it is possible to use particles obtained by combining the metal or metalloid containing a carbon material and the element M ¹ as described above. Further, these composite particles can be further mixed with graphite or amorphous carbon particles and used as a negative electrode active material.

  When the particulate negative electrode active material selected from the above is used, the negative electrode active material particles are made of conductive material (conductivity imparting material) such as carbon black, polyvinylidene fluoride (PVDF), etc. The layer 13 to be the negative electrode can be obtained by a method such as dispersion and kneading in a solvent such as N-methyl-2-pyrrolidone (NMP) together with the above binder and applying this onto a substrate such as a copper foil. When a plurality of particles are dispersed, those previously mixed by a method such as mechanical milling can be used.

Further, the metal or metalloid containing the element M ^1, and simultaneously deposited and carbon material, may also be complexed. In that case, the selected negative electrode active material is appropriately selected from a melt cooling method, a liquid quenching method, an atomizing method, a vacuum deposition method, a sputtering method, a plasma CVD method, a photo CVD method, a thermal CVD method, a sol-gel method, and the like. Thus, a layer 13 to be a negative electrode can be obtained by forming a film on the substrate.

It may have a structure of at least two layers of a layer mainly containing layer and a carbon material mainly composed of a metal or metalloid containing the element M ^1. In particular, it is preferable to form a layer forming a layer mainly composed of carbon material on the negative electrode current collector, composed mainly of a metal or metalloid containing the element M ¹ thereon. If you this structure, the metal or metalloid containing the element M ¹ can preferentially form coatings on layer mainly, and the high conductivity, good cycle characteristics can be expected.

Furthermore, it is also possible to the layer containing a composite material of a metal or metalloid and the carbon material containing the above element M ^1, the structure of at least two layers of a layer containing carbon as a main component material. If you this structure, a high conductivity, the expression of the cushion effect of the volume change due to charging and discharging of the metal or metalloid containing the element M ¹ can be expected. In particular, it is preferable to form a layer containing a composite material of a metal or metalloid and the carbon material comprising forming a layer mainly composed of carbon material on an anode current collector, the element M ¹ thereon . If you this structure, on the layer containing the composite material of a metal or metalloid and the carbon material containing the above element M ¹ can preferentially form film, a high conductivity, good cycle characteristics can be expected.

The layer mainly composed of a carbon material can be formed by a coating method or a vacuum film forming method such as a CVD method, a vacuum evaporation method, or a sputtering method. For example, when the coating method is used, in addition to carbon particles, a conductive material (conductivity-imparting material) such as carbon black and a binder such as polyvinylidene fluoride (PVDF) and N-methyl-2- It can be formed by a method of dispersing and kneading in a solvent such as pyrrolidone (NMP), and applying this to a substrate such as a copper foil. The layer mainly containing the metal or metalloid containing the element M ^1, melt cooling method, liquid quenching method, an atomizing method, a vacuum deposition method, sputtering method, plasma CVD method, optical CVD method, thermal CVD method, sol-gel method The film can be formed on the substrate by an appropriate method such as. The layer mainly composed of a metal or metalloid containing the element M ¹ is a particle mainly composed of a metal or metalloid containing the element M ^1, carbon black, conductive material (conductivity-imparting agent), It is formed by a method of dispersing and kneading in a solvent such as N-methyl-2-pyrrolidone (NMP) together with a binder such as polyvinylidene fluoride (PVDF), and applying this onto a substrate such as copper foil. Can do.

Layer containing a composite material of a metal or metalloid and the carbon material containing the above element M ¹ may be a coating method, or is formed by a vacuum deposition method, a sputtering method or a vacuum deposition method such as CVD .

  The negative electrode active material using the above oxide and carbon material will be described in more detail as follows.

  The above oxide and carbon material may simply be mixed in the form of particles. Or as shown in FIG. 4, the said oxide 2c may be coat | covered with the carbon material 2a, and may be compounded. Alternatively, as shown in FIG. 5, the carbon material 3a may be covered with the oxide 3c to be combined. When combined, it can be expected to exhibit high conductivity and a cushioning effect against the volume change accompanying the charge / discharge of the oxide.

  Particles composed of the oxide, particles composed of the oxide and the element X, and particles composed of the oxide and the element X and a lithium metal or a lithium alloy are added to the normal manufacturing method Further, it can also be produced by using a vacuum film formation method or a pressure contact method.

  As a composite method, a vacuum film formation method such as a CVD method, a pressure contact method such as a mechanical milling method or a mechanofusion method, or a sol-gel method can be used.

  When the oxide is coated with a carbon material to be combined, the oxide can be coated with a carbon material film by, for example, a CVD method. Alternatively, the particles composed of the oxide can be coated with a carbonaceous material such as tar, and the particles composed of the oxide can be coated with carbon by firing at about 1000 ° C. in an inert atmosphere. . Further, the carbon material film can be coated on the oxide by a vacuum deposition method.

  Even when a pressure welding method such as mechanical milling or mechanofusion is used, the oxide can be coated with a carbon material to be compounded. For example, the oxide particles and the carbon material particles are mixed and mechanically milled to embed and compound the oxide particles in the carbon material particles. Further, after the carbon material and the oxide are combined by mechanical milling as described above, the carbon material may be coated by CVD or carbon material vapor deposition.

  When the carbon material is coated and compounded with the above oxide, an oxide film can be formed on the carbon material particles by, for example, a CVD method and compounded. Alternatively, an oxide film can be formed on the carbon material particles by a sol-gel method and combined.

  As the negative electrode active material, particles in which the carbon material and the oxide are combined as described above can be used. Further, these composite particles can be further mixed with graphite or amorphous carbon particles and used as a negative electrode active material.

  When the particulate negative electrode active material selected from the above is used, the negative electrode active material particles are made of conductive material (conductivity imparting material) such as carbon black, polyvinylidene fluoride (PVDF), etc. The layer 13 to be the negative electrode can be obtained by a method such as dispersion and kneading in a solvent such as N-methyl-2-pyrrolidone (NMP) together with the above binder and applying this onto a substrate such as a copper foil. When a plurality of particles are dispersed, those previously mixed by a method such as mechanical milling can be used.

  In addition, the oxide and the carbon material can be simultaneously formed and combined. In this case, the selected negative electrode active material is appropriately selected from a melt cooling method, a liquid quenching method, an atomizing method, a vacuum deposition method, a sputtering method, a plasma CVD method, a photo CVD method, a thermal CVD method, a sol-gel method, and the like. Thus, a layer 13 to be a negative electrode can be obtained by forming a film on the substrate.

  A structure having at least two layers of a layer containing the oxide as a main component and a layer containing a carbon material as the main component can also be used. In particular, it is preferable to form a layer mainly composed of a carbon material on the negative electrode current collector, and form a layer mainly composed of an oxide thereon. When this structure is adopted, a film can be formed preferentially on the layer mainly composed of oxide, and high conductivity and good cycle characteristics can be expected.

  Further, a structure including at least two layers of a layer containing a composite material of the oxide and the carbon material and a layer containing the carbon material as a main component can be used. In the case of this structure, high conductivity and a cushioning effect with respect to a volume change accompanying charging / discharging of the oxide can be expected. In particular, it is preferable to form a layer containing a carbon material as a main component on the negative electrode current collector and to form a layer containing a composite material of the oxide and the carbon material on the layer. In this structure, a film can be preferentially formed on the layer containing the composite material of the oxide and the carbon material, and high conductivity and good cycle characteristics can be expected.

  The layer mainly composed of a carbon material can be formed by a coating method or a vacuum film forming method such as a CVD method, a vacuum evaporation method, or a sputtering method. For example, when the coating method is used, in addition to carbon particles, a conductive material (conductivity-imparting material) such as carbon black and a binder such as polyvinylidene fluoride (PVDF) and N-methyl-2- It can be formed by a method of dispersing and kneading in a solvent such as pyrrolidone (NMP), and applying this to a substrate such as a copper foil. The oxide-based layer is formed by an appropriate method such as a melt cooling method, a liquid quenching method, an atomizing method, a vacuum deposition method, a sputtering method, a plasma CVD method, a photo CVD method, a thermal CVD method, or a sol-gel method. It can be formed by forming a film on a substrate. In addition, the layer mainly composed of an oxide is composed of particles mainly composed of an oxide, a conductive material (conductivity imparting material) such as carbon black, and a binder such as polyvinylidene fluoride (PVDF). -It can be formed by a method of dispersing and kneading in a solvent such as methyl-2-pyrrolidone (NMP) and applying it to a substrate such as a copper foil.

  The layer containing a composite material of the oxide and the carbon material can be formed by a coating method or a vacuum film formation method such as a vacuum evaporation method, a sputtering method, or a CVD method.

(Electrolyte)
The electrolytic solution 15 includes at least an electrolyte, an aprotic solvent, and an additive.

(Electrolytes)
As the electrolyte, in the case of a lithium secondary battery, a lithium salt is used and dissolved in an aprotic solvent. The lithium salt, lithium imide _{salt, LiPF 6, LiAsF 6, LiAlCl} 4, LiClO 4, LiBF 4, LiSbF 6 , and the like. The lithium imide _{salt, LiN (C k F 2k +} 1 SO 2) (C m F 2m + 1 SO 2) (k, m is 1 or 2 independently) and the like. Among these, LiPF ₆ and LiBF ₄ are particularly preferable. These can be used alone or in combination of two or more. By including these lithium salts, a high energy density can be achieved.

(Aprotic solvent)
The aprotic electrolyte is selected from cyclic carbonates, chain carbonates, aliphatic carboxylic acid esters, γ-lactones, cyclic ethers, chain ethers, and organic solvents of these fluorinated derivatives. At least one organic solvent is used. More specifically,
Cyclic carbonates: propylene carbonate (hereinafter abbreviated as PC), ethylene carbonate (hereinafter abbreviated as EC), butylene carbonate (BC), and their derivative chain carbonates: dimethyl carbonate (DMC), diethyl carbonate ( Hereinafter, abbreviated as DEC.), Ethyl methyl carbonate (EMC), dipropyl carbonate (DPC), and their derivatives aliphatic carboxylic acid esters: methyl formate, methyl acetate, ethyl propionate, and their derivatives γ-lactone Class: γ-butyrolactone and derivatives thereof Cyclic ethers: Tetrahydrofuran, 2-methyltetrahydrofuran, and derivatives thereof Chain ethers: 1,2-diethoxyethane (DEE), ethoxymethoxyethane (EME), Diethyl ether, and derivatives thereof, etc .: dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, acetonitrile, propionitrile, nitromethane, ethyl monoglyme, phosphoric acid triester, trimethoxymethane, dioxolane derivative, methyl Sulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, anisole, N-methylpyrrolidone, fluorinated carboxylic acid ester These may be used alone or in combination of two or more. .

(Additive)
As the additive, a chain disulfonic acid ester represented by the general formula (1) is used.

(However, in the said General formula (1), R < ₁ > and R < ₄ > are respectively independently a hydrogen atom, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C1-C5. An alkoxy group, a substituted or unsubstituted fluoroalkyl group having 1 to 5 carbon atoms, a polyfluoroalkyl group having 1 to 5 carbon atoms, —SO ₂ X ₁ (X ₁ is a substituted or unsubstituted carbon atom having 1 to 5 carbon atoms, Alkyl group), -SY ₁ (Y ₁ is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms), -COZ (Z is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms), And R ₂ and R ₃ each independently represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted carbon group having 1 to 5 carbon atoms. An alkoxy group, Or an unsubstituted phenoxy group, a substituted or unsubstituted fluoroalkyl group having 1 to 5 carbon atoms, a polyfluoroalkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted fluoroalkoxy group having 1 to 5 carbon atoms, a carbon number 1-5 polyfluoroalkoxy group, a hydroxyl group, a halogen _atom, -NX ₂ X 3 _{(X 2} and _{X 3} are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms) , and _{-NY 2 CONY 3 Y 4 (Y} 2 ~Y 4 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms) shows a atom or a group selected from. )

  The compound represented by the general formula (1) is an acyclic compound and does not involve a cyclization reaction during synthesis, and can be synthesized using, for example, Non-Patent Documents 1 to 4. It can also be obtained as a by-product of the synthesis of the cyclic disulfonic acid ester disclosed in Patent Document 9. Thus, the compound represented by the general formula (1) has an advantage that an inexpensive electrolytic solution can be provided because the synthesis process is easy.

Preferred molecular structures of R ₁ and R _{4 in} the general formula (1) include ease of forming a reactive film on the electrode, stability of the compound, ease of handling, solubility in a solvent, From the viewpoint of ease of synthesis, cost, etc., each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, and —SO ₂ X ₁ (X ₁ is a substituted or unsubstituted carbon atom having 1 to Atoms or groups selected from (5 alkyl groups), each independently preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group. Particularly preferred embodiments of R ₁ and _{R 4} is where _{R 1} and _{R 4} is a hydrogen atom. This is because when R ₁ and R ₄ are hydrogen atoms, a methylene moiety sandwiched between two sulfonyl groups is activated and a reaction film on the electrode is easily formed.

In R ₂ and R ₃ , from the viewpoints of stability of the compound, ease of synthesis of the compound, solubility in a solvent, price, and the like, each independently, a substituted or unsubstituted alkyl having 1 to 5 carbon atoms. A group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted phenoxy group, a hydroxyl group, a halogen atom, and —NX ₂ X ₃ (X ₂ and X ₃ are each independently a hydrogen atom; Or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms) is preferable, and each independently is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or substituted or unsubstituted. Is more preferably an alkoxy group having 1 to 5 carbon atoms, more preferably one or both of R ₂ and R ₃ is a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms. . For the same reason, the substituted or unsubstituted alkyl group having 1 to 5 carbon atoms is preferably a methyl group or ethyl group, and the substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms is a methoxy group or An ethoxy group is preferable.

  The compound of the general formula (1) has two sulfonyl groups, has a small LUMO, and has a smaller LUMO value than solvent molecules and monosulfonic acid esters in the electrolytic solution, and thus is easily reduced. For example, Compound No. 1 shown in Table 1 below. The LUMO of 1 is as small as -0.86 eV according to semiempirical molecular orbital calculation. For this reason, compound No. 1 is preceded by a solvent (LUMO: about 1.2 eV) comprising a cyclic carbonate or a chain carbonate. It is considered that 1 reduction film is formed on the negative electrode and plays a role of suppressing decomposition of the solvent molecules. In order to suppress the decomposition of the solvent molecules, it is difficult to form a highly resistant solvent molecule decomposition film on the negative electrode, so that an increase in resistance and an improvement in cycle characteristics can be expected. Moreover, it is considered that two electron-withdrawing sulfonyl groups are bonded to the carbon atom, and a film is easily formed on the electrode by the activation of the carbon atom. Furthermore, the carbanion produced by deprotonation of active methylene may coordinate Li or react on the positive electrode to form a film.

  Although the specific example of General formula (1) is shown below, this invention is not specifically limited to these.

  Although the compound represented by General formula (1) is not specifically limited, It is preferable that 0.1 to 5.0 mass% is contained in electrolyte solution. If it is less than 0.1% by mass, a sufficient effect may not be exhibited in forming a film by an electrochemical reaction on the electrode surface. Moreover, when it exceeds 5.0 mass%, it not only becomes difficult to melt | dissolve, but the viscosity of electrolyte solution may be enlarged. In the present invention, more preferably, a sufficient film effect can be obtained by adding in the range of 0.5% by mass to 3.0% by mass.

You may use the compound shown in General formula (1) individually or in combination of 2 or more types. When two or more types are used in combination, although not particularly limited, at least one compound containing an active methylene group (that is, a compound in which R ₁ and R ₄ are hydrogen) is included from the viewpoint of easy film formation with an electrode. Is effective. As a specific combination, the above-mentioned compound no. 1 (compound having an active methylene group) and compound no. 5 compounds.

  When two or more types of the compound of the general formula (1) are added to the electrolytic solution, the proportion of the electrolytic solution in the electrolytic solution is not particularly limited, but for the same reason as described above, the two types are combined to be 0.1% by mass or more and 5.0% by mass. The following is preferred. Further, when two or more kinds of the compound of the general formula (1) are added, the ratio of each compound to the total mass of the compound of the general formula (1) is not particularly limited, but the ratio of the smallest compound is 5 It is preferable that the ratio of the compound with the most mass% is 95 mass%.

  Further, the electrolyte solution containing the compound of the general formula (1) contains at least one of a cyclic monosulfonic acid ester, a cyclic sulfonic acid ester having two sulfonyl groups, an alkanesulfonic acid anhydride, and a sulfolene compound. This is also effective here using an electrolyte solution.

  Examples of the cyclic monosulfonic acid ester include compounds represented by the following general formula (2).

(However, in the general formula (2), n is 0 to 2 integer. _Also, R 5 _{to R 10} each independently represent a hydrogen atom, a substituted or unsubstituted 1 to 12 carbon atoms An atom or group selected from an alkyl group, a substituted or unsubstituted fluoroalkyl group having 1 to 6 carbon atoms, and a polyfluoroalkyl group having 1 to 6 carbon atoms.

In the compound represented by the general formula (2), n is preferably 0 or 1, from the viewpoints of stability of the compound, ease of synthesis of the compound, solubility in a solvent, price, and the like, and R _{5 to} R ₁₀ Are preferably each independently an atom or group selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and a polyfluoroalkyl group having 1 to 5 carbon atoms. A hydrogen atom or a polyfluoroalkyl group having 1 to 5 carbon atoms is more preferable. More preferably, all of R _{5 to} R ₁₀ are hydrogen atoms, or one or two of R _{5 to} R ₁₀ are polyfluoroalkyl groups having 1 to 5 carbon atoms, and the other is a hydrogen atom. As said C1-C5 polyfluoroalkyl group, a trifluoromethyl group is preferable.

  Specifically, 1,3-propane sultone (1,3-PS), α-trifluoromethyl-γ-sultone, β-trifluoromethyl-γ-sultone, γ-trifluoromethyl-γ-sultone, α -Methyl-γ-sultone, α, β-di (trifluoromethyl) -γ-sultone, α, α-di (trifluoromethyl) -γ-sultone, α-undecafluoropentyl-γ-sultone, α- Examples include heptafluoropropyl-γ-sultone and 1,4-butane sultone (1,4-BS).

  Among these, 1,3-propane sultone (1,3-PS) is considered to form a decomposition film on the negative electrode of a lithium ion secondary battery. 1,3-PS has a LUMO of 0.07 eV. It is larger than that of 1 (−0.86 eV). For example, compound no. When 1 and 1,3-PS were added to the electrolyte and charged, compound No. 1 was first prepared. One substance may form a film on the negative electrode, and then 1,3-PS forms a film. At the initial stage of charging, a portion having a negative electrode surface and compound No. 1 reacts mainly, but compound no. 1 progresses to charge at the part that did not react with 1 (the part that may react with the solvent molecule) and reacts with 1,3-PS. A composite film of 1 and 1,3-PS is formed, and a further resistance increase suppressing effect, battery swelling expansion, and the like can be expected.

  When the compound of the general formula (2) is added to the electrolytic solution, the content in the electrolytic solution is not particularly limited, but 0.5% by mass to 10.0% by mass is contained in the electrolytic solution. Is preferred. If the amount is less than 0.5% by mass, the effect may not be sufficiently exerted on the film formation by the electrochemical reaction on the electrode surface. If it exceeds 10.0 mass%, the viscosity of the electrolytic solution may be increased. Moreover, as a ratio of the general formula (2) in the compound of the general formula (1) and the general formula (2), the total mass of the compound of the general formula (1) and the compound of the general formula (2), respectively. 10 to 90% by mass is preferable.

  Examples of the cyclic sulfonic acid ester having two sulfonyl groups include compounds represented by the following general formula (3).

(However, in the said General formula (3), Q is an oxygen atom, a methylene group, or a single bond, A is a substituted or unsubstituted C1-C5 alkylene group, a carbonyl group, a sulfinyl group, C1-C5. At least one C—C bond in the polyfluoroalkylene group, a substituted or unsubstituted fluoroalkylene group having 1 to 5 carbon atoms, or a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms is a C—O—C bond A group in which at least one C—C bond in the polyfluoroalkylene group having 1 to 5 carbon atoms is a C—O—C bond, and a substituted or unsubstituted fluoroalkylene having 1 to 5 carbon atoms A group selected from a group in which at least one C—C bond in the group is a C—O—C bond, B is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, carbon number 5 of polyfluoroalkylene group, and a substituted or unsubstituted fluoroalkylene group having 1 to 5 carbon atoms, a group selected from shown.)

  In the compound represented by the general formula (3), A is a substituted or unsubstituted carbon number of 1 to 5 from the viewpoints of stability of the compound, ease of synthesis of the compound, solubility in a solvent, price, and the like. At least a C-C bond in the alkylene group, a polyfluoroalkylene group having 1 to 5 carbon atoms, a substituted or unsubstituted fluoroalkylene group having 1 to 5 carbon atoms, and a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms. A group in which one site is a C—O—C bond, a group in which at least one C—C bond in a C 1-5 polyfluoroalkylene group is a C—O—C bond, and a substituted or unsubstituted group A group selected from a group in which at least one C—C bond in the fluoroalkylene group having 1 to 5 carbon atoms is a C—O—C bond is preferable. A group selected from a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, a polyfluoroalkylene group having 1 to 5 carbon atoms, and a substituted or unsubstituted fluoroalkylene group having 1 to 5 carbon atoms is more preferable. Alternatively, an unsubstituted alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group, an ethylene group, or a 2,2-propanediyl group is particularly preferable. The C1-C5 fluoroalkylene group preferably includes a methylene group and a difluoromethylene group, and more preferably includes a methylene group and a difluoromethylene group.

  For the same reason, B is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group, a 1,1-ethanediyl group, or a 2,2-propanediyl group.

  These cyclic sulfonic acid esters having two sulfonyl groups include those disclosed in Patent Document 9. Specific compounds represented by the general formula (3) are listed below, but are not limited thereto.

  These compounds have the same level of LUMO as the compound of the general formula (1) of the present invention and have two or more sulfonyl groups. 1 and compound no. When 21 (MMDS) is added to the electrolyte, a high ion conductive composite film is easily formed in the initial stage of charging. MMDS is a cyclic compound and is considered to be a compound that easily reacts with the negative electrode by ring opening and forms a film.

  If MMDS contributes to the film formation fairly selectively on the negative electrode, compound no. In the case of 1 substance, the film formation probability on the negative electrode is relatively reduced, but on the contrary, the reaction probability on the positive electrode is increased and the film formation on the positive electrode is achieved. As a result, suppression of solvent decomposition on the positive electrode can also be expected.

  When the compound of the general formula (3) is added to the electrolytic solution, the content of the compound of the general formula (3) in the electrolytic solution is not particularly limited, but 0.5% by mass or more and 10. It is preferably contained in an amount of 0% by mass or less. If the amount is less than 0.5% by mass, the effect may not be sufficiently exerted on the film formation by the electrochemical reaction on the electrode surface. If it exceeds 10.0 mass%, the viscosity of the electrolytic solution may be increased. As a ratio of the compound of general formula (3) in general formula (1) and general formula (3), 10-90 mass% of the total mass of the compound of general formula (1) and general formula (3) is preferable. . Moreover, when using the compound of General formula (2) in addition to this, 10-90 mass% of the total mass of the compound of General formula (1), General formula (2), and General formula (3) is preferable.

  In the present invention, in some cases, at least one of vinylene carbonate (VC) and a derivative thereof can be added to the electrolytic solution. By adding at least one of vinylene carbonate (VC) and its derivatives, the cycle characteristics can be further improved. The LUMO of VC is 0.09 eV and is less susceptible to the reduction reaction than the compound of general formula (1). It is considered that it exists in the electrolyte for a long time without being consumed after receiving the reduction reaction in the initial charge and discharge. Therefore, it is possible to contribute to the improvement of cycle characteristics by being gradually consumed during the charge / discharge cycle. When at least one of the vinylene carbonate and derivatives thereof is used as an additive for an electrolytic solution, the effect can be obtained by including 0.05% by mass to 3.0% by mass in the electrolytic solution.

  When the compound of the general formula (1) and VC, the compound of the general formula (1) and other additives, and VC are further added to the electrolytic solution, the proportion of VC in the whole electrolytic solution is not particularly limited. Is preferably 0.5% by mass to 10.0% by mass. If the amount is less than 0.5% by mass, the effect may not be sufficiently exerted on the film formation by the electrochemical reaction on the electrode surface. If it exceeds 10.0 mass%, the viscosity of the electrolytic solution may be increased.

  The electrolytic solution of the present invention is brought about by adding and dissolving the compound represented by the general formula (1) in the electrolytic solution in advance. By appropriately adding other additive materials (cyclic monosulfonic acid ester, cyclic sulfonic acid ester having two sulfonyl groups, sulfolane, alkanesulfonic acid anhydride, sulfolene compound or vinylene carbonate compound) to this electrolytic solution, The electrolyte solution can be obtained.

  The shape of the secondary battery according to the present invention is not particularly limited, and examples thereof include a cylindrical shape, a square shape, a coin shape, and a laminate shape. Among them, the laminate type has a shape sealed by an exterior body made of a flexible film made of a laminate of a synthetic resin and a metal foil, and is a battery can such as a cylindrical type, a square type, or a coin type. It is more susceptible to an increase in internal pressure than that enclosed in an outer package, and therefore control of the chemical reaction between the electrode and the interface between the electrolytic solution is more important. In the case of a secondary battery containing a chain disulfone compound represented by the general formula (1) according to the present invention, even a laminate-type battery can suppress resistance increase and battery swelling (gas generation and internal pressure increase). ) Can be suppressed. Therefore, safety and long-term reliability can be ensured even in a large-sized lithium ion secondary battery such as an automobile.

  In the lithium secondary battery according to the present invention, the negative electrode 13 and the positive electrode 12 are laminated via the separator 16 in a dry air or an inert gas atmosphere, or the laminated one is wound, and then inserted into the outer package. It is obtained by impregnating an electrolytic solution containing a compound represented by the formula (1) and then sealing the battery outer package. The effect of the present invention can be obtained by forming the film on the electrode by charging the battery before or after sealing.

  Moreover, the chain | strand-shaped disulfonic acid ester shown by General formula (1) of this invention can also be used not only as a lithium secondary battery but as an additive of the electrolyte solution for other electrochemical devices. Examples of other electrochemical devices include organic radical batteries, capacitors, and dye-sensitized wet solar cells.

(Production of battery)
A positive electrode active material and a conductivity-imparting agent described in Tables 1 to 5 were dry-mixed and uniformly dispersed in N-methyl-2-pyrrolidone (NMP) in which PVDF as a binder was dissolved to prepare a slurry. Carbon black was used as the conductivity imparting agent. The slurry was applied on an aluminum metal foil (20 μm for square and cylindrical types, 25 μm for laminated types) serving as a positive electrode current collector, and then NMP was evaporated to obtain a positive electrode sheet. The solid content ratio in the positive electrode was positive electrode active material: conductivity imparting agent: PVDF = 80: 10: 10 (mass%).

  On the other hand, the negative electrode active materials other than the carbon material are those shown in Tables 1 to 5. Graphite or amorphous carbon was used as the carbon material. When the negative electrode active material is in the form of particles, a negative active material other than the carbon material: PVDF: conductivity imparting material = 90: 9: 1 (mass%) dry-mixed with an average particle diameter of 10 μm The carbon material particles were dispersed in NMP and coated on a copper foil (10 μm for square and cylindrical types, 20 μm for laminated types) to be a negative electrode current collector. When the negative electrode active material is in the form of a film, unless otherwise specified, dry mixing was performed so that the ratio of carbon material particles having an average particle diameter of 10 μm: PVDF: conductivity imparting material = 90: 9: 1 (mass%). After being dispersed in NMP and coated on a copper foil (10 μm for rectangular and cylindrical types, 20 μm for laminated types) as a negative electrode current collector, vacuum deposition, sputtering, and CVD A negative electrode active material other than the carbon material was formed by appropriately selecting from the methods. In the case of using composite particles in which a metal, metalloid, or oxide and a carbon material are combined as the negative electrode active material, the ratio of composite particles: PVDF: conductivity imparting material = 90: 9: 1 (mass%) is set. A mixture obtained by dry mixing was dispersed in NMP and applied to a copper foil (10 μm) serving as a negative electrode current collector. Unless otherwise specified, the carbon material with respect to the whole negative electrode active material was 50% by mass. The film thickness of these negative electrodes is set by the capacity ratio with the positive electrode (hereinafter referred to as A / C balance), where A is the capacity per unit surface area of the negative electrode, and C is the capacity per unit surface area of the positive electrode. The coating amount of the positive electrode and the negative electrode was determined so that the A / C balance was 1 or more and 1.7 or less.

The electrolytic solution used was a solvent described in Tables 1 to 5, 1 mol / L LiPF ₆ as an electrolyte, and an additive described in Tables 1 to 5 dissolved therein. The numbers in parentheses in the “Additive” column indicate the mass% of the additive in the electrolytic solution.

  Then, a negative electrode and a positive electrode were laminated via a separator made of polyethylene, and square secondary batteries (Examples 1-31, 52-60, 61-91, and 112-143, and Comparative Examples 1-3, 9-13, 19 and 20), cylindrical secondary batteries (Examples 46 to 51 and 106 to 111, and Comparative Examples 8 and 18), and aluminum laminated film type secondary batteries (Examples 32 to 45 and 92 to 105 and Comparative Examples 4 to 7 and 14 to 17) were produced. In the case of an aluminum laminate film type secondary battery, the laminate film used has a structure in which a polypropylene resin (sealing layer, thickness 70 μm), polyethylene terephthalate (20 μm), aluminum (50 μm), and polyethylene terephthalate (20 μm) are laminated in this order. Two pieces of this are cut into a predetermined size, and a concave portion having a bottom surface portion and a side surface portion that match the size of the multilayer electrode body is formed in a part thereof, and these are opposed to wrap the multilayer electrode body. Then, the periphery was thermally fused to produce a film-clad battery. Before the last side was heat-sealed and sealed, the electrolyte solution was impregnated with the laminated electrode body.

(Battery evaluation)
The battery produced by the above process was subjected to a charge / discharge cycle test at a temperature of 20 ° C. with a charge rate of 1.0 C, a discharge rate of 1.0 C, a charge end voltage of 4.2 V, and a discharge end voltage of 3.0 V. The results are shown in Tables 6-10. The capacity retention rate (%) after 400 cycles is obtained by multiplying 100 by the value obtained by dividing the discharge capacity (mAh) after the 400 cycle test by the discharge capacity (mAh) after the 10 cycle test. The resistance maintenance rate after 400 cycles is a relative value of the resistance after the 400 cycle test when the resistance before the cycle test is 1.

Example 1
The layer containing the negative electrode active material was produced by forming a film of Si by a CVD method as a negative electrode active material other than the carbon material. Graphite was used as the carbon material. LiCoO ₂ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolytic solution, EC / DEC / EMC = 30/50/20 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.5% by mass was used. An aluminum square container was used as the battery casing. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 2)
The layer containing the negative electrode active material was formed by depositing Sn as a negative electrode active material other than the carbon material by vapor deposition. The other conditions were the same as in Example 1.

(Example 3)
The layer containing the negative electrode active material was formed by sputtering Al as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 1.

Example 4
The layer containing the negative electrode active material was prepared using Pb having an average particle diameter of 10 μm as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 1.

(Example 5)
The layer containing the negative electrode active material was prepared using Ag having an average particle size of 10 μm as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 1.

(Example 6)
The layer containing the negative electrode active material was formed by sputtering Ge as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 1.

(Example 7)
The layer containing the negative electrode active material was formed by depositing Sb as a negative electrode active material other than the carbon material by vapor deposition. The other conditions were the same as in Example 1.

(Example 8)
The layer containing the negative electrode active material was formed by simultaneously forming a film using two sputtering sources of Si and Al as the negative electrode active material other than the carbon material (number of Si atoms: number of Al atoms = 5: 5). The other conditions were the same as in Example 1.

Example 9
The layer containing the negative electrode active material was prepared using particles obtained by mixing Si having an average particle diameter of 10 μm and Sn having an average particle diameter of 10 μm by mechanical milling as a negative electrode active material other than the carbon material (number of Si atoms: Sn atom). Number = 5: 5). The other conditions were the same as in Example 1.

(Example 10)
The layer containing the negative electrode active material was produced by forming a film by simultaneous vapor deposition using two vapor deposition sources of Si and Li as the negative electrode active material other than the carbon material (the number of Si atoms: the number of Li atoms = 5: 5). ). The other conditions were the same as in Example 1.

(Example 11)
The additive is compound no. 2 was used. The other conditions were the same as in Example 1.

(Example 12)
The additive is compound no. 3 was used. The other conditions were the same as in Example 1.

(Example 13)
The additive is compound no. 4 was used. The other conditions were the same as in Example 1.

(Example 14)
The additive is compound no. 6 was used. The other conditions were the same as in Example 1.

(Example 15)
The additive is compound no. 9 was used. The other conditions were the same as in Example 1.

(Example 16)
The additive is compound no. 10 was used. The other conditions were the same as in Example 1.

(Example 17)
The additive is compound no. 15 was used. The other conditions were the same as in Example 1.

(Example 18)
The additive is compound no. 16 was used. The other conditions were the same as in Example 1.

(Example 19)
The additive is compound no. 19 was used. The other conditions were the same as in Example 1.

(Example 20)
The layer containing the negative electrode active material was prepared using Si having an average particle size of 10 μm as a negative electrode active material other than the carbon material. Amorphous carbon was used as the carbon material. The other conditions were the same as in Example 1.

(Example 21)
The layer containing the negative electrode active material was prepared using Sn having an average particle size of 10 μm as a negative electrode active material other than the carbon material. Amorphous carbon was used as the carbon material. The other conditions were the same as in Example 1.

(Comparative Example 1)
The layer containing the negative electrode active material was formed by depositing Si by vapor deposition as a negative electrode active material other than the carbon material. In addition, no additive was used in the electrolytic solution. The other conditions were the same as in Example 1.

(Comparative Example 2)
The layer containing the negative electrode active material was prepared using Si having an average particle size of 10 μm as a negative electrode active material other than the carbon material. Amorphous carbon was used as the carbon material. In addition, no additive was used in the electrolytic solution. The other conditions were the same as in Example 1.

(Example 22)
The layer containing the negative electrode active material was produced by forming a film of Si by a CVD method as a negative electrode active material other than the carbon material. Graphite was used as the carbon material. LiMnO ₂ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolyte, PC / EC / DEC = 20/20/60 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.5% by mass was used. An aluminum square container was used as the battery casing. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 23)
The layer containing the negative electrode active material was formed by depositing Sn as a negative electrode active material other than the carbon material by vapor deposition. The other conditions were the same as in Example 22.

(Example 24)
The layer containing the negative electrode active material was formed by sputtering Al as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 22.

(Example 25)
The layer containing the negative electrode active material was prepared using Pb having an average particle diameter of 10 μm as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 22.

(Example 26)
The layer containing the negative electrode active material was prepared using Ag having an average particle size of 10 μm as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 22.

(Example 27)
The layer containing the negative electrode active material was formed by sputtering Ge as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 22.

(Example 28)
The layer containing the negative electrode active material was formed by depositing Sb as a negative electrode active material other than the carbon material by vapor deposition. The other conditions were the same as in Example 22.

(Example 29)
The layer containing the negative electrode active material was formed by simultaneously forming a film using two sputtering sources of Si and Al as the negative electrode active material other than the carbon material (number of Si atoms: number of Al atoms = 5: 5). The other conditions were the same as in Example 22.

(Example 30)
The layer containing the negative electrode active material was prepared using particles obtained by mixing Si having an average particle diameter of 10 μm and Sn having an average particle diameter of 10 μm by mechanical milling as a negative electrode active material other than the carbon material (number of Si atoms: Sn atom). Number = 5: 5). The other conditions were the same as in Example 22.

(Example 31)
The layer containing the negative electrode active material was produced by forming a film by simultaneous vapor deposition using two vapor deposition sources of Si and Li as the negative electrode active material other than the carbon material (the number of Si atoms: the number of Li atoms = 5: 5). ). The other conditions were the same as in Example 22.

(Comparative Example 3)
The layer containing the negative electrode active material was formed by depositing Si by vapor deposition as a negative electrode active material other than the carbon material. In addition, no additive was used in the electrolytic solution. The other conditions were the same as in Example 22.

(Example 32)
The layer containing the negative electrode active material was formed by simultaneous vapor deposition using two vapor deposition sources of Si and Fe corresponding to the element X as the negative electrode active material other than the carbon material (number of Si atoms: Fe atoms Number = 19: 1). Graphite was used as the carbon material. LiCoO ₂ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolytic solution, EC / DEC / EMC = 30/50/20 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.5% by mass was used. A container was made of a member coated with an aluminum foil with a laminate for the battery outer body. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 33)
The layer containing the negative electrode active material was formed by simultaneously forming a film using two sputtering sources of Sn and Cu corresponding to the element X as the negative electrode active material other than the carbon material (the number of Sn atoms: the number of Cu atoms = 3: 7). The other conditions were the same as in Example 32.

(Example 34)
The layer containing the negative electrode active material uses particles obtained by mixing mechanically milled Si-Al alloy particles having an average particle diameter of 10 μm and Ni particles corresponding to the element X having an average particle diameter of 10 μm as a negative electrode active material other than the carbon material. (The number of Si atoms: the number of Al atoms: the number of Ni atoms = 10: 9: 1). The other conditions were the same as in Example 32.

(Example 35)
For the layer containing the negative electrode active material, particles obtained by mixing mechanically milled Si-Sn alloy particles having an average particle diameter of 10 μm and Ti particles corresponding to the element X having an average particle diameter of 10 μm as a negative electrode active material other than the carbon material are used. (Number of Si atoms: Number of Sn atoms: Number of Ti atoms = 5: 5: 90). The other conditions were the same as in Example 32.

(Example 36)
The layer containing the negative electrode active material uses particles obtained by mixing mechanically milled Si-Li alloy particles having an average particle diameter of 10 μm and Fe particles corresponding to the element X having an average particle diameter of 10 μm as a negative electrode active material other than the carbon material. (Number of Si atoms: number of Li atoms: number of Fe atoms = 9: 4: 1). The other conditions were the same as in Example 32.

(Example 37)
The layer containing the negative electrode active material used was a composite of Si particles having an average particle size of 10 μm and Fe particles corresponding to the element X having an average particle size of 10 μm by mechanical milling as a negative electrode active material other than the carbon material ( Si atom number: Fe atom number = 9: 1). Amorphous carbon was used as the carbon material. The other conditions were the same as in Example 32.

(Comparative Example 4)
The layer containing the negative electrode active material was formed by simultaneous vapor deposition using two vapor deposition sources of Si and Fe corresponding to the element X as the negative electrode active material other than the carbon material (number of Si atoms: Fe atoms Number = 19: 1). In addition, no additive was used in the electrolytic solution. The other conditions were the same as in Example 32.

(Comparative Example 5)
The layer containing the negative electrode active material used was a composite of Si particles having an average particle size of 10 μm and Fe particles corresponding to the element X having an average particle size of 10 μm by mechanical milling as a negative electrode active material other than the carbon material ( Si atom number: Fe atom number = 9: 1). Amorphous carbon was used as the carbon material. In addition, no additive was used in the electrolytic solution. The other conditions were the same as in Example 32.

(Example 38)
The layer containing the negative electrode active material was formed by depositing Si by vapor deposition as a negative electrode active material other than the carbon material. Graphite was used as the carbon material. LiMn ₂ O ₄ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolyte, PC / EC / DEC = 20/20/60 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.5% by mass was used. A container was made of a member coated with an aluminum foil with a laminate for the battery outer body. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 39)
The layer containing the negative electrode active material was formed by depositing Sn as a negative electrode active material other than the carbon material by vapor deposition. The other conditions were the same as in Example 38.

(Example 40)
The layer containing the negative electrode active material was prepared by simultaneously forming a film using two sputtering sources of Si and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). The other conditions were the same as in Example 38.

(Example 41)
The layer containing the negative electrode active material was formed by depositing Si by vapor deposition as a negative electrode active material other than the carbon material. In addition, the additive is compound no. 0.5% by mass of 1 and 3% by mass of 1,3-PS were used. The other conditions were the same as in Example 38.

(Example 42)
The layer containing the negative electrode active material was formed by depositing Sn as a negative electrode active material other than the carbon material by vapor deposition. In addition, the additive is compound no. 0.5% by mass of 1 and 3% by mass of 1,3-PS were used. The other conditions were the same as in Example 38.

(Example 43)
The layer containing the negative electrode active material was prepared by simultaneously forming a film using two sputtering sources of Si and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). In addition, the additive is compound no. 0.5% by mass of 1 and 3% by mass of 1,3-PS were used. The other conditions were the same as in Example 38.

(Example 44)
The layer containing the negative electrode active material was prepared by simultaneously forming a film using two sputtering sources of Si and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). In addition, the additive is compound no. 1 mass%, 1,3-PS 3 mass%, and VC 1 mass%. The other conditions were the same as in Example 38.

(Example 45)
The layer containing the negative electrode active material was prepared by simultaneously forming a film using two sputtering sources of Si and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). In addition, the additive is compound no. 0.5% by mass of 1 and 0.5% by mass of MMDS were used. The other conditions were the same as in Example 38.

(Comparative Example 6)
The layer containing the negative electrode active material was prepared by simultaneously forming a film using two sputtering sources of Si and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). In addition, no additive was used in the electrolytic solution. The other conditions were the same as in Example 38.

(Comparative Example 7)
The layer containing the negative electrode active material was prepared by simultaneously forming a film using two sputtering sources of Si and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). Further, 3% by mass of 1,3-PS was used as an additive in the electrolytic solution. The other conditions were the same as in Example 38.

(Example 46)
The layer containing the negative electrode active material was prepared by simultaneously forming a film using two sputtering sources of Si and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). Graphite was used as the carbon material. LiCoO ₂ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolytic solution, EC / DEC / EMC = 30/50/20 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.01% by mass was used. A 18650 cylindrical container was used for the battery outer casing. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 47)
The additive is compound no. 0.1% by mass of 1 was used. The other conditions were the same as in Example 46.

(Example 48)
The additive is compound no. 1 was used at 0.75 mass%. The other conditions were the same as in Example 46.

(Example 49)
The additive is compound no. 1 was used in an amount of 3% by mass. The other conditions were the same as in Example 46.

(Example 50)
The additive is compound no. 1 was used in an amount of 5% by mass. The other conditions were the same as in Example 46.

(Example 51)
The additive is compound no. 1 was used in an amount of 8% by mass. The other conditions were the same as in Example 46.

(Comparative Example 8)
No additive was used in the electrolyte. The other conditions were the same as in Example 46.

(Example 52)
The layer containing the negative electrode active material was prepared using composite particles obtained by combining graphite particles having an average particle diameter of 10 μm and Si particles having an average particle diameter of 1 μm by mechanical milling. LiCoO ₂ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolytic solution, EC / DEC / EMC = 30/50/20 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.5% by mass was used. A square container was used for the battery outer casing. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 53)
The layer containing the negative electrode active material was prepared using composite particles in which graphite particles having an average particle diameter of 10 μm and Sn particles having an average particle diameter of 1 μm were combined by mechanical milling. The other conditions were the same as in Example 52.

(Example 54)
The layer containing the negative electrode active material is composed of composite particles obtained by combining mechanically milled Si particles having an average particle diameter of 1 μm and Ni particles having an average particle diameter of 1 μm, and graphite particles having an average particle diameter of 10 μm by mechanofusion. The composite particles were prepared (number of Si atoms: number of Ni atoms = 9: 1). The other conditions were the same as in Example 52.

(Comparative Example 9)
No additive was used in the electrolyte. The other conditions were the same as in Example 52.

(Example 55)
The layer containing the negative electrode active material is composed of composite particles obtained by combining graphite particles having an average particle diameter of 10 μm and Si particles having an average particle diameter of 1 μm by mechanical milling and further carbon coating by a CVD method. Produced. LiCoO ₂ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolytic solution, EC / DEC / EMC = 30/50/20 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.5% by mass was used. A square container was used for the battery outer casing. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 56)
The layer containing the negative electrode active material is a composite of particles obtained by alloying Sn particles having an average particle diameter of 1 μm and Cu particles having an average particle diameter of 1 μm by mechanical milling and graphite particles having an average particle diameter of 10 μm by mechanical milling. Furthermore, it produced using the composite particle | grains obtained by carbon coating by CVD (Sn atom number: Cu atom number = 4: 1). The other conditions were the same as in Example 55.

(Example 57)
The layer containing the negative electrode active material is prepared using composite particles obtained by combining graphite particles having an average particle diameter of 10 μm and Sn particles having an average particle diameter of 1 μm by mechanical milling and further carbon coating by CVD. did. The other conditions were the same as in Example 55.

(Comparative Example 10)
No additive was used in the electrolyte. The other conditions were the same as in Example 55.

(Example 58)
The content of the carbon material was 5% by mass. The other conditions were the same as in Example 1.

(Example 59)
The content of the carbon material was 95% by mass. The other conditions were the same as in Example 1.

(Example 60)
A layer containing a negative electrode active material was prepared by first forming a graphite film by a sputtering method and then forming Si as a negative electrode active material other than a carbon material by a CVD method. The other conditions were the same as in Example 1.

(Example 61)
The layer containing the negative electrode active material was formed by depositing SiO as a negative electrode active material other than the carbon material by vapor deposition. Graphite was used as the carbon material. LiCoO ₂ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolytic solution, EC / DEC / EMC = 30/50/20 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.5% by mass was used. An aluminum square container was used as the battery casing. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 62)
The layer containing the negative electrode active material was formed by sputtering SnO as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 61.

(Example 63)
The layer containing the negative electrode active material was formed by sputtering SnO ₂ as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 61.

(Example 64)
The layer containing the negative electrode active material is prepared using particles obtained by mixing mechanically milled Fe ₂ O ₃ particles having an average particle diameter of 10 μm and B ₂ O ₃ particles having an average particle diameter of 10 μm as a negative electrode active material other than the carbon material. (Fe atom number: B atom number = 5: 5). The other conditions were the same as in Example 61.

(Example 65)
The layer containing the negative electrode active material is prepared using particles obtained by mixing mechanically milled Fe ₂ O ₃ particles having an average particle diameter of 10 μm and P ₂ O ₅ particles having an average particle diameter of 10 μm as a negative electrode active material other than the carbon material. did. The other conditions were the same as in Example 61 (Fe atom number: P atom number = 5: 5).

Example 66
The layer containing the negative electrode active material was formed by sputtering W ₂ O ₅ as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 61.

(Example 67)
The layer containing the negative electrode active material was prepared using Li ₄ Ti ₅ O ₁₂ having an average particle size of 10 μm as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 61.

Example 68
The layer containing the negative electrode active material was prepared using particles obtained by mixing mechanically milled SiO particles having an average particle diameter of 10 μm and SnO particles having an average particle diameter of 10 μm as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 61 (Si atom number: Sn atom number = 5: 5).

(Example 69)
The layer containing the negative electrode active material was prepared by forming a film by simultaneous vapor deposition using two vapor deposition sources of SnO and Li as the negative electrode active material other than the carbon material (the number of Sn atoms: the number of Li atoms = 5: 5). ). The other conditions were the same as in Example 61.

(Example 70)
The layer containing the negative electrode active material was formed by simultaneous vapor deposition using two vapor deposition sources of SiO and Li as the negative electrode active material other than the carbon material (Si atom number: Li atom number = 5: 5). The other conditions were the same as in Example 61.

(Example 71)
The additive is compound no. 2 was used. The other conditions were the same as in Example 61.

(Example 72)
The additive is compound no. 3 was used. The other conditions were the same as in Example 61.

(Example 73)
The additive is compound no. 4 was used. The other conditions were the same as in Example 61.

(Example 74)
The additive is compound no. 6 was used. The other conditions were the same as in Example 61.

(Example 75)
The additive is compound no. 9 was used. The other conditions were the same as in Example 61.

(Example 76)
The additive is compound no. 10 was used. The other conditions were the same as in Example 61.

(Example 77)
The additive is compound no. 15 was used. The other conditions were the same as in Example 61.

(Example 78)
The additive is compound no. 16 was used. The other conditions were the same as in Example 61.

(Example 79)
The additive is compound no. 19 was used. The other conditions were the same as in Example 61.

(Example 80)
The layer containing the negative electrode active material was produced using SiO having an average particle size of 10 μm as a negative electrode active material other than the carbon material. Amorphous carbon was used as the carbon material. The other conditions were the same as in Example 61.

(Example 81)
The layer containing the negative electrode active material was prepared using SnO having an average particle size of 10 μm as a negative electrode active material other than the carbon material. Amorphous carbon was used as the carbon material. The other conditions were the same as in Example 61.

(Comparative Example 11)
The layer containing the negative electrode active material was formed by depositing SiO as a negative electrode active material other than the carbon material by vapor deposition. In addition, no additive was used in the electrolytic solution. The other conditions were the same as in Example 61.

(Comparative Example 12)
The layer containing the negative electrode active material was produced using SiO having an average particle size of 10 μm as a negative electrode active material other than the carbon material. Amorphous carbon was used as the carbon material. In addition, no additive was used in the electrolytic solution. The other conditions were the same as in Example 61.

(Example 82)
The layer containing the negative electrode active material was formed by depositing SiO as a negative electrode active material other than the carbon material by vapor deposition. Graphite was used as the carbon material. LiMnO ₂ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolyte, PC / EC / DEC = 20/20/60 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.5% by mass was used. An aluminum square container was used as the battery casing. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 83)
The layer containing the negative electrode active material was formed by sputtering SnO as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 82.

(Example 84)
The layer containing the negative electrode active material was formed by sputtering SnO ₂ as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 82.

(Example 85)
The layer containing the negative electrode active material is prepared using particles obtained by mixing mechanically milled Fe ₂ O ₃ particles having an average particle diameter of 10 μm and B ₂ O ₃ particles having an average particle diameter of 10 μm as a negative electrode active material other than the carbon material. (Fe atom number: B atom number = 5: 5). The other conditions were the same as in Example 82.

(Example 86)
The layer containing the negative electrode active material is prepared using particles obtained by mixing mechanically milled Fe ₂ O ₃ particles having an average particle diameter of 10 μm and P ₂ O ₅ particles having an average particle diameter of 10 μm as a negative electrode active material other than the carbon material. (Fe atom number: P atom number = 5: 5). The other conditions were the same as in Example 82.

(Example 87)
The layer containing the negative electrode active material was formed by sputtering W ₂ O ₅ as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 82.

(Example 88)
The layer containing the negative electrode active material was prepared using Li ₄ Ti ₅ O ₁₂ having an average particle size of 10 μm as a negative electrode active material other than the carbon material. The other conditions were the same as in Example 82.

Example 89
The layer containing the negative electrode active material was prepared using particles obtained by mixing mechanically milled SiO particles having an average particle size of 10 μm and SnO particles having an average particle size of 10 μm as negative electrode active materials other than the carbon material (number of Si atoms: Number of Sn atoms = 5: 5). The other conditions were the same as in Example 82.

(Example 90)
The layer containing the negative electrode active material was prepared by forming a film by simultaneous vapor deposition using two vapor deposition sources of SnO and Li as the negative electrode active material other than the carbon material (the number of Sn atoms: the number of Li atoms = 5: 5). ). The other conditions were the same as in Example 82.

(Example 91)
The layer containing the negative electrode active material was formed by simultaneous vapor deposition using two vapor deposition sources of SiO and Li as the negative electrode active material other than the carbon material (Si atom number: Li atom number = 5: 5). The other conditions were the same as in Example 82.

(Comparative Example 13)
The layer containing the negative electrode active material was formed by depositing SiO as a negative electrode active material other than the carbon material by vapor deposition. In addition, no additive was used in the electrolytic solution. The other conditions were the same as in Example 82.

(Example 92)
The layer containing the negative electrode active material was formed by simultaneous vapor deposition using two vapor deposition sources of SiO and Fe corresponding to the element X as the negative electrode active material other than the carbon material (number of Si atoms: Fe atoms Number = 14: 1). Graphite was used as the carbon material. LiCoO ₂ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolytic solution, EC / DEC / EMC = 30/50/20 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.5% by mass was used. A container was made of a member coated with an aluminum foil with a laminate for the battery outer body. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 93)
The layer containing the negative electrode active material was formed by simultaneously forming a film using two sputtering sources of SnO and Cu corresponding to the element X as the negative electrode active material other than the carbon material (the number of Sn atoms: the number of Cu atoms = 3: 7). The other conditions were the same as in Example 92.

(Example 94)
The layer containing the negative electrode active material is prepared using particles obtained by mixing mechanically milled SnO ₂ particles having an average particle diameter of 10 μm and Ni particles corresponding to the element X having an average particle diameter of 10 μm as a negative electrode active material other than the carbon material. (Sn atom number: Ni atom number = 19: 1). The other conditions were the same as in Example 92.

(Example 95)
The layer containing the negative electrode active material was prepared by simultaneously forming films using three sputtering sources of SnO, Li, and Ti corresponding to the element X as the negative electrode active material other than the carbon material (Sn atom number: Li atom). Number: Ti atom number = 1: 1: 9). The other conditions were the same as in Example 92.

Example 96
The layer containing the negative electrode active material was formed by simultaneously forming films using three sputtering sources of SiO, Li, and Fe corresponding to the element X as the negative electrode active material other than the carbon material (number of Si atoms: Li atoms Number: Fe atom number = 9: 3: 1). The other conditions were the same as in Example 92.

(Example 97)
The layer containing the negative electrode active material used was a composite of mechanically milled SiO particles having an average particle size of 10 μm and Fe particles corresponding to the element X having an average particle size of 10 μm as a negative electrode active material other than the carbon material ( Si atom number: Fe atom number = 9: 1). Amorphous carbon was used as the carbon material. The other conditions were the same as in Example 92.

(Comparative Example 14)
The layer containing the negative electrode active material was formed by simultaneous vapor deposition using two vapor deposition sources of SiO and Fe corresponding to the element X as the negative electrode active material other than the carbon material (number of Si atoms: Fe atoms Number = 14: 1). In addition, no additive was used in the electrolytic solution. The other conditions were the same as in Example 92.

(Comparative Example 15)
The layer containing the negative electrode active material used was a composite of mechanically milled SiO particles having an average particle size of 10 μm and Fe particles corresponding to the element X having an average particle size of 10 μm as a negative electrode active material other than the carbon material ( Si atom number: Fe atom number = 9: 1). Amorphous carbon was used as the carbon material. In addition, no additive was used in the electrolytic solution. The other conditions were the same as in Example 92.

(Example 98)
The layer containing the negative electrode active material was formed by depositing SiO as a negative electrode active material other than the carbon material by vapor deposition. Graphite was used as the carbon material. LiMn ₂ O ₄ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolyte, PC / EC / DEC = 20/20/60 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.5% by mass was used. A container was made of a member coated with an aluminum foil with a laminate for the battery outer body. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

Example 99
The layer containing the negative electrode active material was formed by depositing SnO as a negative electrode active material other than the carbon material by vapor deposition. The other conditions were the same as in Example 98.

(Example 100)
The layer containing the negative electrode active material was formed by simultaneously forming a film using two sputtering sources of SiO and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). The other conditions were the same as in Example 98.

(Example 101)
The layer containing the negative electrode active material was formed by depositing SiO as a negative electrode active material other than the carbon material by vapor deposition. In addition, the additive is compound no. 0.5% by mass of 1 and 3% by mass of 1,3-PS were used. The other conditions were the same as in Example 98.

(Example 102)
The layer containing the negative electrode active material was formed by depositing SnO as a negative electrode active material other than the carbon material by vapor deposition. In addition, the additive is compound no. 0.5% by mass of 1 and 3% by mass of 1,3-PS were used. The other conditions were the same as in Example 98.

(Example 103)
The layer containing the negative electrode active material was formed by simultaneously forming a film using two sputtering sources of SiO and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). In addition, the additive is compound no. 0.5% by mass of 1 and 3% by mass of 1,3-PS were used. The other conditions were the same as in Example 98.

(Example 104)
The layer containing the negative electrode active material was formed by simultaneously forming a film using two sputtering sources of SiO and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). In addition, the additive is compound no. 1 mass%, 1,3-PS 3 mass%, and VC 1 mass%. The other conditions were the same as in Example 98.

(Example 105)
The layer containing the negative electrode active material was formed by simultaneously forming a film using two sputtering sources of SiO and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). In addition, the additive is compound no. 0.5% by mass of 1 and 0.5% by mass of MMDS were used. The other conditions were the same as in Example 98.

(Comparative Example 16)
The layer containing the negative electrode active material was formed by simultaneously forming a film using two sputtering sources of SiO and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). In addition, no additive was used in the electrolytic solution. The other conditions were the same as in Example 98.

(Comparative Example 17)
The layer containing the negative electrode active material was formed by simultaneously forming a film using two sputtering sources of SiO and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). Further, 3% by mass of 1,3-PS was used as an additive. The other conditions were the same as in Example 98.

(Example 106)
The layer containing the negative electrode active material was formed by simultaneously forming a film using two sputtering sources of SiO and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom number: Fe atom number = 7: 3). Graphite was used as the carbon material. LiCoO ₂ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolytic solution, EC / DEC / EMC = 30/50/20 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.01% by mass was used. A 18650 cylindrical container was used for the battery outer casing. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 107)
The additive is compound no. 0.1% by mass of 1 was used. The other conditions were the same as in Example 106.

(Example 108)
The additive is compound no. 1 was used at 0.75 mass%. The other conditions were the same as in Example 106.

(Example 109)
The additive is compound no. 1 was used in an amount of 3% by mass. The other conditions were the same as in Example 106.

(Example 110)
The additive is compound no. 1 was used in an amount of 5% by mass. The other conditions were the same as in Example 106.

(Example 111)
The additive is compound no. 1 was used in an amount of 8% by mass. The other conditions were the same as in Example 106.

(Comparative Example 18)
No additive was used in the electrolyte. The other conditions were the same as in Example 106.

(Example 112)
The layer containing the negative electrode active material was prepared using composite particles in which graphite particles having an average particle size of 10 μm and SiO particles having an average particle size of 1 μm were combined by mechanical milling. LiCoO ₂ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolytic solution, EC / DEC / EMC = 30/50/20 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.5% by mass was used. A square container was used for the battery outer casing. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 113)
The layer containing the negative electrode active material was prepared using composite particles obtained by combining graphite particles having an average particle diameter of 10 μm and SnO particles having an average particle diameter of 1 μm by mechanical milling. The other conditions were the same as in Example 112.

(Example 114)
The layer containing the negative electrode active material is composed of composite particles in which SiO particles having an average particle diameter of 1 μm and Ni particles having an average particle diameter of 1 μm are combined by mechanical milling and graphite particles having an average particle diameter of 10 μm by mechanical fusion. It was produced using composite particles that were combined (number of Si atoms: number of Ni atoms = 9: 1). The other conditions were the same as in Example 112.

(Comparative Example 19)
No additive was used in the electrolyte. The other conditions were the same as in Example 112.

(Example 115)
The layer containing the negative electrode active material is prepared using composite particles obtained by combining graphite particles having an average particle diameter of 10 μm and SiO particles having an average particle diameter of 1 μm by mechanical milling and further carbon coating by CVD. did. LiCoO ₂ was used as the positive electrode active material contained in the layer containing the positive electrode active material. In the electrolytic solution, EC / DEC / EMC = 30/50/20 (volume ratio), 1 mol / L LiPF ₆ as an electrolyte, and Compound No. 1 containing 0.5% by mass was used. A square container was used for the battery outer casing. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 116)
The layer containing the negative electrode active material is a composite of mechanically milled particles obtained by alloying SnO particles having an average particle diameter of 1 μm and Cu particles having an average particle diameter of 1 μm by mechanical milling and graphite particles having an average particle diameter of 10 μm. Furthermore, it produced using the composite particle | grains obtained by carbon coating by CVD (Sn atom number: Cu atom number = 4: 1). The other conditions were the same as in Example 115.

(Example 117)
The layer containing the negative electrode active material is prepared using composite particles obtained by combining graphite particles having an average particle diameter of 10 μm and SnO particles having an average particle diameter of 1 μm by mechanical milling and further carbon coating by CVD. did. The other conditions were the same as in Example 115.

(Comparative Example 20)
No additive was used in the electrolyte. The other conditions were the same as in Example 115.

(Example 118)
The content of the carbon material was 5% by mass. The other conditions were the same as in Example 61.

(Example 119)
The content of the carbon material was 95% by mass. The other conditions were the same as in Example 61.

(Example 120)
A layer containing a negative electrode active material was prepared by first forming a graphite film by a sputtering method, and then forming SiO as a negative electrode active material other than a carbon material by a CVD method. The other conditions were the same as in Example 61.

(Example 121)
The layer containing the negative electrode active material was formed by using two vapor deposition sources of Si and SiO as the negative electrode active material other than the carbon material and forming a film by simultaneous vapor deposition (Si atom number: O atom number = 2: 1). The other conditions were the same as in Example 1.

(Example 122)
The layer containing the negative electrode active material was prepared by using two sputtering sources of Sn and SnO as the negative electrode active material other than the carbon material and forming a film by simultaneous sputtering (Sn atom number: O atom number = 2: 1). The other conditions were the same as in Example 1.

(Example 123)
The layer containing the negative electrode active material was prepared by using three vapor deposition sources of Si, SiO ₂ and Li as the negative electrode active material other than the carbon material, and formed by simultaneous vapor deposition (number of Si atoms: number of O atoms : Number of Li atoms = 1: 1: 1). The other conditions were the same as in Example 1.

(Example 124)
The layer containing the negative electrode active material was prepared by using three vapor deposition sources of Sn, SnO _2, and Li as the negative electrode active material other than the carbon material, and was formed by simultaneous vapor deposition (the number of Sn atoms: the number of O atoms : Number of Li atoms = 1: 1: 1). The other conditions were the same as in Example 1.

(Example 125)
The layer containing the negative electrode active material was prepared by mixing Si having an average particle diameter of 1 μm and SiO having an average particle diameter of 1 μm as a negative electrode active material other than the carbon material. The mixing ratio was such that the ratio of the number of Si atoms in Si having an average particle diameter of 1 μm and the number of molecules of SiO having an average particle diameter of 1 μm was 1: 1. The other conditions were the same as in Example 1.

(Example 126)
The layer containing the negative electrode active material is a particle in which Sn having an average particle diameter of 1 μm and SnO having an average particle diameter of 1 μm are mixed as a negative electrode active material other than a carbon material by mechanical milling (the number of Sn atoms: the number of O atoms = 2: 1). It was produced using. The other conditions were the same as in Example 1.

(Example 127)
The layer containing the negative electrode active material was prepared by using three vapor deposition sources of Si, SiO, and Fe corresponding to the element X as a negative electrode active material other than the carbon material, and forming a film by simultaneous vapor deposition (number of Si atoms : O atom number: Fe atom number = 14: 7: 6). The other conditions were the same as in Example 1.

(Example 128)
The layer containing the negative electrode active material is a particle in which Sn having an average particle diameter of 1 μm, SnO having an average particle diameter of 1 μm, and Fe having an average particle diameter of 1 μm are mixed by mechanical milling as a negative electrode active material other than a carbon material (number of Sn atoms: The number of O atoms: the number of Fe atoms = 14: 7: 6) was prepared, and then the particles and graphite particles having an average particle size of 10 μm were prepared using composite particles by mechanical milling. The other conditions were the same as in Example 1.

(Example 129)
The additive is compound no. 2 was used. The other conditions were the same as in Example 127.

(Example 130)
The additive is compound no. 3 was used. The other conditions were the same as in Example 127.

(Example 131)
The additive is compound no. 4 was used. The other conditions were the same as in Example 127.

(Example 132)
The additive is compound no. 6 was used. The other conditions were the same as in Example 127.

(Example 133)
The additive is compound no. 9 was used. The other conditions were the same as in Example 127.

(Example 134)
The additive is compound no. 10 was used. The other conditions were the same as in Example 127.

(Example 135)
The additive is compound no. 15 was used. The other conditions were the same as in Example 127.

(Example 136)
The additive is compound no. 16 was used. The other conditions were the same as in Example 127.

(Example 137)
The additive is compound no. 19 was used. The other conditions were the same as in Example 127.

(Example 138)
The layer containing the negative electrode active material was formed by using two vapor deposition sources of Si and SiO as the negative electrode active material other than the carbon material and forming a film by simultaneous vapor deposition (Si atom number: O atom number = 2: 1). The other conditions were the same as in Example 22.

(Example 139)
The layer containing the negative electrode active material was prepared by using two sputtering sources of Sn and SnO as the negative electrode active material other than the carbon material and forming a film by simultaneous sputtering (Sn atom number: O atom number = 2: 1). The other conditions were the same as in Example 22.

(Example 140)
The layer containing the negative electrode active material was prepared by using three vapor deposition sources of Si, SiO ₂ and Li as the negative electrode active material other than the carbon material, and formed by simultaneous vapor deposition (number of Si atoms: number of O atoms : Number of Li atoms = 1: 1: 1). The other conditions were the same as in Example 22.

(Example 141)
The layer containing the negative electrode active material was prepared by using three vapor deposition sources of Sn, SnO _2, and Li as the negative electrode active material other than the carbon material, and was formed by simultaneous vapor deposition (the number of Sn atoms: the number of O atoms : Number of Li atoms = 1: 1: 1). The other conditions were the same as in Example 22.

(Example 142)
The layer containing the negative electrode active material was prepared by mixing Si having an average particle diameter of 1 μm and SiO having an average particle diameter of 1 μm as a negative electrode active material other than the carbon material. The mixing ratio was such that the ratio of the number of Si atoms in Si having an average particle diameter of 1 μm and the number of molecules of SiO having an average particle diameter of 1 μm was 1: 1. The other conditions were the same as in Example 22.

(Example 143)
The layer containing the negative electrode active material is a particle in which Sn having an average particle diameter of 1 μm and SnO having an average particle diameter of 1 μm are mixed as a negative electrode active material other than a carbon material by mechanical milling (the number of Sn atoms: the number of O atoms = 2: 1). It was produced using. The other conditions were the same as in Example 22.

(Verification of the effect of the compound represented by the general formula (1))
The capacity retention ratios in Examples 1 to 10 are much higher than the capacity retention ratio of Comparative Example 1. This is compound no. 1, at least one element M ¹ (M ¹ is an element selected from Si, Sn, Al, Pb, Ag, Ge, and Sb) that occludes / releases alkali metal or alkaline earth metal as a negative electrode active material. In the case of the battery using the metal or metalloid and carbon material including the above, it is considered that the irreversible reaction is suppressed by the stabilization of the surface film present on the negative electrode surface and the high ion conductivity of the film. Moreover, the same tendency was seen also in Examples 11-19, and the effect by the compound shown by General formula (1) was confirmed. A similar tendency was observed in comparison between Examples 20 and 21 and Comparative Example 2 using amorphous carbon as the carbon material. The capacity retention rates of Examples 22 to 31 using LiMnO ₂ as the positive electrode active material are also shown in Compound No. Thus, it was confirmed that the same effect as in Example 1 was obtained.

  It can be seen that Examples 32 to 36 have a higher capacity retention rate during the cycle than Comparative Example 4. A similar tendency was observed in comparison between Example 37 and Comparative Example 5 using amorphous carbon as the carbon material. From this result, even in the case of a battery using the above metal or metalloid and carbon material and an element X not alloyed with an alkali metal or alkaline earth metal as a negative electrode active material, the same effect as in Example 1 is obtained. Was confirmed.

The capacity maintenance ratios in Examples 61 to 70 are much higher than the capacity maintenance ratio of Comparative Example 11. This is compound no. 1, in the case of a battery using an oxide or a carbon material that occludes / releases alkali metal or alkaline earth metal as a negative electrode active material, stabilization of the surface film existing on the negative electrode surface and high ionic conductivity of the film This is considered to be because the irreversible reaction was suppressed. Moreover, the same tendency was seen also in Examples 71-79, and the effect by the compound shown by General formula (1) was confirmed. A similar tendency was observed in comparison between Examples 80 and 81 and Comparative Example 12 using amorphous carbon as the carbon material. The capacity retention rates of Examples 82 to 91 using LiMnO ₂ as the positive electrode active material are also shown in Compound No. 1 and the capacity retention rate of Comparative Example 13 not including 1 was greatly exceeded, and it was confirmed that the same effect as Example 61 was obtained.

  It can be seen that Examples 92 to 96 have a higher capacity retention rate during the cycle than Comparative Example 14. A similar tendency was observed in comparison between Example 97 and Comparative Example 15 using amorphous carbon as the carbon material. From this result, it was carried out even in the case of a battery using an oxide and carbon material that occludes / releases alkali metal or alkaline earth metal and element X that does not alloy with alkali metal or alkaline earth metal as a negative electrode active material. It was confirmed that the same effect as in Example 61 was obtained.

The capacity maintenance rates in Examples 121 to 125 are significantly higher than the capacity maintenance rates of Comparative Examples 1 and 11. This is compound no. 1, in the case of a battery using a metal or metalloid and an oxide as a negative electrode active material and further using a carbon material, the stabilization of the surface film present on the negative electrode surface and the high ionic conductivity of the film, This may be because the irreversible reaction is suppressed. The capacity retention ratios of Examples 138 to 142 using LiMnO ₂ as the positive electrode active material are also shown in Compound Nos. 1 and the capacity retention rate of Comparative Examples 3 and 13 which do not include 1 was greatly exceeded, and it was confirmed that the same effect as Example 121 was obtained.

  It can be seen that Examples 126, 127, and 143 have a higher capacity retention rate during the cycle than Comparative Examples 4 and 14. From this result, even in the case of a battery using a metal or a semimetal and an oxide as a negative electrode active material, and further using a carbon material and an element X that does not alloy with an alkali metal or alkaline earth metal as a negative electrode active material. It was confirmed that the same effects as in Example 121 were obtained. Moreover, the same tendency was seen also in Examples 129-137, and the effect by the compound shown by General formula (1) was confirmed.

  Further, regarding the batteries prepared in Examples 1 and 61, when the surface of the negative electrode after the 400 cycle test was examined using X-ray photoelectron spectroscopy (XPS), there was a substance having a peak near 164 eV based on sulfur atoms. It was confirmed. In the system containing no additive, there was no substance having a peak near 164 eV, and in the system using only 1,3-PS, there was a substance having a peak near 164 eV. Was weak. Therefore, Compound No. 1 is preferentially formed.

(Verification of effects of adding cyclic sulfonate ester)
The capacity maintenance rate after the cycle test in Examples 38 to 40 was higher than that of Comparative Example 6, and the capacity maintenance rate after the cycle test in Examples 41 to 43 to which 1,3-PS was added was This is a further improvement over Examples 38-40. A similar tendency was also observed in Example 45 to which MMDS was added. This is because the irreversible reaction was further suppressed by the addition of cyclic sulfonate esters such as 1,3-PS and MMDS, and the further stabilization of the film on the negative electrode surface and the higher ion conductivity of the film. The reason is considered. However, when 1,3-PS is used alone as an additive as in Comparative Example 7, the effect of improving the capacity retention rate is not so great.

  The capacity maintenance rate after the cycle test in Examples 98 to 100 is higher than that of Comparative Example 16, and the capacity maintenance rate after the cycle test in Examples 101 to 103 to which 1,3-PS is added is This is a further improvement over Examples 98-100. A similar tendency was also observed in Example 105 to which MMDS was added. This is because the irreversible reaction was further suppressed by the addition of cyclic sulfonate esters such as 1,3-PS and MMDS, and the further stabilization of the film on the negative electrode surface and the higher ion conductivity of the film. The reason is considered. However, when 1,3-PS is used alone as an additive as in Comparative Example 17, the effect of improving the capacity retention rate is not so great.

(Verification of the effects of adding VC)
In the battery shown in Example 44, the capacity retention rate after the cycle test is further improved as compared with Example 43, that is, the cycle characteristics are improved by further adding VC to the electrolytic solution. Was confirmed. The reason for this is also considered to be the same as the reason when 1,3-PS is added.

  Compared to Example 103, the battery shown in Example 104 has a further improved capacity retention rate after a cycle test, that is, improved cycle characteristics by further adding VC to the electrolyte. Was confirmed. The reason for this is also considered to be the same as the reason when 1,3-PS is added.

(Verification of effects of concentration change of additive in electrolyte)
From Examples 46 to 51, the capacity retention after 400 cycles was determined as Compound No. There was a tendency for the concentration of 1 to decrease at concentrations of less than 0.1% by weight and greater than 5.0% by weight. In addition, the resistance increase rate tended to increase. From this result, it was confirmed that the concentration of the compound represented by the general formula (1) in the electrolytic solution is preferably 0.1% by mass or more and 5.0% by mass or less.

  From Examples 106-111, the capacity retention after 400 cycles was determined as Compound No. There was a tendency for the concentration of 1 to decrease at concentrations of less than 0.1% by weight and greater than 5.0% by weight. In addition, the resistance increase rate tended to increase. From this result, it was confirmed that the concentration of the compound represented by the general formula (1) in the electrolytic solution is preferably 0.1% by mass or more and 5.0% by mass or less.

(Verification when composite particles are used for the negative electrode active material)
The capacity retention ratio and resistance retention ratio after the cycle test in Examples 52 to 54 are higher than those in Comparative Example 9. From this result, it was confirmed that the same effect as in Example 1 was also obtained in the case of a battery using composite particles as the negative electrode active material.

  The capacity retention ratio and resistance retention ratio after the cycle test in Examples 112 to 114 are higher than those in Comparative Example 9. From this result, it was confirmed that the same effect as in Example 61 was obtained even in the case of a battery using composite particles as the negative electrode active material.

  The capacity retention rate and resistance retention rate after the cycle test in Example 128 are higher than those in Comparative Examples 9 and 19. From this result, it was confirmed that the same effect as in Example 121 was obtained even in the case of a battery using composite particles as the negative electrode active material.

(Verification when composite particles and graphite particles are used for the negative electrode active material)
The capacity retention ratio and resistance retention ratio after the cycle test in Examples 55 to 57 are higher than those in Comparative Example 10. From this result, it was confirmed that the same effect as in Example 1 was also obtained in the case of a battery using composite particles as the negative electrode active material.

  The capacity retention ratio and resistance retention ratio after the cycle test in Examples 115 to 117 are higher than those in Comparative Example 20. From this result, it was confirmed that the same effect as in Example 61 was obtained even in the case of a battery using composite particles as the negative electrode active material.

(Verification of effects due to differences in carbon material content)
It was confirmed that the results of Example 1 (carbon material content: 50% by mass) and Examples 58 (5% by mass) and 59 (95% by mass) are all good.

  The results of Example 61 (carbon material content: 50% by mass) and Examples 118 (5% by mass) and 119 (95% by mass) were all confirmed to be good.

(Verification of effects of carbon material film formation method)
It was confirmed that the results of Example 1 (coating method) and Example 60 (sputtering method) were good.

  The results of Example 61 (application method) and Example 120 (sputtering method) were both confirmed to be good.

Claims (52)

In a secondary battery comprising at least a positive electrode, a negative electrode, and an electrolyte solution,
The negative electrode contains, as a negative electrode active material, a metal or a semimetal or oxide that absorbs and releases alkali metal or alkaline earth metal, and a carbon material, and
The said electrolyte solution contains the aprotic solvent by which the electrolyte was melt | dissolved at least, and the compound shown by following General formula (1), The secondary battery characterized by the above-mentioned.

(However, in the said General formula (1), R < ₁ > and R < ₄ > are respectively independently a hydrogen atom, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C1-C5. An alkoxy group, a substituted or unsubstituted fluoroalkyl group having 1 to 5 carbon atoms, a polyfluoroalkyl group having 1 to 5 carbon atoms, —SO ₂ X ₁ (X ₁ is a substituted or unsubstituted carbon atom having 1 to 5 carbon atoms, Alkyl group), -SY ₁ (Y ₁ is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms), -COZ (Z is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms), And R ₂ and R ₃ each independently represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted carbon group having 1 to 5 carbon atoms. An alkoxy group, Or an unsubstituted phenoxy group, a substituted or unsubstituted fluoroalkyl group having 1 to 5 carbon atoms, a polyfluoroalkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted fluoroalkoxy group having 1 to 5 carbon atoms, a carbon number 1-5 polyfluoroalkoxy group, a hydroxyl group, a halogen _atom, -NX ₂ X 3 _{(X 2} and _{X 3} are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms) , and _{-NY 2 CONY 3 Y 4 (Y} 2 ~Y 4 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms) shows a atom or a group selected from. ) At least an element M ¹ (M ¹ is an element selected from Si, Sn, Al, Pb, Ag, Ge, and Sb) that occludes and releases alkali metal or alkaline earth metal as the negative electrode active material as the negative electrode. The secondary battery according to claim 1, comprising a metal or a semimetal including at least one kind and a carbon material.   3. The secondary battery according to claim 2, wherein the negative electrode active material contained in the negative electrode further contains an element X that does not alloy with an alkali metal or an alkaline earth metal.   4. The secondary battery according to claim 3, wherein the element X is an element selected from Fe, Ni, Cu, and Ti. 5. The secondary battery according to claim 3, wherein a ratio of the element M ¹ and the element X is an atomic ratio of element M ¹ : element X = 19: 1 to 1: 9.   The carbon material is at least one selected from graphite, amorphous carbon, carbon nanotube, carbon nanohorn, fullerene, diamond-like carbon, soft carbon, hard carbon, and a mixture thereof. The secondary battery in any one of -5.   The secondary battery according to claim 2, wherein a content of the carbon material with respect to the whole of the negative electrode active material is 5 to 95 mass%.   The secondary battery according to claim 2, wherein the negative electrode active material includes particles containing at least one of the metal or metalloid and the carbon material.   The secondary battery according to claim 8, wherein the particles are composite particles containing both the metal or metalloid and the carbon material.   The secondary battery according to claim 9, wherein the composite particles are obtained by coating at least a part of the periphery of the metal or metalloid particles with the carbon material.   The secondary battery according to claim 9, wherein the composite particles are obtained by coating at least a part of the periphery of the carbon material particles with the metal or metalloid.   The secondary battery according to claim 8, wherein a surface of the particle is coated with a carbon film.   The secondary battery according to claim 2, wherein the negative electrode active material is formed by a vacuum film formation method or a pressure contact method.   The secondary battery according to claim 13, wherein the vacuum film forming method is any one of a vacuum deposition method, a sputtering method, and a CVD method.   The secondary battery according to claim 13, wherein the pressure welding method is a mechano-fusion method or a mechanical milling method.   The secondary battery according to claim 2, wherein the negative electrode has a layer formed by a coating method or a vacuum film-forming method, containing at least a part of the negative electrode active material.   The negative electrode active material forms a layered structure having a layer containing the metal or metalloid as a main component and a layer containing the carbon material as a main component. A secondary battery according to any one of the above.   The compound represented by the general formula (1) is contained in the electrolytic solution in an amount of 0.1 to 5.0% by mass with respect to the total mass of the electrolytic solution. A secondary battery according to any one of the above. The secondary battery according to claim 2, wherein the electrolytic solution further contains a cyclic monosulfonic acid ester represented by the following general formula (2).

(However, in the general formula (2), n is 0 to 2 integer. _Also, R 5 _{to R 10} each independently represent a hydrogen atom, a substituted or unsubstituted 1 to 12 carbon atoms An atom or group selected from an alkyl group, a substituted or unsubstituted fluoroalkyl group having 1 to 6 carbon atoms, and a polyfluoroalkyl group having 1 to 6 carbon atoms. The secondary battery according to claim 2, wherein the electrolytic solution further includes a cyclic sulfonic acid ester having two sulfonyl groups represented by the following general formula (3).

(However, in the said General formula (3), Q is an oxygen atom, a methylene group, or a single bond, A is a substituted or unsubstituted C1-C5 alkylene group, a carbonyl group, a sulfinyl group, C1-C5. At least one C—C bond in the polyfluoroalkylene group, a substituted or unsubstituted fluoroalkylene group having 1 to 5 carbon atoms, or a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms is a C—O—C bond A group in which at least one C—C bond in the polyfluoroalkylene group having 1 to 5 carbon atoms is a C—O—C bond, and a substituted or unsubstituted fluoroalkylene having 1 to 5 carbon atoms A group selected from a group in which at least one C—C bond in the group is a C—O—C bond, B is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, carbon number 5 of polyfluoroalkylene group, and a substituted or unsubstituted fluoroalkylene group having 1 to 5 carbon atoms, a group selected from shown.)   21. The secondary battery according to claim 2, wherein the electrolytic solution further contains at least one of vinylene carbonate and a derivative thereof.   The secondary battery according to claim 2, wherein the electrolyte contains a lithium salt. The lithium salt is LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiSbF ₆ , LiClO ₄ , LiAlCl ₄ , and LiN (C _k F _{2k + 1} SO ₂ ) (C _m F _{2m + 1} SO ₂ ) (k and m are independent of each other) The secondary battery according to claim 22, wherein the secondary battery is at least one lithium salt selected from the group consisting of 1 and 2).   The aprotic solvent is at least selected from the group consisting of cyclic carbonates, chain carbonates, aliphatic carboxylic acid esters, γ-lactones, cyclic ethers, chain ethers and their fluorinated derivatives. The secondary battery according to claim 2, wherein the secondary battery is an organic solvent.   The secondary battery according to claim 2, wherein the secondary battery is covered with a laminate outer package. The secondary battery according to claim 1, wherein the negative electrode contains, as a negative electrode active material, an oxide that absorbs and releases alkali metal or alkaline earth metal and a carbon material. The oxide is an element ^M 2 ^{(M 2} is Si, Sn, Al, Pb, Ag, Ge, Sb, B, P, from elements selected from W and Ti) in claim 26, characterized in that it comprises The secondary battery as described.   28. The secondary battery according to claim 27, wherein the negative electrode active material included in the negative electrode further includes an element X that does not alloy with an alkali metal or an alkaline earth metal.   29. The secondary battery according to claim 28, wherein the element X is an element selected from Fe, Ni, Cu and Ti. The ratio of the element ^{M 2} and the element X, the element ^{M 2} in atomic ratio: element X = 19: 1 to 1: 9 secondary battery according to claim 28 or 29, wherein the a.   27. The secondary battery according to claim 26, wherein the negative electrode active material contained in the negative electrode further contains an element X that does not alloy with an alkali metal or an alkaline earth metal. The element X, Fe, Ni, secondary battery according to claim 31, wherein it is an element selected from Cu and Ti.   27. The carbon material is at least one selected from graphite, amorphous carbon, carbon nanotube, carbon nanohorn, fullerene, diamond-like carbon, soft carbon, hard carbon, and a mixture thereof. 32. The secondary battery according to any one of -32.   The secondary battery according to any one of claims 26 to 33, wherein a content of the carbon material with respect to the whole of the negative electrode active material is 5 to 95 mass%.   The secondary battery according to claim 26, wherein the negative electrode active material includes particles containing at least one of the oxide and the carbon material.   36. The secondary battery according to claim 35, wherein the particles are composite particles containing both the oxide and the carbon material.   37. The secondary battery according to claim 36, wherein the composite particles are obtained by coating at least a part of the periphery of the oxide particles with the carbon material.   37. The secondary battery according to claim 36, wherein the composite particles are obtained by coating at least a part of the periphery of the particles of the carbon material with the oxide.   The secondary battery according to any one of claims 35 to 38, wherein a surface of the particle is coated with a carbon film.   The secondary battery according to any one of claims 26 to 39, wherein the negative electrode active material is formed by a vacuum film formation method or a pressure contact method.   41. The secondary battery according to claim 40, wherein the vacuum film forming method is any one of a vacuum vapor deposition method, a sputtering method, and a CVD method.   The secondary battery according to claim 40, wherein the pressure welding method is a mechano-fusion method or a mechanical milling method.   43. The secondary battery according to any one of claims 26 to 42, wherein the negative electrode has a layer formed by a coating method or a vacuum film-forming method containing at least a part of the negative electrode active material.   The negative electrode active material forms a layered structure having a layer mainly composed of the oxide and a layer mainly composed of the carbon material. Secondary battery described in 1.   45. The compound represented by the general formula (1) is contained in the electrolytic solution in an amount of 0.1 to 5.0% by mass with respect to the total mass of the electrolytic solution. A secondary battery according to any one of the above. The secondary battery according to any one of claims 26 to 45, wherein the electrolytic solution further contains a cyclic monosulfonic acid ester represented by the following general formula (2).

(However, in the general formula (2), n is 0 to 2 integer. _Also, R 5 _{to R 10} each independently represent a hydrogen atom, a substituted or unsubstituted 1 to 12 carbon atoms An atom or group selected from an alkyl group, a substituted or unsubstituted fluoroalkyl group having 1 to 6 carbon atoms, and a polyfluoroalkyl group having 1 to 6 carbon atoms. 47. The secondary battery according to claim 26, wherein the electrolytic solution further contains a cyclic sulfonic acid ester having two sulfonyl groups represented by the following general formula (3).

(However, in the said General formula (3), Q is an oxygen atom, a methylene group, or a single bond, A is a substituted or unsubstituted C1-C5 alkylene group, a carbonyl group, a sulfinyl group, C1-C5. At least one C—C bond in the polyfluoroalkylene group, a substituted or unsubstituted fluoroalkylene group having 1 to 5 carbon atoms, or a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms is a C—O—C bond A group in which at least one C—C bond in the polyfluoroalkylene group having 1 to 5 carbon atoms is a C—O—C bond, and a substituted or unsubstituted fluoroalkylene having 1 to 5 carbon atoms A group selected from a group in which at least one C—C bond in the group is a C—O—C bond, B is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, carbon number 5 of polyfluoroalkylene group, and a substituted or unsubstituted fluoroalkylene group having 1 to 5 carbon atoms, a group selected from shown.)   48. The secondary battery according to claim 26, wherein the electrolytic solution further contains at least one kind of vinylene carbonate and a derivative thereof.   The secondary battery according to any one of claims 26 to 48, wherein the electrolyte contains a lithium salt. The lithium salt is LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiSbF ₆ , LiClO ₄ , LiAlCl ₄ , and LiN (C _k F _{2k + 1} SO ₂ ) (C _m F _{2m + 1} SO ₂ ) (k and m are independent of each other) The secondary battery according to claim 49, wherein the secondary battery is at least one lithium salt selected from the group consisting of 1 and 2).   The aprotic solvent is at least selected from the group consisting of cyclic carbonates, chain carbonates, aliphatic carboxylic acid esters, γ-lactones, cyclic ethers, chain ethers and their fluorinated derivatives. 51. The secondary battery according to claim 26, wherein the secondary battery is an organic solvent.   The secondary battery according to any one of claims 26 to 51, wherein the secondary battery is covered with a laminate outer package.

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