WO2005057715A1

WO2005057715A1 - Secondary battery

Info

Publication number: WO2005057715A1
Application number: PCT/JP2004/018715
Authority: WO
Inventors: Mariko Miyachi; Koji Utsugi; Yuki Kusachi; Hironori Yamamoto
Original assignee: Nec Corporation
Priority date: 2003-12-15
Filing date: 2004-12-15
Publication date: 2005-06-23
Also published as: JPWO2005057715A1; JP4951969B2

Abstract

The present invention aims to provide a lithium secondary battery with excellent characteristics such as energy density and electromotive force, which is also excellent in cycle life and shelf life stability. Disclosed is a secondary battery comprising at least a positive electrode, a negative electrode and an electrolyte solution wherein the negative electrode contains a metal, metalloid or oxide, which adsorbs/desorbs an alkali metal or alkaline earth metal, and a carbon material as the negative electrode active material, and the electrolyte solution contains a non-protic solvent wherein at least an electrolyte is dissolved and a chain disulfone compound.

Description

Specification

Rechargeable battery

Technical field

The present invention relates to a secondary battery.

Background art

[0002] Non-aqueous electrolyte lithium-ion or lithium secondary batteries that use a carbon material or lithium metal for the negative electrode and a lithium-containing composite oxide for the positive electrode can achieve high energy densities, and are used for mobile phones and notebook computers. It is attracting attention as a power source. In this secondary battery, it is generally known that a film called a surface film, a protective film, or an SE film is formed on the surface of the electrode. It is known that control of the surface film is indispensable for improving the performance of the electrode, since the surface film has a large effect on charge / discharge efficiency, cycle life, and safety. In other words, when a carbon material is used as the negative electrode material, its irreversible capacity needs to be reduced. In the case of a lithium metal negative electrode, it is necessary to solve the problems of reduction in charge / discharge efficiency and safety due to dendrite generation.

[0003] Various methods have been proposed as methods for solving these problems. For example, when lithium metal is used as a negative electrode material, it has been proposed to suppress the generation of dendrite by providing a film layer made of lithium fluoride or the like by using a chemical reaction on the surface thereof. .

[0004] Patent Document 1 discloses a technique in which a lithium negative electrode is exposed to an electrolytic solution containing hydrofluoric acid, and the surface of the negative electrode is reacted with hydrofluoric acid to cover the surface with a lithium fluoride film. Have been. Hydrofluoric acid is produced by the reaction of LiPF and a small amount of water. Meanwhile, Lichi

6

A surface film of lithium hydroxide or lithium oxide is formed on the surface of the negative electrode by natural oxidation in air. These react to form a surface film of lithium fluoride on the surface of the negative electrode. However, this lithium fluoride film is formed by utilizing the reaction between the electrode interface and the liquid, and it is difficult to obtain a uniform film as soon as side reaction components are mixed in the surface film. There was a case. In addition, there are cases where the surface film of lithium hydroxide or lithium oxide is not formed uniformly, or where there is a part where lithium is exposed. In these cases, a uniform thin film cannot be formed in these cases, and a safety problem has arisen due to the reaction of lithium with water or hydrogen fluoride. In addition, when the reaction is insufficient, unnecessary compound components other than the fluoride remain, which may cause adverse effects such as a decrease in ionic conductivity. Further, 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 high yield. There was a case.

[0005] In Patent Document 2, a mixed gas of argon and hydrogen fluoride is reacted with an aluminum-lithium alloy to obtain a lithium fluoride surface film on the negative electrode surface. However, when a surface film already exists on the surface of the lithium metal, especially when there are a plurality of types of compounds, the reaction tends to be uneven, and it is difficult to form a uniform film of lithium fluoride. There was a case. In this case, it is difficult to obtain a lithium secondary battery having sufficient cycle characteristics.

[0006] Patent Document 3 discloses that a surface film structure mainly composed of a material having a rock salt type crystal structure is formed on a surface of a lithium sheet having a uniform crystal structure, that is, a (100) crystal plane is preferentially oriented. A technique for performing this is disclosed. By doing so, a uniform precipitation-dissolution reaction, that is, charging and discharging of the battery can be performed, dendrite deposition of lithium metal can be suppressed, and the cycle life of the battery can be improved. As the substance used for the surface film, it is preferable to use a solid solution of at least one selected from the group consisting of LiCl, LiBr, and Lil, which preferably has a halide of lithium, and LiF. Has been stated. Specifically, in order to form a solid solution film of LiF and at least one selected from the group consisting of LiCl, LiBr and Lil, a (100) crystal plane formed by pressing (rolling) has priority. A lithium sheet oriented in a non-aqueous state is immersed in an electrolytic solution containing at least one of chlorine molecules or chloride ions, bromine molecules or bromine ions, iodine molecules or iodine ions, and fluorine molecules or fluorine ions to thereby obtain non-aqueous solution. We are making negative electrodes for electrolyte batteries. In the case of this technology, a rolled lithium metal sheet is used, and since the lithium sheet is easily exposed to the air, the existence of active sites where a film derived from moisture or the like is easily formed on the surface becomes nonuniform. In some cases, it was difficult to produce a stable surface film having a uniform thickness, and in this case, the effect of suppressing dendrites was not always sufficiently obtained. [0007] In addition, there has been reported a technology relating to improvement in capacity and charge / discharge efficiency when a carbon material such as graphite or hard carbon capable of occluding and releasing lithium ions is used as a negative electrode.

[0008] Patent Document 4 proposes a negative electrode in which a carbon material is coated with aluminum. This allegedly suppresses the reductive decomposition of the solvent molecules solvated with lithium ions on the carbon surface, thereby suppressing the deterioration of the cycle life. However, since aluminum reacts with a very small amount of water, the capacity may decrease rapidly when the cycle is repeated.

[0009] Patent Document 5 discloses a negative electrode in which a surface of a carbon material is coated with a thin film of a lithium ion conductive solid electrolyte. As a result, the decomposition of the solvent that occurs when a carbon material is used is suppressed, and in particular, a lithium ion secondary battery that can use propylene carbonate can be provided. However, cracks that occur in the solid electrolyte due to stress changes during the insertion and desorption of lithium ions sometimes lead to characteristic deterioration. In addition, due to non-uniformity such as crystal defects of the solid electrolyte, a uniform reaction was not obtained on the negative electrode surface, which sometimes led to a deterioration in cycle life.

[0010] Further, in Patent Document 6, the negative electrode is made of a material containing graphite, and has a cyclic carbonate and a chain carbonate as main components as an electrolytic solution, and 0.1 to 4 mass% in the electrolytic solution. Disclosed is a secondary battery that contains 1,3-propane sultone and / or 1,4-butane sultone, which are less than or equal to 1% of a cyclic monosulfonic acid ester. Here, 1,3_propane sultone and 1,4-butane sultone contribute 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 and artificial graphite is used as a passive film. It is considered to have the effect of suppressing the decomposition of the electrolyte solution without impairing the normal reaction of the battery by coating. Patent Documents 7 and 8 report that similar effects can be obtained by using a linear disulfonate ester in addition to the cyclic monosulfonate ester. However, the cyclic monosulfonic acid ester of Patent Document 6 or the chain disulfonic acid ester of Patent Documents 7 and 8 mainly forms a film on the negative electrode, for example, a film is formed on the positive electrode. Sometimes it was difficult.

[0011] Patent Documents 9 and 10 disclose a method for producing a cyclic sulfonic acid ester having two sulfonyl groups, and Non-Patent Documents 14 to 14 disclose a method for producing a chain disulfonic acid ester. . [0012] In Patent Document 11, by adding an aromatic compound to an electrolyte solution solvent, oxidation of the electrolyte solution solution is prevented, thereby suppressing the capacity deterioration of the secondary battery when the charge and discharge are repeated for a long time. . 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 effect of improving the cycle characteristics may not be sufficient because the surface of the positive electrode is not covered in some cases.

[0013] Patent Document 12 describes a technique for improving the 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 improved the charge and discharge efficiency of the negative electrode, it did not improve the charge and discharge efficiency of the positive electrode.

[0014] In addition to the case where the above-mentioned 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, an electrode using only silicon absorbs an alkali metal or the like. When released, the volume expands and contracts to about four times, and when the volume expansion becomes large, the active material becomes fine powder or a current collector. Since the adhesion to the electrode is lost or the electrode surface is oxidized, the solid solution using copper or the like reduces the amount of occlusion of alkali metals and the like, and the active material is pulverized. It is said that the volume expansion and contraction of the active material can be controlled so as not to occur.

[0015] As a negative electrode active material, a method of using a metal or a semimetal that absorbs and releases an alkali metal or an alkaline earth metal such as lithium and a carbon material has been studied. Patent Document 14 reports a negative electrode material comprising a metal or metalloid particle nucleus capable of forming a lithium alloy and a carbon layer covering the surface thereof.

[0016] As an anode active material, a method of using an oxide and a carbon material that occlude and release an alkali metal such as lithium or an alkaline earth metal has been studied. Patent Document 15 has an oxide particle and a carbonaceous material particle containing at least one element selected from Si, Sn, Ge, Al, Zn, Bi, and Mg, and the oxide particle is a carbonaceous material. The negative electrode active material carried in the particles has been reported.

Patent Document 1: JP-A-7-302617

Patent Document 2: JP-A-8-250108 Patent Document 3: JP-A-11-288706

Patent Document 4: Japanese Patent Application Laid-Open No. Hei 5-2344583

Patent Document 5: JP-A-5-275077

Patent Document 6: JP-A-2000-3724

Patent Document 7: JP-A-2000-133304

Patent Document 8: US Patent No. 6436582

Patent Document 9: Japanese Patent Publication No. 5-44946

Patent Document 10: U.S. Pat.No. 4,950,768

Patent Document 11: JP-A-2003-7334

Patent Document 12: JP 2003-115324 A

Patent Document 13: JP-A-2002-075350

Patent Document 14: JP-A-2000-215887

Patent Document 15: JP-A-2000-243396

Non-Patent Document 1: J. Am. Pham. Assoc., Vol. 126, pp. 485-493, 1937 Non-Patent Document 2: G. Schroeter, Lieb, Ann, Der Chemie, Vol. 418, 161- 257 pages, 1919

Non-Patent Document 3: Biol. Aktiv. Soedin., Ρρ64_69 (1968).

Non-Patent Document 4: Armyanskii Khimicheskii Zhurnal, 21, pp393-396 (1968).

Problems to be solved by the invention

[0017] The above prior arts have the following common problems.

[0018] The surface film formed on the electrode surface is closely related to the charge / discharge efficiency, cycle life, and safety by its properties, but there is no method capable of controlling the film for a long time. For example, when a surface film made of a lithium halide or a glassy oxide is formed on a layer made of lithium, the effect of suppressing dentite can be obtained to a certain extent during initial use. Was deteriorated and the function as a protective film was sometimes reduced. This is because while the layer made of lithium changes its volume by absorbing and releasing lithium, the layer of lithium halide or the like located above it changes its volume. It is thought that the internal stress is generated in these layers and their interfaces because the coatings made of them hardly change in volume. It is considered that the generation of such an internal stress particularly damages a part of the surface film made of lithium halide or the like, and reduces the function of suppressing dendrite.

[0019] When a carbon material such as graphite is used for the negative electrode, the charge due to the decomposition of the solvent molecule or the anion appears as an irreversible capacity component, which may lead to a decrease in the initial charge / discharge efficiency. In addition, the composition, crystal state, stability, and the like of the film generated at this time greatly affect the subsequent efficiency and cycle life. In this way, studies have been conducted to improve the charge / discharge efficiency and the life of the batteries by forming a film on the electrodes for secondary batteries, but generally sufficient battery characteristics have not yet been obtained. Absent.

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

Here, the use of a metal, metalloid, or oxide that absorbs and 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 higher capacity can be achieved than when used as a substance, it is expected as a method to realize small and light batteries. However, the above-mentioned metal, metalloid, or oxide has a problem in that the battery has a large volume expansion and contraction due to charge and discharge, and has insufficient cycle characteristics of the obtained battery. That is, cracks and the like may be formed in the SEI formed on the surface due to the stress caused by the expansion and contraction of the volume. If 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 to cause oxidative deterioration of the negative electrode active material. Carbon materials are expected to have an improved conductivity and a cushion effect against the volume change caused by the charge / discharge of the metal, metalloid, or oxide, but the cushion effect of the carbon material alone is not sufficient. Cannot prevent the occurrence of cracks. Therefore, sufficient battery characteristics have not yet been obtained for such a metal or metalloid or oxide and carbon material as a negative electrode active material.

[0022] The present invention has been made in view of the above-mentioned problems, and has a negative electrode active material such as lithium. Stable on the electrode surface by adding chain-like disulfonate to the electrolyte of secondary batteries using metals or metalloids, oxides and carbon materials that occlude and release alkali metals or alkaline earth metals This prevents the decomposition of solvent molecules by forming a coated film. As a result, RCR II is aimed at obtaining a secondary battery with excellent cycle characteristics and charge / discharge efficiency.

Four

OH HH means to solve the problem

[0023] In order to solve the above problems, the present invention has the following configurations. That is, the present invention provides a secondary battery including at least a positive electrode, a negative electrode, and an electrolytic solution,

The negative electrode contains, as a negative electrode active material, a metal or a metalloid or an oxide that occludes and releases an alkali metal or an alkaline earth metal, and a carbon material, and

The secondary battery is characterized in that the electrolytic solution contains at least an aprotic solvent in which an electrolyte is dissolved and a compound represented by the following general formula (1).

[0024] [Formula 1]

(1)

(However, in the above general formula (1), R and R are each independently a hydrogen atom,

14

Substituted or unsubstituted alkyl group having 15 carbon atoms, substituted or unsubstituted alkoxy group having 15 carbon atoms, substituted or unsubstituted fluoroalkyl group having 15 carbon atoms, polyfluoro group having 15 carbon atoms Alkyl group, —SO X (X is a substituted or unsubstituted carbon atom 1

--15 alkyl groups), --SY (Y is a substituted or unsubstituted alkyl group having 15 carbon atoms), --COZ (Z is a hydrogen atom or a substituted or unsubstituted alkyl group having 15 carbon atoms) Group), and a halogen atom, a selected atom or group. R and R are each independently

twenty three

Substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, substituted or unsubstituted alkyl group having 1 to 5 carbon atoms An alkoxy group, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted fluoroalkyl group having 15 carbon atoms, a polyfluoroalkyl group having 15 carbon atoms, a substituted or unsubstituted A chloroalkoxy group, a polyfluoroalkoxy group having 115 carbon atoms, a hydroxyl group, a halogen atom,-NX ^ X ¹ and X ² each independently represent a hydrogen atom or a substituted or unsubstituted carbon atom 5 alkyl groups) and one NY CONY ^^ X ¹ -X ³ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 15 carbon atoms), Show. )

[0026] In the present specification, "polyfluoroalkylene group", "polyfluoroalkyl group", and "polyfluoroalkoxy group" are bonded to carbon atoms of the corresponding alkylene group, alkyl group, and alkoxy group, respectively. Represents all hydrogen atoms replaced by fluorine atoms, `` fluoroalkylene group '', `` fluoroalkyl group '', `` fluoroalkoxy group '' is the carbon atom of the corresponding alkylene group, alkyl group, alkoxy group respectively It represents one in which part of the bonded hydrogen atoms has been replaced by fluorine atoms.

In the “substituted fluoroalkylene group”, “substituted fluoroalkyl group”, and “substituted fluoroalkoxy group”, “substitution” means that at least one of the hydrogen atoms bonded to the carbon atom is an atom other than fluorine or It means that it is substituted by a functional group. Examples of the atom or functional group other than fluorine include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, a hydroxyl group, an alkoxy group having 15 to 15 carbon atoms, or a halogen atom or a hydroxyl group. Or a group in which one SO — is introduced into these groups (eg, -OSO C

twenty two

H 2 SO 2 C1). When a carbon atom is contained in this functional group, this carbon atom is not included in the number of "C15-C5" in the description such as "Substituted or unsubstituted alkyl group of C15" And

The invention's effect

According to the present invention, by using an electrolyte solution for a secondary battery in which the linear disulfone conjugate according to the present invention is contained in an aprotic solvent, an alkali metal such as lithium can be used as a negative electrode active material. Even when a metal or metalloid, oxide or carbon material that absorbs or releases alkaline earth metal is used, the resulting secondary battery has excellent charge / discharge efficiency, good cycle characteristics, and capacity retention. An excellent lithi that can suppress the rise in resistance during storage with high rate A secondary battery can be obtained.

Brief Description of Drawings

FIG. 1 is a schematic configuration diagram of a secondary battery according to the present invention.

[2] metal containing element M ¹ or metalloid is a schematic diagram showing a state of composite is coated with a carbon material.

3 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.

FIG. 4 is a schematic diagram showing a state in which an oxide is covered with a carbon material to form a composite.

FIG. 5 is a schematic diagram showing a state in which a carbon material is covered with an oxide to form a composite. Explanation of symbols

[0030] 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 Non-aqueous electrolyte solution

16 Porous separator

2a, 3a Carbon material

2b, the metal or metalloid containing 3b element M ¹

2c, 3c oxide

BEST MODE FOR CARRYING OUT THE INVENTION

(Description of Battery Configuration According to the Present Invention)

FIG. 1 shows a schematic structure of an example of the battery according to the present invention. A positive electrode current collector 11; a layer 12 containing a positive electrode active material capable of absorbing and releasing lithium ions; a layer 13 containing a negative electrode active material capable of absorbing and releasing lithium ions; a negative electrode current collector 14; It is composed of a liquid 15 and a separator 16 containing the liquid. Here, the chain disulfonate compound (chain disulfonate) represented by the general formula (1) is contained in the electrolytic solution 15.

[0032] (Current collector)

The positive electrode current collector 11 may be made of aluminum, stainless steel, nickel, titanium or any of these. An alloy or the like can be used, and as the negative electrode current collector 14, copper, stainless steel, nickel, titanium, or an alloy thereof can be used.

[0033] (Separator)

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

[0034] (Positive electrode)

As the positive electrode active material, a commonly used lithium-containing composite oxide is used. Specifically, LiMO (M is selected from Mn, Fe, Co, and a part thereof is other cations such as Mg, Al, Ti)

2

And a material such as LiMnO can be used. Selected cathode active material

twenty four

And kneading with a conductive material such as carbon black and a binder such as polyvinylidene fluoride (PVDF) in a solvent such as N-methyl-2-pyrrolidone (NMP), The layer 12 to be the positive electrode can be obtained by a method such as coating on the top.

(Negative electrode)

In the present invention, as the negative electrode active material contained in the negative electrode, a metal or metalloid, an oxide, and a carbon material that occlude and release an alkali metal or an alkaline earth metal such as lithium are used.

[0036] Examples of the metal or metalloid, element M ¹ (M ¹ is Si, Sn, Al, Pb, Ag, Ge and from elements selected from S b) using a metal or metalloid and at least one more . As the metals or semimetals, 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 two or more even one But it's fine. When containing the element M ¹ 2 or more, these elements may include a state of even good tool alloys contain respectively metals or semi-metallic state. Among them, a metal or metalloid containing an element selected from Si, Sn and A1 is preferably used, and a metal or metalloid containing at least one of Si and Sn is more preferably used.

[0037] As the oxide, an oxide that can be alloyed with an alkali metal or an alkaline earth metal can be used, and an element M ² (M ² is Si, Sn, Al , Pb, Ag, Ge, Sb, B, P, W, and Ti). Acid contained in this oxide For elements other than element, one or two or more elements are good. Two or more oxides can be used in combination. Above all, it is preferable to use an oxide containing an element selected from Si, Sn, Al, Pb, Ag, Ge and Sb, and it is more preferable to use an oxide containing at least one of Si and Sn. Sile,. The composition of the oxide may be stoichiometry or non-stoichiometry.

[0038] A metal or semimetal and an oxide can be used in combination. In particular, the above element M ¹

(M ¹ is an element selected from Si, Sn, Al, Pb, Ag, Ge, and Sb) and a metal or metalloid containing at least one of the above-mentioned metals and earth metal. It is preferable to use together with an alloyable oxide.

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 kind or two or more kinds. It is preferable to use at least one of graphite and amorphous carbon. The content of the carbon material with respect 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 more preferably in the range of 30 to 60% by mass. Is more preferable. The carbon material is expected to improve conductivity and exhibit a cushioning effect against a volume change caused by charge / discharge of the metal or metalloid or oxide.

[0040] The use of a metal, metalloid, oxide, or carbon material as the negative electrode active material as described above has a higher capacity than when only a carbon material such as amorphous carbon is used as the negative electrode active material. Therefore, it is expected as a technique for realizing small and lightweight batteries. However, the above-mentioned metals, metalloids and oxides have a large volume expansion and contraction due to charge and discharge, and although the cushioning effect of a carbon material can be expected, the cycle characteristics of the obtained batteries are still insufficient. As in the present invention, by using an additive represented by the general formula (1) described below in combination, even if cracks or the like enter the SEI formed on the surface due to stress due to expansion and contraction of the volume, the film can be formed quickly. It is considered that the consumption of the solvent of the electrolytic solution is suppressed due to the formation of. That is, this can prevent gas generation due to solvent decomposition. In addition, since the formation of the film also interrupts the supply of oxygen to the surface, it is considered that the deterioration of the active material due to oxidation is also suppressed. As a result, the battery of the present invention can be obtained by using the above-mentioned metal or metalloid or oxide, and carbon material as a negative electrode active material. It is considered that good cycle characteristics were obtained.

In the present invention, the negative electrode active material contained in the negative electrode contains an element X that is not alloyed with an alkali metal or an alkaline earth metal, in addition to the above-mentioned metal, metalloid, or element contained in the oxide. You can also. These elements X are effective in suppressing the volume change due to charge / discharge of the negative electrode active material and improving the conductivity. 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 an element selected from Fe, Ni, Cu, and Ti. These elements X may be present in any state as long as they do not alloy with the alkali metal or alkaline earth metal. However, for example, the Ti element cannot be alloyed with an alkali metal or an alkaline earth metal in a metal state, but may be alloyable with an alkali metal or an alkaline earth metal in an oxide state. The Ti element in the alloyed state shall not be classified as this element X (for example, Li Ti O

Ti element in the state of 4 51). The element X contained in the negative electrode active material may be one or more.

2

It can be on. When two or more elements X are contained in the negative electrode active material, each of those elements may be contained in the form of a metal or metal compound, or may be contained in the form of an alloy or alloy compound. Further, it may be in a state of being alloyed with the above-mentioned metal, metalloid or oxide.

[0042] an anode active the element M ¹ (M ¹ is Si, Sn, Al, Pb, Ag, from elements selected from Ge and Sb) comprising a metal or metalloid containing both one or more less, the element X for materials, the ratio of the element M ¹ and the element X, the element M ¹ in atomic ratio: element X = 19: 1-1: is preferably 9. If the amount of the element X is too large, the ratio of the metal or metalloid involved in charge / discharge decreases, and therefore the volume energy density and the weight energy density of the negative electrode tend to decrease.If the amount of the element X is too small, the element X There is a tendency that the effect of adding, that is, the effect of suppressing the volume change due to the charge and discharge of the negative electrode active material and the effect of improving the conductivity is reduced. More preferably, the atomic ratio of the elements is M ¹ : element X = 14: l 3: 7, and still more preferably, the element M ¹ : element X = 9: 1-5: 5.

[0043] the element and oxide containing M ^2, of the negative electrode active material containing the above element X case, the element M ² and the ratio of the element X, the element M ² in atomic ratio: element X = 19: 1 -Preferably 1: 9. If the element X is too large, the proportion of oxides involved in charge and discharge will decrease, The volume energy density and the weight energy density tend to decrease.If the element X is too small, the effect of adding the element X, that is, the suppression of the volume change due to the charge and discharge of the negative electrode active material and the improvement in conductivity. The effect tends to be small. More preferably, the element ratio is the element M ² : element X = 14: 1-3: 7, and further preferably, the element M ² : element X = 9: 1-15: 5.

[0044] 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.

[0045] The negative electrode active material may be in a form containing particles containing at least one of the above-mentioned metal, metalloid or oxide, and the above-mentioned carbon material. Particles containing both the metal or metalloid or oxide and the carbon material, i.e., composite particles, include at least a portion of the periphery of the metal or metalloid or oxide particle as the carbon material. And a composite particle in which at least a part of the periphery of the carbon material particle is coated with the metal, metalloid or oxide. These particles may be further coated on the surface with a carbon film.

[0046] The negative electrode active material as described above can also be formed by a vacuum film forming method or a pressure welding method. Vacuum evaporation, sputtering, CVD, etc. can be used as the vacuum film forming method. As the pressure welding method, a mechanofusion 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 a vacuum film forming method, a vacuum evaporation method, a sputtering method, a CVD method, etc. can be used.

[0048] The negative electrode of the secondary battery of the present invention is formed by forming a layered structure including a layer mainly containing the above-mentioned metal, metalloid or oxide, and a layer mainly containing the above-mentioned carbon material. Is preferred. Here, it is assumed that the “layer containing the main component” occupies 50% by mass or more of the entire material constituting the layer. When the above-mentioned layered structure is formed, it is preferable that the main component of each layer accounts for 70% by mass or more.

[0049] and have negative active material Nitsu using metal or metalloid and carbon material containing an element M ¹ above, is described below with more detail.

[0050] Additional elemental metal containing M ¹ or metalloid and carbon material, simply, each particle They may be mixed in a child state. Or, metallic 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.

Particles composed of metal or metalloid containing element M ¹ , particles composed of metal or metalloid containing element M ¹ and element X, and metal or metalloid containing element M ¹ The particles composed of the element X and the lithium metal or the lithium alloy are produced by using a vacuum film forming method or a pressure welding method in addition to a usual production method.

As a method of compounding, a vacuum film forming method such as a CVD method, a pressure welding method such as a mechanical milling method ゃ mechanofusion method, or a sol-gel method can be used.

[0053] When the composite was coated with a carbon material a metal or metalloid containing the element M ^1, for example, CVD Rukoto force to coat the carbon material film on the metal or metalloid containing the element M ¹ S can. Or, coated with carbonaceous material, such as data Lumpur the particles composed of a metal or metalloid containing the element M ^1, including the element M ¹ by firing at about 1000 ° C under an inert atmosphere Ability to apply carbon coating to particles composed of metal or metalloid. Further, it is possible to coat the carbon material film on the metal or metalloid containing the element M ¹ by vacuum evaporation.

[0054] Further, even when using a pressure method such as mechanical milling Ya mechanofusion, the metal or metalloid containing the elemental 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 two Carmi ring, embedding a metal or metalloid particles containing the element M ¹ in the carbon material particle composite Can be changed. 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.

[0055] The carbon material, when the composite coated with a metal or metalloid containing the element M ^1, for example by a CVD method, form a metal or semi-metal film containing an element M to the carbon material particles And can be compounded. Or, a metal or semi-metal film containing an element M ¹ to the carbon material particles by sol-gel method, can be conjugated.

[0056] As the anode active material, can as described above to the metal or metalloid was allowed to composite particles containing a carbon material and the element M ¹ use Le, is Rukoto. Further, these composited particles can be further mixed with graphite or amorphous carbon particles and used as a negative electrode active material.

When a particulate negative electrode active material selected from the above is used, the negative electrode active material particles are converted to a conductive material such as carbon black (a conductivity-imparting material), polyvinylidene fluoride, or the like. Layer 13 serving as a negative electrode by a method such as dispersing and kneading in a solvent such as N-methyl-2-pyrrolidone (NMP) together with a binder such as chloride (PVDF), and applying the mixture on a substrate such as a copper foil. Gaining power S When dispersing a plurality of particles, it is also possible to use those that have been previously mixed by a method such as mechanical milling.

Further, a metal or metalloid containing the above-described element M ¹ and a carbon material can be simultaneously formed into a film to form a composite. In such a case, the selected negative electrode active material is appropriately cooled by a melt cooling method, a liquid quenching method, an atomizing method, a vacuum deposition method, a sputtering method, a plasma CVD method, an optical CVD method, a thermal CVD method, a Zonoray gel method, or the like. A layer 13 serving as a negative electrode can be obtained by forming a film on a substrate by a method.

[0059] may have a structure of at least two of the layers shall be the main component 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 of carbon material on an anode current collector to form a layer mainly components, mainly composed 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.

[0060] 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 can be expected expression of cushioning effect for the volume change accompanying with charge and discharge of the metal or metalloid containing the element M ^1. 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 . With this structure, The layer on containing a composite material of a metal or metalloid and the carbon material containing the serial element M ¹ can preferentially form film, a high conductivity can be expected good cycle characteristics.

[0061] The layer containing a carbon material as a main component can be formed by a coating method or a vacuum film formation 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, N-methyl_2_pyrrolidone may be used together with a conductive substance such as carbon black (a conductivity-imparting material) and a binder such as polyvinylidene phthaleolide (PVDF). (NMP) or the like, and can be formed by a method such as dispersing and kneading in a solvent, and applying this on a substrate such as a copper foil. Layer mainly containing a metal or metalloid containing the element M ¹ is melt cooling method, liquid quick cooling method, atomizing method, a vacuum deposition method, sputtering method, plasma CVD method, optical CVD method, thermal CVD method, Zonoregeru It can be formed by forming a film on the substrate by an appropriate method such as a method. 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 dispersing and kneading in a solvent such as N-methyl-2-pyrrolidone (NMP) with a binder such as polyvinylidene fluoride (PVDF) and applying it to a substrate such as copper foil. can do.

[0062] layer containing a composite material of a metal or metalloid and the carbon material containing the above element M ¹ is a coating method, or a vacuum deposition method, by a sputtering method or a vacuum deposition method such as CVD That power S can.

[0063] The negative electrode active material using the above oxide and carbon material will be described in more detail as follows.

[0064] The oxide and the carbon material may be simply mixed in the form of particles. Alternatively, as shown in FIG. 4, the oxide 2c may be covered with the carbon material 2a to form a composite. Alternatively, as shown in FIG. 5, the carbon material 3a may be covered with the oxide 3c to form a composite. When compounded, high conductivity and a cushioning effect against volume change due to charge and discharge of the oxide can be expected.

[0065] 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 lithium metal or lithium alloy are prepared by a usual production method. In addition to the above, Talk about things.

As a method of compounding, a vacuum film forming 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 above oxide is coated with a carbon material to form a composite, the oxide can be coated with a carbon material film by, for example, a CVD method. Alternatively, the particles composed of the above oxide are coated with a carbonaceous substance such as tar, and then calcined at about 1000 ° C in an inert atmosphere, so that the particles composed of the above oxide are carbon-coated. be able to. The oxide can be coated with a carbon material film by a vacuum evaporation method.

[0068] Also, when a pressure welding method such as mechanical milling / mechanofusion is used, the above oxide can be coated with a carbon material to form a composite. For example, by mixing the oxide particles and the carbon material particles and performing mechanical milling, the oxide particles can be embedded in the carbon material particles to form a composite. It is also possible to combine the carbon material and the oxide by mechanical milling as described above, and then coat the carbon material by CVD or carbon material deposition.

[0069] When the carbon material is coated with the above-described oxide to form a composite, the oxide film can be formed on the carbon material particles by, for example, a CVD method, and the composite film can be formed. Alternatively, an oxide film can be formed on the carbon material particles by a sol-gel method to form a composite.

[0070] As the negative electrode active material, particles obtained by complexing the carbon material and the oxide as described above can be used. Further, these composited particles can be further mixed with graphite or amorphous carbon particles and used as a negative electrode active material.

[0072] Further, the oxide and the carbon material can be simultaneously formed into a film to form a composite film. In this case, the selected negative electrode active material is melt-cooled, liquid quenched, atomized, It is possible to obtain a layer 13 serving as a negative electrode by forming a film on a substrate by an appropriate method such as an empty deposition method, a sputtering method, a plasma CVD method, a light CVD method, a thermal CVD method, a sol-gel method, or the like.

[0073] A structure having at least two layers of a layer mainly containing the oxide and a layer mainly containing a carbon material can be employed. 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. With this structure, a film can be formed preferentially on a layer mainly composed of an oxide, and high conductivity and good vital characteristics can be expected.

Further, a structure having at least two layers of a layer containing the composite material of the oxide and the carbon material and a layer containing the carbon material as a main component may be employed. With this structure, high conductivity and a cushioning effect against a volume change due to charge and discharge 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. With this structure, a film can be formed preferentially on the layer containing the composite material of the oxide and the carbon material, and high resilience, conductivity, and good cycle characteristics can be expected.

[0075] The layer containing a carbon material as a main component can be formed by a coating method or a vacuum film formation 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, N-methyl-2-pyrrolidone may be used together with a conductive substance such as carbon black (a conductivity-imparting material) and a binder such as polyvinylidene phthaleolide (PVDF). (NMP) or the like, and can be formed by a method such as dispersing and kneading in a solvent, and applying this on a substrate such as a copper foil. The layer mainly composed of an oxide is formed by an appropriate method such as a melt cooling method, a liquid quenching method, an atomizing method, a vacuum evaporation method, a sputtering method, a plasma CVD method, an optical CVD method, a thermal CVD method, or a sol-gel method. It can be formed by forming a film on a substrate. The layer containing an oxide as a main component includes N particles, a conductive material such as carbon black (a conductivity-imparting material), and a binder such as polyvinylidene fluoride (PVDF). —It can be formed by dispersing and kneading in a solvent such as methyl-2-pyrrolidone (NMP) and applying it to a substrate such as a copper foil.

[0076] The layer containing the composite material of the oxide and the carbon material is formed by a coating method or a vacuum deposition method. It can be formed by a vacuum film forming method such as a sputtering method, a sputtering method, or a CVD method.

[0077] (Electrolyte)

The electrolytic solution 15 has at least an electrolyte, an aprotic solvent and an additive.

[0078] (Electrolyte)

As the electrolyte, in the case of a lithium secondary battery, a lithium salt is used, and this is dissolved in an aprotic solvent. As lithium salts, lithium imide salts, LiPF, LiAsF, LiAICl, Li

6 6 4

CIO, LiBF, LiSbF and the like. As the lithium imide salt, LiN (C F SO

4 4 6 k 2k + l

) (C F SO) (k and m are each independently 1 or 2). Special among them

2 m 2m + l 2

LiPF and LiBF are preferred. These may be used alone or in combination.

6 4

Can be. High energy density can be achieved by including these lithium salts.

(Aprotic solvent)

In addition, the aprotic electrolytic solution may include cyclic carbonates, chain carbonates, aliphatic carboxylic acid esters, γ-ratatanes, cyclic ethers, chain ethers, and organic solvents of these fluorinated derivatives. Use at least one selected organic solvent. More specifically,

Cyclic carbonates: propylene carbonate (hereinafter abbreviated as PC), ethylene carbonate (hereinafter abbreviated as EC), butylene carbonate (BC), and derivatives thereof Linear carbonates: dimethyl carbonate (DMC) Getyl carbonate (hereinafter abbreviated as DEC), ethyl methyl carbonate (EMC), dipropyl carbonate (DPC), and derivatives thereof

Aliphatic carboxylic esters: methyl formate, methyl acetate, ethyl propionate, and derivatives thereof

T-latatatones: γ-petit ratatone, and derivatives thereof

Cyclic ethers: tetrahydrofuran, 2-methyltetrahydrofuran, and derivatives thereof

Chain ethers: 1,2-diethoxytan (DEE), ethoxymethoxyethane (ΕΜΕ), dimethyl ether, and derivatives thereof Others: dimethylsulfoxide, 1,3-dioxolane, honolemamide, acetamide, dimethylenolenomolemide, acetonitrile, propionitrile, nitromethane, ethyl monoglyme, phosphoric acid triester, trimethoxymethane, dioxolane derivative, methylsulfolane, 1,3-Dimethinole_2_imidazolidinone, 3_methyl_2_oxazolidinone, anisol, N-methylbilidone, fluorinated carboxylate

These can be used alone or in combination of two or more.

[0080] (Additive)

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

[0081]

14

Substituted or unsubstituted alkyl group having 15 carbon atoms, substituted or unsubstituted alkoxy group having 15 carbon atoms, substituted or unsubstituted fluoroalkyl group having 15 carbon atoms, polyfluoro group having 15 carbon atoms SO X (X is a substituted or unsubstituted carbon atom 1

2 1 1 1 5 alkyl group), -SY (Y is a substituted or unsubstituted carbon atom 1

1 1 1 5 alkyl group), 1 CO

Z (Z is a hydrogen atom or a substituted or unsubstituted alkyl group having 15 to 15 carbon atoms), a halogen atom, and an atom or group selected from the following. R and R are each independently

twenty three

A substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted fluoroalkyl group having 1 to 5 carbon atoms, C15 polyfluoroalkyl group, substituted or unsubstituted C15 fluoroalkoxy group, C15 polyfluoroalkoxy group, hydroxyl group, halogen atom, -NX X ( X and X are each independently a hydrogen atom, Or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms) and NY CONY Y (Υ

2 3 4 2 1 Υ independently represents a hydrogen atom or a substituted or unsubstituted

Four

Alkyl group), force Indicates an atom or group to be selected. )

[0083] The compound represented by the general formula (1) is an acyclic compound, does not involve a cyclization reaction at the time of synthesis, and can be synthesized using, for example, Non-Patent Documents 14 to 14. It can also be obtained as a by-product of the synthesis of the cyclic disulfonic acid ester shown in Patent Document 9. As described above, since the compound represented by the general formula (1) is easily synthesized, there is a U point at which an inexpensive electrolytic solution can be provided.

[0084] The preferable molecular structure of R and R in the general formula (1) is a reaction occurring on an electrode.

14

From the viewpoints of easy formation of a functional film, stability of the compound, ease of handling, solubility in a solvent, ease of compound synthesis, and price, etc. An alkyl group, a halogen atom, and one SO X (X is a substituted or unsubstituted carbon

2 1 1

An atom or group selected from (prime number 15 alkyl groups) is preferred, and each independently is a hydrogen atom or a hydrogen atom or a methyl group, more preferably an unsubstituted alkyl group having 115 carbon atoms. . Particularly preferred forms of R and R are those in which R and R are hydrogen

This is the case of 14 atoms. When R and R are hydrogen atoms, a methyl group sandwiched between two sulfonyl groups

14

This is because the ren moiety is activated and a reaction film on the electrode is easily formed.

[0085] In R and R, the stability of the compound, the ease of synthesis of the compound,

twenty three

From the viewpoints of solubility, price, etc., each independently represents a substituted or unsubstituted alkyl group having 15 to 15 carbon atoms, a substituted or unsubstituted alkoxy group having 15 to 15 carbon atoms, a substituted or unsubstituted phenoxy group, Hydroxyl group, halogen atom, and NX X (X and X are

2 3 2 3

Independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms), and is preferably an independently substituted or unsubstituted alkyl having 1 to 5 carbon atoms. Group, or a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms is more preferable, and more preferably, one or both of R and R are substituted or unsubstituted.

twenty three

It is an alkoxy group having 115 carbon atoms. For the same reason, the substituted or unsubstituted alkyl group having 115 carbon atoms is preferably a methyl group or an ethyl group, and the substituted or unsubstituted alkoxy group having 115 carbon atoms is methoxy. Groups or ethoxy groups are preferred. [0086] The compound represented by the general formula (1) has two sulfonyl groups and has a small LUMO. The solvent molecule in the electrolytic solution, and the LUMO has a smaller value than the monosulfonate, so that the compound is reduced. easy. For example, the LUMO of compound No. 1 shown in Table 1 below is as small as 0.86 eV according to semi-empirical molecular orbital calculations. Therefore, it is thought that a reduced film of Compound No. 1 is formed on the negative electrode before the solvent composed of cyclic carbonate or chain carbonate (LUMO: about 1.2 eV), and plays a role in suppressing the decomposition of solvent molecules. Since the decomposition of solvent molecules is suppressed, a decomposition film of high-resistance solvent molecules is less likely to be formed on the negative electrode, so that suppression of resistance increase and improvement of cycle characteristics can be expected. It is also possible that the carbon atom has two electron-attractive sulfonyl groups bonded to it, and that the activation of the carbon atom can easily form a film on the electrode. Furthermore, it is conceivable that the carbanion generated by deprotonation of active methylene coordinates Li or reacts on the positive electrode to form a film.

[0087] Specific examples of the general formula (1) are shown below, but the present invention is not particularly limited thereto.

[0088]

No. 1

o

s (s009

〇〇

"..S0

s (008 io¾o¾oo—o 〇

L '° N

[6 ^>] [600]

[s6oo]

Q,

⁰ 〇

[2600]

Sl .8T0 / l700Zdf / X3d VZ ST ..SO / SOOZ OAV [0095] [Formula 10]

N 8

[0096] [Formula 11]

[0097] [Formula 12]

N 1 0

[0098] [Formula 13]

N 1

[0099] [Formula 14]

[0100] [Formula 15]

No. 1 3

[0101] [Formula 16]

[0102] [Formula 17]

[0103] [Formula 18]

[0104] [Formula 19]

[0105] [Formula 20]

N 1 8

[0106] [Formula 21]

[0107] [Formula 22]

N o. 20

[0108] The compound represented by the general formula (1) is not particularly limited, but is preferably contained in the electrolytic solution at 0.1 mass% to 5.0 mass%. If the amount is less than 0.1% by mass, the effect of forming a film by an electrochemical reaction on the electrode surface may not be sufficiently exerted. On the other hand, if it exceeds 5.0% by mass, not only is it difficult to dissolve, but also the viscosity of the electrolyte may be increased. More preferably, in the present invention, a more sufficient film effect can be obtained by adding in the range of 0.5% by mass to 3.0% by mass.

[0109] The compounds represented by the general formula (1) may be used alone or in combination of two or more. When two or more kinds are used in combination, at least one compound having an active methylene group (ie, R and

One

It is effective to include a compound in which R is hydrogen). As a specific combination,

Four

Compound No. 1 (a compound having an active methylene group) and compound No. 5.

[0110] When two or more compounds of the general formula (1) are added to the electrolytic solution, the proportion of the compound in the electrolytic solution is not particularly limited, but for the same reason as described above, the total of the two types is 0.1% by mass or more.

0 mass% or less is preferable. When two or more compounds 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 least compound is 5% by mass, 95% of the most compound

% Is preferable.

[0111] Furthermore, a cyclic monosulfonic acid ester, a cyclic sulfonic acid ester having two sulfonyl groups, an alkanesulfonic acid anhydride, It is also effective here to use an electrolytic solution containing at least one of the Renyidani products.

[0112] Examples of the cyclic monosulfonic acid ester include compounds represented by the following general formula (2).

[0113] [Formula 23]

(However, in the above general formula (2), n is an integer of 0 or more and 2 or less.

5 10 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 6 carbon atoms, and a polyfluoroalkyl group having 1 to 6 carbon atoms. Indicates the selected atom or group. )

[0115] 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 compound synthesis, solubility in a solvent, and price. So

51 R is independently an atom or a group selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 11 to 12 carbon atoms, and a polyfluoroalkyl group having 115 carbon atoms. Independently, each is more preferably a hydrogen atom or a polyfluoroalkyl group having 1 to 5 carbon atoms. More preferably, all R are hydrogen atoms, or one or two of R—R

5 of R

10 5 10

Is a polyfluoroalkyl group having 15 carbon atoms, and the others are hydrogen atoms. As the above-mentioned polyfluoroalkyl group having 115 carbon atoms, a trifluoromethyl group is preferable.

[0116] Specifically, 1,3_propane sultone (1,3_PS), α-trifluoromethyl-γ-sultone, j3-trifluoromethylinone, γ-sultone, γ-trifluoromethylinole 1 γ-sultone, 1 methinole 1 γ_snoretone, 1 j-di (trifnorolelomethinole) 1 γ _snoreton, 1 h, Hichiji (trif noreolomethinole) 1 γ-sultone, 1d Gamma-sultone, Tafluoropropyl- _γ -sultone, 1,4-butansnoretone (1,4-BS), etc.

[0117] Among them, 1,3-propane sultone (1,3-PS) is considered to form a decomposition film on the negative electrode of a lithium ion secondary battery. The LUMO of 1,3-PS is 0.07 eV, which is larger than that of compound No. 1 of the present invention (0.86 eV). For example, when compound No. 1 of the present invention and 1,3-PS are added to the electrolyte and charged, first, the substance of compound No. 1 forms a film on the negative electrode, and then 1,3-PS is formed. It is conceivable to form a film. In the initial stage of charging, the power S that mainly reacts with a certain part of the negative electrode surface and Compound No. 1 and the charging progresses in the part that did not react with Compound No. 1 (the part that may react with solvent molecules). As a result, it reacts with 1,3-PS, and as a result, a composite film of compound No. 1 and 1,3-PS is formed, and it can be expected to further suppress the rise in resistance and to suppress battery swelling.

[0118] 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 it is 0.5% by mass to 10.0% by mass in the electrolytic solution. % Or less is preferable. If the content is less than 0.5% by mass, the effect of electrochemical reaction on the electrode surface may not be sufficiently exerted to form a film. If it exceeds 10.0% by mass, the viscosity of the electrolyte may be increased. The ratio of the compound of the general formula (2) in the compound of the general formula (1) and the compound of the general formula (2) is calculated based on the total mass of the compound of the general formula (1) and the compound of the general formula (2). 10-90% by weight is preferred.

[0119] Examples of the cyclic sulfonic acid ester having two sulfonyl groups include a compound represented by the following general formula (3).

[0120] [Formula 24]

(Wherein, in the above general formula (3), Q is an oxygen atom, a methylene group or a single bond, A is a substituted or unsubstituted alkylene group having 115 carbon atoms, a carbonyl group, C-C bond in a sulfinyl group, a polyfluoroalkylene group having 15 to 15 carbon atoms, a substituted or unsubstituted fluoroalkylene group having 15 to 15 carbon atoms, or a substituted or unsubstituted alkylene group having 15 to 15 carbon atoms A group in which at least one of the groups is a C-C bond, a group in which at least one of the C-C bonds in the C5-C15 polyfluoroalkylene group is a C-C bond, and A substituted or unsubstituted fluoroalkylene group having 1 to 5 carbon atoms in which at least one of the C—C bonds is a C_〇_C bond, and a group selected from the group consisting of: Unsubstituted alkylene group with 115 carbon atoms, polyfluoroal with 115 carbon atoms And a group selected from a kylene group and a substituted or unsubstituted fluoroalkylene group having 115 carbon atoms.)

[0122] In view of the stability of the compound represented by the above general formula (3), the stability of the compound, the ease of compound synthesis, the solubility in a solvent, the price, and the like, A is a substituted or unsubstituted C1-C5 alkylene group, C5-C15 polyfluoroalkylene group, substituted or unsubstituted C5-C15 fluoroalkylene group, substituted or unsubstituted C1-C5 alkylene At least one of the C-C bonds in the C-C bond is a C-O-C bond, and at least one of the C_C bonds in a C5-C15 polyfluoroalkylene group is a C-C bond. A group in which at least one of the C-C bonds in the substituted or unsubstituted fluoroalkylene group having 1 to 5 carbon atoms is a coc bond, or a group selected by force . A substituted or unsubstituted alkylene group having 15 to 15 carbon atoms, a polyfluoroalkylene group having 15 to 15 carbon atoms, and a substituted or unsubstituted fluoroalkylene group having 15 to 15 carbon atoms; A substituted or unsubstituted alkylene group having 15 carbon atoms is more preferred, and a methylene group, an ethylene group or a 2,2-propanezyl group is particularly preferred. The fluoroalkylene group having 115 carbon atoms described above is more preferably composed of a methylene group and a difluoromethylene group, which preferably contains a methylene group and a difluoromethylene group. New

[0123] For the same reason, B is more preferably a methylene group, a 1,1-ethanediyl group, or a 2,2-propanediyl group, which is preferably an alkylene group having 115 carbon atoms.

[0124] 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.

[0125] [Formula 25]

[0126] [Formula 26]

N o. 2 2

[0127] [Formula 27]

Ν

[0128]

[0129] [Formula 29]

No. 2 5

[0130] [Formula 30]

[0131] [Formula 31]

N o. 2 7 ooo ° 〇, [0132] [Formula 32]

N o 8

[0133] [Formula 33]

N 2 9

[0134] [Formula 34]

N o. 30

[0135] [N35] o N〇

",

N

o

.

3 o 3 £ —

Four

Yes

[0136] [Formula 36]

0,

II

〇

[0137] [Formula 37]

N 0

[0138] [Formula 38]

[0139] [Formula 39]

N o 3 5

[0140] [Formula 40]

N 3 6

[0141] [Formula 41]

No. 3 7

[0142] [Formula 42]

No. 3 8

[0143] [Formula 43]

N 3 9

[0144] [Formula 44]

N o. 40

[0145] [Formula 45]

N. 4 1

[0146] [Formula 46]

No. 4 2

o o

. 1Λ

[0147] Since 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, for example, the compound No. 1 and the compound No. 21 (MMDS When the substance is added to the electrolytic solution, a highly ion-conductive composite film is easily formed at the initial stage of charging. MMDS is a cyclic compound, and is considered to be a compound which reacts with the negative electrode by ring opening to form a film.

[0148] Assuming that MMDS significantly selectively contributes to film formation on the negative electrode, the compound No. 1 has a relatively low probability of film formation on the negative electrode, and conversely, the reaction probability on the positive electrode. And film formation on the positive electrode is achieved. As a result, suppression of solvent decomposition on the positive electrode can be expected.

[0149] 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 may be 0.5% by mass in the electrolytic solution. It is preferable that the content is not less than 10.0% by mass. If the amount is less than 0.5% by mass, the effect of forming a film on the electrode surface by an electrochemical reaction may not be sufficiently exerted. If it exceeds 10.0% by mass, the viscosity of the electrolyte may be increased. The ratio of the compound of the general formula (3) in the general formulas (1) and (3) is 1090% by mass of the total mass of the compounds of the general formulas (1) and (3). preferable. In addition, when the compound of the general formula (2) is used in addition, 1090% by mass of the total mass of the compounds of the general formulas (1), (2) and (3) is preferable. ,.

[0150] In the present invention, at least one of vinylene carbonate (VC) and a derivative thereof can be optionally added to the electrolytic solution. Cycle characteristics can be further improved by adding at least one of vinylene carbonate (VC) and a derivative thereof. The LUMO of VC is 0.09 eV, which makes it less susceptible to reduction than the compound of general formula (1). Les ,. It is thought that it is present in the electrolyte for a long time without being consumed by the reduction reaction in the initial charge and discharge. Therefore, by gradually being consumed during the charge / discharge cycle, it is possible to contribute to improvement in cycle characteristics. When at least one of vinylene carbonate and its derivative is used as an additive in the electrolytic solution, the effect can be obtained by adding 0.05% by mass and 3.0% by mass in the electrolytic solution.

[0151] When the compound of general formula (1) and VC, the compound of general formula (1) and other additives, and further VC are added to the electrolytic solution, the ratio of VC to the total electrolytic solution is particularly limited. 0.5% by mass 10.0% by mass is preferred. If the amount is less than 0.5% by mass, the effect of forming a film by an electrochemical reaction on the electrode surface may not be sufficiently exhibited. If it exceeds 10.0% by mass, the viscosity of the electrolyte may be increased.

[0152] The electrolytic solution of the present invention is obtained by adding and dissolving the compound represented by the general formula (1) to the electrolytic solution. Other additives (cyclic monosulfonate, cyclic sulfonate having two sulfonyl groups, sulfolane, alkanesulfonic anhydride, sulfolene compound or vinylene carbonate compound) may be added to this electrolyte as appropriate. Thus, a desired electrolyte can be obtained.

[0153] 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 outer package made of a flexible film or the like which is a laminate of a synthetic resin and a metal foil, and is a battery can of cylindrical type, square type, coin type and the like. As soon as it is affected by the increase of the internal pressure as compared with the one enclosed in an outer package, control of the chemical reaction between the electrode and the electrolyte is more important. As long as the secondary battery contains the chain disulfone compound represented by the general formula (1) according to the present invention, even if it is a laminate type battery, it suppresses a rise in resistance and swells the battery (gas generation and internal pressure reduction). Rise) can be suppressed. Therefore, it is possible to secure safety and long-term reliability even for large-sized lithium-ion secondary batteries such as those for automobiles.

[0154] 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 inert gas atmosphere, or the laminated product is wound, and then inserted into the exterior body. And impregnated with an electrolytic solution containing the compound represented by the general formula (1). After that, it is obtained by sealing the battery exterior body. The effect of the present invention can be obtained by charging the battery before or after sealing to form a film on the electrode.

[0155] Further, the chain disulfonate represented by the general formula (1) of the present invention is not limited to a lithium secondary battery, and can also be used as an additive for other electrolytic solutions for electrochemical devices. Other electrochemical devices include, for example, organic radical batteries, capacitors, and dye-sensitized wet solar cells.

Example

[0156] (Production of Battery)

A positive electrode active material and a conductivity-imparting agent shown in Table 15 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 is applied on an aluminum metal foil (20 / m in the case of square or cylindrical type, 25 / im in the case of laminate type) serving as a positive electrode current collector, and NMP is evaporated to form a positive electrode sheet. did. The solid content ratio in the positive electrode was positive electrode active material: conductivity imparting agent: PVDF = 80: 10: 10 (% by mass).

[0157] On the other hand, negative electrode active materials other than the carbon material were those shown in Table 15-15. Graphite or amorphous carbon was used as the carbon material. When the negative electrode active material is in the form of particles, the negative electrode active material other than the carbon material: dry-mixed so that the ratio of PVDF: conductivity-imparting material = 90: 9: 1 (% by mass), and the average particle diameter Zm carbon material particles are dispersed in NMP and coated on copper foil (10 xm for square or cylindrical, 20 zm for laminate) as negative electrode current collector . When the negative electrode active material is in the form of a film, unless otherwise specified, the ratio of carbon material particles having an average particle diameter of 10 μm: PVDF: conductivity imparting material = 90: 9: 1 (% by mass). The dry mixture is dispersed in NMP and applied on copper foil (10 xm for square or cylindrical, 20 zm for laminate) as negative electrode current collector, followed by vacuum evaporation. A negative electrode active material other than a carbon material was appropriately selected from a sputtering method, a sputtering method, and a CVD method. When using composite particles obtained by compounding a metal, metalloid, or oxide and a carbon material as the negative electrode active material, the ratio of the composite particles: PVDF: conductivity imparting material = 90: 9: 1 (% by mass) The dry mixture is dispersed in NMP and mixed with the negative electrode current collector. On a copper foil (10 μΐη). Unless otherwise specified, the carbon material was 50% by mass based on the entire negative electrode active material. The film thickness of these negative electrodes is set according to the capacity ratio with the positive electrode (hereinafter referred to as A / C balance), where Α 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 this A / C balance was 1 or more and 1.7 or less.

[0158] The electrolytic solution used was a solvent described in Table 15-5, lmol / L LiPF as the electrolyte, and Table 1

A solution prepared by dissolving the additive described in 1-5 was used. The number in parentheses in the column of the additive indicates the mass% of the additive in the electrolytic solution.

[0159] Thereafter, the negative electrode and the positive electrode were laminated with a separator made of polyethylene interposed therebetween, and a prismatic secondary battery (exemplified in the column 1-31, 52 60, 61 91, and 112-143, and]: ί Rows 1-3, 9-13, 19, and 20), cylindrical secondary batteries (Examples 46-51 and 106 111, and Comparative Examples 8 and 18), and aluminum laminated film secondary batteries (Examples 32 to 45 and 92 to 105, and Comparative Examples 417 and 14 to 117) were produced. In the case of an aluminum laminated film type secondary battery, the laminated film used was a polypropylene resin (sealing layer, thickness 70 / im), polyethylene terephthalate (20 / im), aluminum (50 μΐη), polyethylene terephthalate (20 / m ). Two pieces of this are cut out to a predetermined size, and a recess having a bottom portion and a side portion corresponding to the size of the above-mentioned laminated electrode body is formed in a part thereof, and these are opposed to each other to wrap the above-mentioned laminated electrode body. Then, the periphery was heat-sealed to produce a film-covered battery. The electrolytic solution was impregnated into the laminated electrode body before the last one side was sealed by heat sealing.

[0160] (Evaluation of battery)

The battery fabricated by the above process was subjected to a charge / discharge cycle test at a temperature of 20 ° C with a charge rate of 1.0C, a discharge rate of 1.0C, a charge end voltage of 4.2V, and a discharge end voltage of 3.0V. The results are shown in Table 6-10. The capacity retention rate (%) after 400 cycles is the value obtained by dividing the discharge capacity (mAh) after the 400 cycle test by the discharge capacity (mAh) after the 10 cycle test and multiplying by 100. The resistance retention rate after 400 cycles is the relative value of the resistance after the 400 cycles test, where the resistance before the sitar test is 1. [0161] (Example 1)

The layer containing the negative electrode active material was formed by depositing Si as a negative electrode active material other than the carbon material by CVD. Graphite was used as the carbon material. LiCoO was used as the positive electrode active material contained in the layer containing the positive electrode active material. EC / DEC / EMC = 3 for electrolyte

2

In 0/50/20 (volume ratio), lmol / L LiPF as electrolyte and compound as additive

6

A material containing 0.5% by mass of the product No. 1 was used. A rectangular aluminum container was used for the battery exterior. The capacity ratio A / C balance between the positive and negative electrodes 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. Other conditions were the same as in Example 1.

(Example 3)

The layer containing the negative electrode active material was formed by sputtering A1 as a negative electrode active material other than the carbon material. 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 size of 10 μΐη as a negative electrode active material other than the carbon material. 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 μΐη as a negative electrode active material other than the carbon material. 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. 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. Other conditions were the same as in Example 1.

[0168] (Example 8)

The layer containing the negative electrode active material was prepared by simultaneously forming films using two sputtering sources, Si and A1, as the negative electrode active material other than the carbon material (the number of S ^ g elements: the number of A1 atoms = 5: 5 ). Beyond 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 mechanically milling Si having an average particle size of 10 μΐη and Sn having an average particle size of 10 am as a negative electrode active material other than the carbon material (the number of Si atoms). : Number of Sn atoms = 5: 5). Other conditions were the same as in Example 1.

(Example 10)

The layer containing the negative electrode active material was formed by simultaneous deposition using two deposition sources, 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 ). Other conditions were the same as in Example 1.

(Example 11)

Compound No. 2 was used as an additive. Other conditions were the same as in Example 1.

(Example 12)

Compound No. 3 was used as an additive. Other conditions were the same as in Example 1.

(Example 13)

Compound No. 4 was used as an additive. Other conditions were the same as in Example 1.

(Example 14)

Compound No. 6 was used as an additive. Other conditions were the same as in Example 1.

(Example 15)

Compound No. 9 was used as an additive. Other conditions were the same as in Example 1.

(Example 16)

Compound No. 10 was used as an additive. Other conditions were the same as in Example 1.

(Example 17)

Compound No. 15 was used as an additive. Other conditions were the same as in Example 1.

(Example 18)

Compound No. 16 was used as an additive. Other conditions were the same as in Example 1.

(Example 19)

Compound No. 19 was used as an additive. Other conditions were the same as in Example 1.

[0180] (Example 20) The layer containing the negative electrode active material was produced using Si having an average particle size of 10 μΐη as a negative electrode active material other than the carbon material. Amorphous carbon was used as the carbon material. Other conditions were the same as in Example 1.

[0181] (Example 21)

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

[0182] (Comparative Example 1)

The layer containing the negative electrode active material was formed by depositing Si as a negative electrode active material other than the carbon material by vapor deposition. No additives were used in the electrolyte. Other conditions were the same as in Example 1.

[0183] (Comparative Example 2)

The layer containing the negative electrode active material was produced using Si having an average particle size of 10 μΐη as a negative electrode active material other than the carbon material. Amorphous carbon was used as the carbon material. No additives were used in the electrolyte. Other conditions were the same as in Example 1.

(Example 22)

The layer containing the negative electrode active material was formed by depositing Si as a negative electrode active material other than the carbon material by CVD. Graphite was used as the carbon material. LiMnO was used as the positive electrode active material contained in the layer containing the positive electrode active material. PC / EC / DEC = 20 for electrolyte

2

In 20/60 (volume ratio), lmol / L of LiPF as electrolyte and compound as additive

6

(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. Other conditions were the same as in Example 22.

(Example 24)

The layer containing the negative electrode active material was formed by sputtering A1 as a negative electrode active material other than the carbon material. 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 size of 10 μΐη as a negative electrode active material other than the carbon material. 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 diameter of 10 m as a negative electrode active material other than the carbon material. 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. 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. Other conditions were the same as in Example 22.

(Example 29)

The layer containing the negative electrode active material was prepared by simultaneously forming films using two sputtering sources, Si and A1, as the negative electrode active material other than the carbon material (S source number: A1 atom number: 5: 5) . 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 mechanically milled Si having an average particle size of 10 μΐη and Sn having an average particle size of 10 μm as a negative electrode active material other than the carbon material (Si atom Number: Sn atom number = 5: 5). Other conditions were the same as in Example 22.

(Example 31)

The layer containing the negative electrode active material was formed by simultaneous deposition using two deposition sources, 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 ). 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 as a negative electrode active material other than the carbon material by vapor deposition. No additives were used in the electrolyte. Other conditions were the same as in Example 22. (Example 32)

The layer containing the negative electrode active material was formed by simultaneous deposition using two evaporation sources, Si and Fe corresponding to the element X, as the negative electrode active material other than the carbon material (the number of S sources: Fe Atomic number = 19: 1). Graphite was used as the carbon material. LiCoO was used as the positive electrode active material contained in the layer containing the positive electrode active material. EC / DEC / EMC = 30/50 for electrolyte

2

/ 20 (volume ratio), lmol / L LiPF as electrolyte and compound No as additive

6

1 containing 0.5% by mass was used. For the battery exterior, a container was made of a member coated with aluminum foil by lamination and used. The capacity ratio of the positive and negative electrodes A / C balance is

1. Set to 05.

(Example 33)

The layer containing the negative electrode active material was formed by simultaneously forming films using two sputtering sources, 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). Other conditions were the same as in Example 32.

(Example 34)

The layer containing the negative electrode active material is formed by mechanically milling, as a negative electrode active material other than carbon material, Si—A1 alloy particles having an average particle size of 10 μΐη and Ni particles corresponding to element X having an average particle size of 10 μΐη. Made using mixed particles (S source number: A1 atom number: N source number = 10: 9: 1)

. Other conditions were the same as in Example 32.

(Example 35)

The layer containing the negative electrode active material is formed by mechanically milling Si—Sn alloy particles with an average particle diameter of 10 μΐη and Ti particles corresponding to element X with an average particle diameter of 10 μm as the negative electrode active material other than the carbon material. Fabricated using mixed particles (Si atoms: Sn atoms: Ti atoms = 5: 5: 90)

. Other conditions were the same as in Example 32.

(Example 36)

In the layer containing the negative electrode active material, as a negative electrode active material other than carbon material, Si--Li alloy particles with an average particle size of 10 m and Fe particles corresponding to element X with an average particle size of 10 μm are mixed by mechanical milling. (Si atoms: Li atoms: Fe atoms = 9: 4: 1). Other conditions were the same as in Example 32. [0200] (Example 37)

In the layer containing the negative electrode active material, Si particles with an average particle diameter of 10 μΐη and Fe particles corresponding to element X with an average particle diameter of 10 μm were combined by mechanical milling as the negative electrode active material other than the carbon material. (Number of Si atoms: number of Fe atoms = 9: 1). Amorphous carbon was used as the carbon material. Other conditions were the same as in Example 32.

[0201] (Comparative Example 4)

The layer containing the negative electrode active material was formed by simultaneous vapor deposition using two evaporation sources, Si and Fe corresponding to the element X, as the negative electrode active material other than the carbon material (the number of S sources: Fe Atomic number = 19: 1). No additives were used in the electrolyte. Other conditions were the same as in Example 32.

[0202] (Comparative Example 5)

The layer containing the negative electrode active material is a composite of mechanically milled Si particles with an average particle size of 10 m and Fe particles corresponding to element X with an average particle size of 10 μm as the negative electrode active material other than the carbon material. (Number of Si atoms: number of Fe atoms = 9: 1). Amorphous carbon was used as the carbon material. No additives were used in the electrolyte. Other conditions were the same as in Example 32.

[0203] (Example 38)

The layer containing the negative electrode active material was formed by depositing Si as a negative electrode active material other than the carbon material by vapor deposition. Graphite was used as the carbon material. LiMn 2 O was used as the positive electrode active material contained in the layer containing the positive electrode active material. PC / EC / DEC = 20/2 for electrolyte

twenty four

In 0/60 (volume ratio), lmol / L of LiPF as electrolyte and compound N as additive

6

o.1 containing 0.5% by mass was used. For the battery exterior, a container was made of a member coated with aluminum foil by lamination and used. The capacity ratio A / C balance between the positive and negative electrodes was set to 1.05.

[0204] (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. Other conditions were the same as in Example 38.

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

(Example 41)

The layer containing the negative electrode active material was formed by depositing Si as a negative electrode active material other than the carbon material by vapor deposition. In addition, 0.5% by mass of Compound No. 1 and 3% by mass of 1,3-PS were used as additives. 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, 0.5% by mass of Compound No. 1 and 3% by mass of 1,3-PS were used as additives. Other conditions were the same as in Example 38.

(Example 43)

The layer containing the negative electrode active material was formed by simultaneously forming films using two sputtering sources, Si and Fe corresponding to the element X, as the negative electrode active material other than the carbon material (the number of Si atoms: the number of Fe atoms = 7: 3). As additives, 0.5% by mass of Compound No. 1 and 3% by mass of 1,3-PS were used. Other conditions were the same as in Example 38.

(Example 44)

The layer containing the negative electrode active material was formed by simultaneously forming films using two sputtering sources, Si and Fe corresponding to the element X, as the negative electrode active material other than the carbon material (the number of Si atoms: the number of Fe atoms = 7: 3). The additives used were 0.5% by mass of the compound Νο · 1, 3% by mass of 1,3_PS, and 1% by mass of VC. Other conditions were the same as in Example 38.

(Example 45)

The layer containing the negative electrode active material was formed by simultaneously forming films using two sputtering sources, Si and Fe corresponding to the element X, as the negative electrode active material other than the carbon material (the number of Si atoms: the number of Fe atoms = 7: 3). As additives, 0.5% by mass of Compound No. 1 and 0.5% by mass of MMDS were used. Other conditions were the same as in Example 38.

[0211] (Comparative Example 6)

The layer containing the negative electrode active material corresponds to Si and element X as the negative electrode active material other than the carbon material. A film was formed by using two sputtering sources simultaneously with Fe (the number of Si atoms: the number of Fe atoms = 7: 3). No additives were used in the electrolyte. Other conditions were the same as in Example 38.

[0212] (Comparative Example 7)

The layer containing the negative electrode active material was formed by simultaneously forming films using two sputtering sources, Si and Fe corresponding to the element X, as the negative electrode active material other than the carbon material (the number of Si atoms: the number of Fe atoms = 7: 3). In addition, 3% by mass of 1,3-PS was used for the electrolyte. Other conditions were the same as in Example 38.

(Example 46)

The layer containing the negative electrode active material was formed by simultaneously forming films using two sputtering sources, Si and Fe corresponding to the element X, as the negative electrode active material other than the carbon material (the number of Si atoms: the number of Fe atoms = 7: 3). Graphite was used as the carbon material. LiCoO was used as the positive electrode active material contained in the layer containing the positive electrode active material. EC / DEC / EMC = 30/50/20 (body

2

In the product ratio), 1 mol / L of LiPF as an electrolyte and Compound No.

6

One containing 1% by mass was used. An 18650 cylindrical container was used for the battery exterior. The capacity ratio A / C balance between the positive and negative electrodes was set to 1.05.

(Example 47)

As an additive, Compound No. 1 was used in an amount of 0.1% by mass. Other conditions were the same as in Example 46.

(Example 48)

As an additive, 0.75% by mass of Compound No. 1 was used. Other conditions were the same as in Example 46.

(Example 49)

As an additive, 3% by mass of Compound No. 1 was used. Other conditions were the same as in Example 46.

(Example 50)

As an additive, compound No. 1 was used in an amount of 5% by mass. Other conditions were the same as in Example 46. (Example 51)

8% by mass of Compound No. 1 was used as an additive. Other conditions were the same as in Example 46.

[0219] (Comparative Example 8)

No additives were used in the electrolyte. 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 compounding graphite particles having an average particle diameter of 10 μm and Si particles having an average particle diameter of 1 am by mechanical milling. LiCoO was used as the positive electrode active material contained in the layer containing the positive electrode active material. EC / DE as electrolyte

2

In C / EMC = 30/50/20 (volume ratio), lmol / L of LiPF and electrolyte

6 An additive containing 0.5% by mass of Compound No. 1 was used. A rectangular container was used for the battery exterior. The capacity ratio between the positive and negative electrodes AZC balance was set to 1.05.

(Example 53)

The layer containing the negative electrode active material was prepared using composite particles obtained by compounding graphite particles having an average particle size of 10 μm and Sn particles having an average particle size of 1 μm by mechanical milling. Other conditions were the same as in Example 52.

(Example 54)

The layer containing the negative electrode active material consists of composite particles obtained by mechanically milling Si particles with an average particle size of 1 μm and Ni particles with an average particle size of 1 μm, and graphite particles with an average particle size of 10 μm. And were prepared using composite particles obtained by mechanofusion (number of Si atoms: number of Ni atoms = 9: 1). Other conditions were the same as in Example 52.

(Comparative Example 9)

No additives were used in the electrolyte. Other conditions were the same as in Example 52.

(Example 55)

The layer containing the negative electrode active material is a composite particle obtained by combining graphite particles with an average particle size of 10 μm and Si particles with an average particle size of 1 am by mechanical milling and carbon coating by CVD. It was produced using. LiCoO was used as the positive electrode active material contained in the layer containing the positive electrode active material. ECZDEC / EMC = 30/50/20 (volume ratio) for electrolyte Inside, lmol / L LiPF as electrolyte and 0.5 mass of Compound No. 1 as additive

6

% Was used. A rectangular container was used for the outer package of the battery. The capacity ratio A / C balance between the positive electrode and the negative electrode was set to 1.5.

[0225] (Example 56)

The layer containing the negative electrode active material consists of mechanically milled particles of Sn particles with an average particle size of 1 μm and Cu particles with an average particle size of 1 μm and graphite particles with an average particle size of 10 μm. It was fabricated using composite particles obtained by compounding by two-car milling and then carbon coating by CVD (number of Sn atoms: number of Cu atoms = 4: 1). Other conditions were the same as in Example 55.

(Example 57)

The layer containing the negative electrode active material is a composite particle obtained by combining graphite particles with an average particle size of 10 μm and Sn particles with an average particle size of 1 am by mechanical milling and carbon coating by CVD. It was produced using. Other conditions were the same as in Example 55.

(Comparative Example 10)

No additives were used in the electrolyte. Other conditions were the same as in Example 55.

(Example 58)

The content of the carbon material was set to 5% by mass. Other conditions were the same as in Example 1.

(Example 59)

The content of the carbon material was set to 95% by mass. Other conditions were the same as in Example 1.

[0230] (Example 60)

A layer containing a negative electrode active material was prepared by first depositing a graphite film by a sputtering method, and then depositing Si thereon by a CVD method as a negative electrode active material other than a carbon material. Other conditions were the same as in Example 1.

[0231] (Example 61)

The layer containing the negative electrode active material was prepared by depositing Si〇 as a negative electrode active material other than the carbon material by vapor deposition. Graphite was used as the carbon material. LiCoO was used as the positive electrode active material contained in the layer containing the positive electrode active material. ECZDEC / EMC = 30 for electrolyte

2

/ 50/20 (volume ratio), lmol / L LiPF as electrolyte and compound as additive A material containing 0.5% by mass of the product No. 1 was used. A rectangular aluminum container was used for the battery exterior. The capacity ratio A / C balance between the positive and negative electrodes was 1.05.

(Example 62)

The layer containing the negative electrode active material was formed by sputtering Sn〇 as a negative electrode active material other than the carbon material. Other conditions were the same as in Example 61.

(Example 63)

The layer containing the negative electrode active material was sputtered with Sn〇 as the negative electrode active material other than the carbon material.

2 Thus, a film was formed. Other conditions were the same as in Example 61.

[0234] (Example 64)

The layer containing the negative electrode active material is composed of particles obtained by mechanically milling FeO particles having an average particle size of 10 m and BO particles having an average particle size of 10 zm as the negative electrode active material other than the carbon material.

2 3 2 3

(The number of Fe atoms: the number of B atoms = 5: 5). Other conditions were the same as in Example 61.

(Example 65)

The layer containing the negative electrode active material is a particle obtained by mixing Fe O particles having an average particle size of 10 μΐη and P O particles having an average particle size of 10 / im by mechanical milling as a negative electrode active material other than the carbon material.

2 3 2 5

It was produced using. Other conditions were the same as those in Example 61 (the number of Fe atoms: the number of P atoms = 5: 5).

(Example 66)

For the layer containing the negative electrode active material, W O was sputtered as the negative electrode active material other than the carbon material.

Films were formed from 25. Other conditions were the same as in Example 61.

(Example 67)

The layer containing the negative electrode active material was prepared using Li Ti 2 O having an average particle size of 10 m as the negative electrode active material other than the carbon material. Other conditions were the same as in Example 61.

4 5 12

(Example 68)

The layer containing the negative electrode active material was prepared by mixing mechanically milled particles of Si〇 particles with an average particle size of 10 m and Sn〇 particles with an average particle size of 10 μm as the negative electrode active material other than the carbon material. Produced. Other conditions were the same as in Example 61 (number of Si atoms: number of Sn atoms = 5: 5).

(Example 69)

The layer containing the negative electrode active material was formed by simultaneous deposition using two deposition sources, Sn〇 and Li, as the negative electrode active material other than the carbon material (the number of Sn atoms: the number of L sources = 5: 5). Other conditions were the same as in Example 61.

[0240] (Example 70)

The layer containing the negative electrode active material was prepared by simultaneous deposition using two evaporation sources, Si〇 and Li, as the negative electrode active material other than the carbon material (the number of S sources: the number of Li atoms = 5: 5) Other conditions were the same as those in Example 61.

[0241] (Example 71)

Compound No. 2 was used as an additive. Other conditions were the same as in Example 61.

[0242] (Example 72)

Compound No. 3 was used as an additive. Other conditions were the same as in Example 61.

[0243] (Example 73)

Compound No. 4 was used as an additive. Other conditions were the same as in Example 61.

(Example 74)

Compound No. 6 was used as an additive. Other conditions were the same as in Example 61.

(Example 75)

Compound No. 9 was used as an additive. Other conditions were the same as in Example 61.

(Example 76)

Compound No. 10 was used as an additive. Other conditions were the same as in Example 61.

(Example 77)

Compound No. 15 was used as an additive. Other conditions were the same as in Example 61.

(Example 78)

Compound No. 16 was used as an additive. Other conditions were the same as in Example 61.

(Example 79)

Compound No. 19 was used as an additive. Other conditions were the same as in Example 61.

[0250] (Example 80) The layer containing the negative electrode active material was formed using Si〇 having an average particle size of 10 μΐη as a negative electrode active material other than the carbon material. Amorphous carbon was used as the carbon material. Other conditions were the same as in Example 61.

(Example 81)

The layer containing the negative electrode active material was prepared using Sn〇 having an average particle diameter of 10 m as a negative electrode active material other than the carbon material. Amorphous carbon was used as the carbon material. Other conditions were the same as in Example 61.

[0252] (Comparative Example 11)

The layer containing the negative electrode active material was prepared by depositing Si〇 as a negative electrode active material other than the carbon material by vapor deposition. No additives were used in the electrolyte. Other conditions were the same as in Example 61.

(Comparative Example 12)

The layer containing the negative electrode active material was formed using Si〇 having an average particle size of 10 μΐη as a negative electrode active material other than the carbon material. Amorphous carbon was used as the carbon material. No additives were used in the electrolyte. Other conditions were the same as in Example 61.

(Example 82)

The layer containing the negative electrode active material was prepared by depositing Si〇 as a negative electrode active material other than the carbon material by vapor deposition. Graphite was used as the carbon material. LiMnO was used as the positive electrode active material contained in the layer containing the positive electrode active material. PC / EC / DEC = 20 /

2

In 20/60 (volume ratio), lmol / L LiPF as electrolyte and compound as additive

6

No. 1 containing 0.5% by mass was used. An aluminum rectangular container was used for the battery exterior. The capacity ratio A / C balance between the positive and negative electrodes was 1.05.

[0255] (Example 83)

The layer containing the negative electrode active material was formed by sputtering Sn〇 as a negative electrode active material other than the carbon material. Other conditions were the same as in Example 82.

(Example 84)

2 Thus, a film was formed. Other conditions were the same as in Example 82. (Example 85)

The layer containing the negative electrode active material is composed of particles obtained by mechanically milling FeO particles having an average particle size of 10 μΐη and BO particles having an average particle size of 10 / im as a negative electrode active material other than the carbon material.

2 3 2 3

(Number of Fe atoms: number of B atoms = 5: 5). Other conditions were the same as in Example 82.

(Example 86)

The layer containing the negative electrode active material is composed of particles obtained by mechanically milling FeO particles having an average particle size of 10 m and PO particles having an average particle size of 10 zm as a negative electrode active material other than the carbon material.

2 3 2 5

(Number of Fe atoms: number of P atoms = 5: 5). Other conditions were the same as in Example 82.

(Example 87)

twenty five

It was formed by film formation. Other conditions were the same as in Example 82.

(Example 88)

The layer containing the negative electrode active material was prepared using Li Ti O having an average particle size of 10 μΐη as the negative electrode active material other than the carbon material. Other conditions were the same as in Example 82.

4 5 12

(Example 89)

The layer containing the negative electrode active material was prepared by using mechanically milled particles of Si〇 particles with an average particle size of 10 μ〇η and Sn〇 particles with an average particle size of 10 μm as the negative electrode active material other than the carbon material. (Number of Si atoms: number of Sn atoms = 5: 5). Other conditions were the same as in Example 82.

(Example 90)

The layer containing the negative electrode active material was formed by simultaneous deposition using two deposition sources, Sn〇 and Li, as the negative electrode active material other than the carbon material (the number of Sn atoms: the number of L sources = 5: 5). Other conditions were the same as in Example 82.

(Example 91)

The layer containing the negative electrode active material was prepared by simultaneous deposition using two evaporation sources, Si〇 and Li, as the negative electrode active material other than the carbon material (the number of S sources: the number of Li atoms = 5: 5) Other conditions were the same as in Example 82.

[0264] (Comparative Example 13)

The layer containing the negative electrode active material was prepared by depositing Si〇 by evaporation as a negative electrode active material other than the carbon material. No additives were used in the electrolyte. 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 evaporation sources, Si〇 and Fe, which corresponds to the element X, as the negative electrode active material other than the carbon material. : Fe atom number = 14: 1). Graphite was used as the carbon material. LiCoO was used as the positive electrode active material contained in the layer containing the positive electrode active material. ECZDEC / EMC = 30 /

2

In 50/20 (volume ratio), lmol / L of LiPF as electrolyte and compound as additive

6

No. 1 containing 0.5% by mass was used. For the battery exterior, a container was prepared from a member coated with aluminum foil and laminated. 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 films using two sputtering sources, Sn〇 and Cu corresponding to element X, as the negative electrode active material other than the carbon material (the number of Sn atoms: Cu source). Number of children = 3: 7). Other conditions were the same as in Example 92.

(Example 94)

The layer containing the negative electrode active material is formed by mechanical milling Sn-- particles with an average particle size of 10 μΐη and Ni particles corresponding to element X with an average particle size of 10 μm as the negative electrode active material other than the carbon material.

2

The mixed particles were prepared by using (number of Sn atoms: number of Ni atoms = 19: 1). 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 Sn〇 and Li and Ti corresponding to the element X as the negative electrode active material other than the carbon material (the number of Sn atoms: Li Atomic number: Ti atomic number = 1: 1: 9). 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 Si〇 and Li and Fe corresponding to the element X as the negative electrode active material other than the carbon material (the number of Si atoms: Li Atomic number: Fe atomic number = 9: 3: 1). Other conditions were the same as in Example 92.

(Example 97)

The layer containing the negative electrode active material was formed by combining mechanically milled Si〇 particles with an average particle size of 10 m and Fe particles corresponding to element X with an average particle size of 10 zm as the negative electrode active material other than the carbon material. Used (number of Si atoms: number of Fe atoms = 9: 1). Amorphous carbon was used as the carbon material. Other conditions were the same as in Example 92.

[0271] (Comparative Example 14)

The layer containing the negative electrode active material was formed by simultaneous deposition using two deposition sources, Si の and Fe, which corresponds to the element X, as the negative electrode active material other than the carbon material. : Fe atoms = 14: 1). No additives were used in the electrolyte. Other conditions were the same as in Example 92.

(Comparative Example 15)

In the layer containing the negative electrode active material, as negative electrode active materials other than carbon material, Si particles with an average particle size of 10 μ 平均 η and Fe particles corresponding to element X with an average particle size of 10 μm were compounded by mechanical milling. (Number of Si atoms: number of Fe atoms = 9: 1). Amorphous carbon was used as the carbon material. No additives were used in the electrolyte. Other conditions were the same as in Example 92.

(Example 98)

The layer containing the negative electrode active material was prepared by depositing Si〇 by evaporation as a negative electrode active material other than the carbon material. Graphite was used as the carbon material. LiMn 2 O was used as the positive electrode active material contained in the layer containing the positive electrode active material. PC / EC / DEC = 20 for electrolyte

twenty four

6

A material containing 0.5% by mass of the product No. 1 was used. For the battery exterior, a container was prepared from a member coated with aluminum foil and laminated. The capacity ratio AZC of the positive and negative electrodes was set to 1.05.

(Example 99) The layer containing the negative electrode active material was formed by depositing Sn〇 as a negative electrode active material other than the carbon material by vapor deposition. Other conditions were the same as in Example 98.

(Example 100)

The layer containing the negative electrode active material was prepared by simultaneously forming films using two sputtering sources of Si〇 and Fe corresponding to the element X as the negative electrode active material other than the carbon material (the number of Si atoms: Fe atom Number = 7: 3). Other conditions were the same as in Example 98.

(Example 101)

The layer containing the negative electrode active material was prepared by depositing Si〇 by evaporation as a negative electrode active material other than the carbon material. As additives, 0.5% by mass of compound No. 1 and 3% by mass of 1,3-PS were used. Other conditions were the same as in Example 98.

(Example 102)

The layer containing the negative electrode active material was formed by depositing Sn〇 as a negative electrode active material other than the carbon material by vapor deposition. As additives, 0.5% by mass of Compound No. 1 and 3% by mass of 1,3-PS were used. Other conditions were the same as in Example 98.

(Example 103)

The layer containing the negative electrode active material was prepared by simultaneously forming films using two sputtering sources of Si〇 and Fe corresponding to the element X as the negative electrode active material other than the carbon material (the number of Si atoms: Fe atom Number = 7: 3). In addition, 0.5% by mass of Compound No. 1 and 3% by mass of 1,3_PS were used as additives. Other conditions were the same as in Example 98.

(Example 104)

The layer containing the negative electrode active material was prepared by simultaneously forming films using two sputtering sources of Si〇 and Fe corresponding to the element X as the negative electrode active material other than the carbon material (the number of Si atoms: Fe atom Number = 7: 3). As additives, 0.5% by mass of compound No. 1, 3% by mass of 1,3-PS, and 1% by mass of VC were used. Other conditions were the same as in Example 98.

[0280] (Example 105)

The layer containing the negative electrode active material was prepared by simultaneously forming films using two sputtering sources of Si〇 and Fe corresponding to the element X as the negative electrode active material other than the carbon material (the number of Si atoms: Fe atom Number = 7: 3). The additives were compound No. 1 at 0.5% by mass and MMDS at 0.5% by mass. %Using. Other conditions were the same as in Example 98.

[0281] (Comparative Example 16)

The layer containing the negative electrode active material was prepared by simultaneously forming films using two sputtering sources of Si〇 and Fe corresponding to the element X as the negative electrode active material other than the carbon material (the number of Si atoms: Fe atom Number = 7: 3). No additives were used in the electrolyte. Other conditions were the same as in Example 98.

[0282] (Comparative Example 17)

The layer containing the negative electrode active material was prepared by simultaneously forming films using two sputtering sources of Si〇 and Fe corresponding to the element X as the negative electrode active material other than the carbon material (the number of Si atoms: Fe atom Number = 7: 3). In addition, 3% by mass of 1,3-PS was used as an additive. Other conditions were the same as in Example 98.

(Example 106)

The layer containing the negative electrode active material was prepared by simultaneously forming films using two sputtering sources of Si〇 and Fe corresponding to the element X as the negative electrode active material other than the carbon material (the number of Si atoms: Fe atom Number = 7: 3). Graphite was used as the carbon material. LiCoO was used as the positive electrode active material contained in the layer containing the positive electrode active material. EC / DEC / EMC = 30/50/20 (

2

In the volume ratio), 1 mol / L of LiPF was used as the electrolyte, and Compound No. 1 was used as an additive.

6

.01% by mass. An 18650 cylindrical container was used for the battery exterior. The capacity ratio A / C balance between the positive electrode and the negative electrode was 1.05.

(Example 107)

As an additive, Compound No. 1 was used in an amount of 0.1% by mass. Other conditions were the same as in Example 106.

(Example 108)

As an additive, 0.75% by mass of Compound No. 1 was used. Other conditions were the same as in Example 106.

(Example 109)

As an additive, 3% by mass of Compound No. 1 was used. Other conditions were the same as in Example 106. (Example 110)

As an additive, compound No. 1 was used in an amount of 5% by mass. Other conditions were the same as in Example 106.

(Example 111)

8% by mass of Compound No. 1 was used as an additive. Other conditions were the same as in Example 106.

(Comparative Example 18)

No additives were used in the electrolyte. Other conditions were the same as in Example 106.

(Example 112)

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 SiO 2 particles having an average particle diameter of 1 am by mechanical milling. LiCoO was used as the positive electrode active material contained in the layer containing the positive electrode active material. EC / D for electrolyte

2

EC / EMC = 30/50/20 (volume ratio), lmol / L LiPF as electrolyte and

6 An additive containing 0.5% by mass of Compound No. 1 was used. A rectangular container was used for the battery exterior. The capacity ratio A / C balance between the positive and negative electrodes was 1.05.

(Example 113)

The layer containing the negative electrode active material was prepared using composite particles obtained by compounding graphite particles having an average particle diameter of 10 μm and Sn 2 O 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 obtained by mechanically milling SiO particles having an average particle size of 1 μm and Ni particles having an average particle size of 1 μm, and graphite particles having an average particle size of 10 μm. Was prepared by using composite particles obtained by compounding by mechanical filtration (number of Si atoms: number of atoms = 9: 1). Other conditions were the same as in Example 112.

[0293] (Comparative Example 19)

No additives were used in the electrolyte. Other conditions were the same as in Example 112.

(Example 115)

The layer containing the negative electrode active material was composed of graphite particles with an average particle size of 10 μm and Si particles with an average particle size of 1 O particles were compounded by mechanical milling, and carbon particles were coated by CVD to produce composite particles. LiCoO was used as the positive electrode active material contained in the layer containing the positive electrode active material. EC / DEC / EMC = 30/50/20 (volume ratio) for electrolyte

2

Inside, lmol / L LiPF as electrolyte and 0.5 mass of Compound No. 1 as additive

6

% Was used. A rectangular container was used for the outer package of the battery. The capacity ratio A / C balance between the positive electrode and the negative electrode was set to 1.05.

(Example 116)

The layer containing the negative electrode active material is composed of SnO particles having an average particle diameter of 1 μm and Cu particles having an average particle diameter of 1 μm alloyed by mechanical milling and graphite particles having an average particle diameter of 10 am. It was fabricated using composite particles obtained by compounding by force-calendering and then carbon coating by CVD (number of Sn atoms: number of Cu atoms = 4: 1). Other conditions were the same as in Example 115.

(Example 117)

The layer containing the negative electrode active material is a composite obtained by combining graphite particles with an average particle size of 10 μm and SnO particles with an average particle size of 1 μm by mechanical milling, and then carbon coating by CVD. It was prepared using particles. Other conditions were the same as in Example 115.

[0297] (Comparative Example 20)

No additives were used in the electrolyte. Other conditions were the same as in Example 115.

(Example 118)

The content of the carbon material was set to 5% by mass. Other conditions were the same as in Example 61.

(Example 119)

The content of the carbon material was set to 95% by mass. Other conditions were the same as in Example 61.

[0300] (Example 120)

A layer containing a negative electrode active material was formed by first depositing a graphite film by a sputtering method and then depositing SiO thereon by a CVD method as a negative electrode active material other than a carbon material. Other conditions were the same as in Example 61.

[0301] (Example 121)

The layer containing the negative electrode active material is composed of two layers of negative electrode active materials other than carbon materials: Si and Si〇. (S source number: 0 atom number: 2: 1). Other conditions were the same as in Example 1.

[0302] (Example 122)

The layer containing the negative electrode active material was formed by simultaneous sputtering using two sputtering sources of Sn and Sn〇 as the negative electrode active material other than the carbon material (the number of Sn atoms: the number of O atoms). = 2: 1). Other conditions were the same as in Example 1.

[0303] (Example 123)

The layer containing the negative electrode active material is composed of a mixture of Si, Si〇, and Li

2

A film was formed by simultaneous evaporation using three evaporation sources (S element number: 0 atom number: Li atom number = 1: 1: 1: 1). Other conditions were the same as in Example 1.

[0304] (Example 124)

The layer containing the negative electrode active material contains Sn, Sn 負極, and Li as the negative electrode active material other than the carbon material.

A film was formed by simultaneous evaporation using three evaporation sources 2 and 3 (the number of Sn atoms: the number of atoms: the number of Li atoms = 1: 1: 1: 1). 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 size of 1 μm and SiO having an average particle size of 1 μm as a negative electrode active material other than the carbon material. Incidentally mixing ratio, and the average particle size 1 _beta m number Si atoms in the Si of the average particle diameter 1 mu m Number of SiO molecules, the ratio of 1: 1 and so as. The other conditions were the same as in Example 1.

(Example 126)

The layer containing the negative electrode active material is composed of particles obtained by mechanically milling Sn having an average particle diameter of 1 βm and Sn〇 having an average particle diameter of 1 μm as the negative electrode active material other than the carbon material (the number of Sn atoms: the number of O atoms). = 2: 1). Other conditions were the same as in Example 1.

(Example 127)

The layer containing the negative electrode active material was formed by simultaneous deposition using three deposition sources of Si, Si〇, and Fe corresponding to the element X as the negative electrode active material other than the carbon material (Si atom Number: O atoms: Fe atoms = 14: 7: 6). Other conditions were the same as in Example 1.

(Example 128) The layer containing the negative electrode active material has an average particle diameter of 1 βm as a negative electrode active material other than the carbon material.

Particles (Sn atoms: O atoms: Fe atoms = 14: 7: 6) were prepared by mechanically milling a mixture of Sn, Sn〇 with an average particle size of 1 μm, and Fe with an average particle size of 1 μm. Thereafter, composite particles were prepared by using mechanical milling to combine the particles with graphite particles having an average particle diameter of 10 μm. Other conditions were the same as in Example 1.

(Example 129)

Compound No. 2 was used as an additive. Other conditions were the same as in Example 127.

[0310] (Example 130)

Compound No. 3 was used as an additive. Other conditions were the same as in Example 127.

[0311] (Example 131)

Compound No. 4 was used as an additive. Other conditions were the same as in Example 127.

[0312] (Example 132)

Compound No. 6 was used as an additive. Other conditions were the same as in Example 127.

[0313] (Example 133)

Compound No. 9 was used as an additive. Other conditions were the same as in Example 127.

[0314] (Example 134)

Compound No. 10 was used as an additive. Other conditions were the same as in Example 127.

[0315] (Example 135)

Compound No. 15 was used as an additive. Other conditions were the same as in Example 127.

[0316] (Example 136)

Compound No. 16 was used as an additive. Other conditions were the same as in Example 127.

[0317] (Example 137)

Compound No. 19 was used as an additive. Other conditions were the same as in Example 127.

[0318] (Example 138)

The layer containing the negative electrode active material was formed by simultaneous deposition using two deposition sources, Si and Si〇, as the negative electrode active material other than the carbon material (the number of Si atoms: 0 atoms = twenty one). Other conditions were the same as in Example 22.

[0319] (Example 139) The layer containing the negative electrode active material was formed by simultaneous sputtering using two sputtering sources of Sn and Sn〇 as the negative electrode active material other than the carbon material (the number of Sn atoms: the number of O atoms). = 2: 1). Other conditions were the same as in Example 22.

[0320] (Example 140)

2

A film was formed by simultaneous evaporation using three evaporation sources (S element number: 0 atom number: Li atom number = 1: 1: 1: 1). Other conditions were the same as in Example 22.

[0321] (Example 141)

A film was formed by simultaneous evaporation using the three evaporation sources 2 and 3 (the number of Sn atoms: the number of atoms: the number of Li atoms = 1: 1: 1: 1). 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 size of 1 μm and SiO having an average particle size of 1 μm as a negative electrode active material other than the carbon material. Incidentally mixing ratio, and the average particle size 1 _beta m number Si atoms in the Si of the average particle diameter 1 mu m Number of SiO molecules, the ratio of 1: 1 and so as. Other conditions were the same as in Example 22.

(Example 143)

The layer containing the negative electrode active material is composed of particles obtained by mechanically milling Sn having an average particle diameter of 1 βm and Sn〇 having an average particle diameter of 1 μm as the negative electrode active material other than the carbon material (the number of Sn atoms: the number of O atoms). = 2: 1). Other conditions were the same as in Example 22.

[0324] [Table 1]

[zm [szso]

OOZdf / IOd 19 SI ..S0 / S00Z ΟΛ \

[S 挲] [92S0]

SlL8l0 / 00Zdr / 13d 89 ST..S0 / S00Z OAV [挲] [Z2S0]

SlL8l0 / P00Zdr / 13d 69 ST ..S0 / S00Z OAV

Capacity retention rate after 400 cycles (capacity retention rate after 400 cycles) (%) Resistance retention rate Example 1 84.1 1.42 Example 2 80.8 1.40 Example 3 77.4 1.50 Example 4 79.4 1.55 Example 5 84.2 1.47 Example 6 78.8 1.62 Example 7 76.5 1.60 Example 8 77.7 1.55 Example 9 81.6 1.36 Example 10 83.5 1.27 Example 1 1 81.5 1.40 Example 12 82.6 1.41 Example 13 85.0 1.51 Example 14 82.6 1.37 Example 15 82.4 1.51 Example 16 80.8 1.41 Example 17 83.8 1.43 Example 18 84.2 1.41 Example 19 83.6 1.38 Example 20 81.1 1.43 Example 21 81.3 1.46 Comparative example 1 14.6 2.70 Comparative example 2 20.1 2.99 Example 22 76.3 1.57 Example 23 74.4 1.59 Example 24 72.5 1.84 Example 25 73.6 1.77 Example 26 80.0 1.58 Example 27 74.9 1.76 Example 28 70.9 1.63 Example 29 70.6 1.70 Example 30 75.1 1.57 Example 31 77.6 1.49 Comparative example 3 11.5 2.89 Example 32 84.2 1.23 Example 33 82.9 1.28 Example 34 82.5 1.54 Example 35 83.7 1.50 Example 36 87.1 1.22 Example 37 82.5 1.39 Comparison 4 24.1 2.89 Comparative Example 5 26.5 3.02 [0330] [Table 7]

[0331] [Table 8]

Capacity maintenance rate after 400 cycles after 400 cycles (%) Resistance maintenance rate Example 61 89.4 1.53 Example 62 85.4 1.53 Example 63 81.5 1.60 Example 64 84.3 1.62 Example 65 88.7 1.52 Example 66 85.9 1.73 Example 67 81.6 1.71 Example 68 82.5 1.70 Example 69 85.3 1.50 Example 70 88.3 1.43 Example 71 84.0 '1.55 Example 72 86.4 1.54 Example 73 85.2 1.46 Example 74 88.3 1.40 Example 75 88.4 1.52 Example 76 86.2 1.55 Example 77 85.8 1.36 Example 78 82.6 1.40 Example 79 86.6 1.47 Example 80 85.6 1.57 Example 81 84.3 1.58 Comparative example 1 1 14.6 2.82 Comparative example 12 18.6 3.03 Example 82 79.7 1.71 Example 83 77.6 1.72 Example 84 74.3 1.88 Example Example 85 80.1 1.95 Example 86 81.6 1.64 Example 87 78.0 1.81 Example 88 76.0 1.68 Example 89 75.4 1.83 Example 90 82.0 1.68 Example 91 82.1 1.55 Comparative example 13 1 1.7 3.06 Example 92 91.6 1.38 Example 93 88.9 1.48 Example 94 88.2 1.61 Example 95 89.6 1.50 Example 96 90.9 1.29 Example 97 86. 1 1.52 Comparative example 14 27.5 3.00 Comparative example 15 29.0 3.33 Capacity retention rate after 400 cycles after 400 cycles (%) Resistance retention rate Example 98 83.9 1.62 Example 99 86.1 1.56 Example 100 85.8 1.55 Example 101 87.9 1.52 Example 102 86.2 1.52 Example 103 91.5 1.46 Example 104 92.8 1.49 Example 105 89.5 1.60 Comparative Example 16 27.1 2.63 Comparative Example 17 44.7 2.17 Example 106 79.3 1.82 Example 107 85.4 1.64 Example 108 86.5 1.42 Example 109 88.9 1.34 Example 110 84.0 1.49 Example 111 81.3 2.00 Comparative Example 18 25.2 2.75 Example 112 86.2 1.55 Example 113 86.7 1.51 Example 114 87.1 1.49 Comparative Example 19 19.1 2.95 Example 115 83.1 1.48 Example 116 83.9 1.44 Example 117 83.2 1.49 Comparative Example 20 28.5 2.89 Example 1 18 ■ 81.5 1.55 Example Example 119 83.0 1.31 Example 120 82.0 1.42]

After 400 cycles After 400 cycles

Capacity maintenance rate (%) Resistance maintenance rate Example 121 84.1 1.51

Example 122 82.7 1.48

Example 123 85.2 1.47

Example 124 83.6 1.45

Example 125 75.6 1.65

Example 126 84.2 1.53

Example 127 83.5 1.47

Example 128 82.6 1.46

Example 129 83.5 1.47

Example 130 82.9 1.45

Example 131 81.9 1.49

Example 132 83.0 1.50

Example 133 82.7 1.44

Example 134 82.4 1.51

Example 135 84.6 1.46

Example 136 83.1 1.45

Example 137 82.8 1.48

Example 138 83.1 1.52

Example 139 82.9 1.50

Example 140 84.0 1.48

Example 141 84.2 1.49

Example 142 78.9 1.61

Example 143 82.9 1.50

(Verification of the effect of the compound represented by the general formula (1))

The capacity retention rate in Examples 1 to 10 is much larger than the capacity retention rate of Comparative Example 1. Elements which, depending on the compound No. 1, occludes' releasing alkali metal or alkaline earth metal as an anode active material, the element M ^ M ¹ is selected Si, Sn, Al, Pb, Ag, Ge, and Sb In the case of batteries using at least one metal or metalloid and carbon material containing at least one), 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. The reason is considered as a reason. A similar tendency was observed in Examples 11 to 19, and the effect of the compound represented by the general formula (1) was confirmed. A similar tendency was observed in a comparison between Examples 20 and 21 using amorphous carbon as the carbon material and Comparative Example 2. Example 22 using LiMnO as positive electrode active material Capacity of 31

2

The retention rate was also significantly higher than the capacity retention rate of Comparative Example 3 not containing Compound No. 1, It was confirmed that the same effect as in Example 1 was obtained.

[0335] It can be seen that Examples 32 to 36 have a higher capacity retention ratio during the cycle than Comparative Example 4. A similar tendency was observed in a comparison between Example 37 using amorphous carbon as the carbon material and Comparative Example 5. From these results, it can be seen that the same effect as in Example 1 can be obtained in the case of a battery using the above-mentioned metal or metalloid and the carbon material and the element X which does not alloy with the alkali metal or alkaline earth metal as the negative electrode active material. Was confirmed.

[0336] The capacity retention ratios of Examples 61 to 70 are much larger than the capacity retention ratio of Comparative Example 11. This is because compound No. 1 stabilizes the surface film present on the negative electrode surface in the case of batteries using oxides and carbon materials that occlude and release alkali metals or alkaline earth metals as the negative electrode active material. This is probably because the high ionic conductivity of the membrane suppressed the irreversible reaction. The same tendency was observed in Example 7179, and the effect of the compound represented by the general formula (1) was confirmed. A similar tendency was observed in the comparison between Examples 80 and 81 using amorphous carbon as the carbon material and Comparative Example 12. Example 82-91 using LiMnO as positive electrode active material

2

The capacity retention ratio of Comparative Example 13 not containing Compound No. 1 was significantly higher than that of Comparative Example 13, and it was confirmed that the same effect as that of Example 61 was obtained.

[0337] It can be seen that Examples 92-96 have a higher capacity retention rate during cycling than Comparative Example 14. A similar tendency was observed in a comparison between Example 97 using amorphous carbon as the carbon material and Comparative Example 15. This result indicates that the oxides and carbon materials that occlude and release alkali metals or alkaline earth metals should not be alloyed with alkali metals or alkaline earth metals. It was confirmed that the same effect as in Example 61 was obtained.

[0338] The capacity retention ratios in Examples 121 to 125 were significantly higher than those in Comparative Examples 1 and 11. This is due to the fact that compound No. 1 stabilizes the surface film present on the negative electrode surface in the case of a battery that uses a metal or metal oxide together with an oxide as the negative electrode active material, and further uses a carbon material. This may be because the irreversible reaction was suppressed due to the high ionic conductivity. Example 138 using LiMnO as positive electrode active material

2

The capacity retention of 142 was also larger than the capacity retention of Comparative Examples 3 and 13, which did not contain Compound No. 1. Thus, it was confirmed that the same effect as in Example 121 was obtained.

[0339] 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 these results, it can be seen that in the case of a battery using a metal or metalloid and an oxide in combination as an anode active material, and further using a carbon material and an element X that does not alloy with an alkali metal or an alkaline earth metal as the anode active material. Also, it was confirmed that the same effect as in Example 121 was obtained. The same tendency was observed in Examples 129 to 137, and the effect of the compound represented by the general formula (1) was confirmed.

Further, when the negative electrode surface of the batteries prepared in Examples 1 and 61 after the 400 cycle test was examined by X-ray photoelectron spectroscopy (XPS), a substance having a peak at around 164 eV based on a sulfur atom was found. Confirmed that it exists. In the system containing no additive, there was no substance having a peak around 164 eV. In the system using only 1,3-PS, the substance had a peak near 164 eV. The strength was weak. Therefore, it is considered that the film derived from Compound No. 1 was formed preferentially.

[0341] (Verification of effect of adding cyclic sulfonic acid ester)

The capacity retention rate after the cycle test in Examples 38 to 40 was higher than that in Comparative Example 6, and the capacity retention rate after the cycle test in Examples 41 to 43 to which 1,3-PS was added was And Example 38-40 are further improved. A similar tendency was observed in Example 45 in which MMDS was added. This is because the addition of a cyclic sulfonate such as 1,3-PS or MMDS further stabilizes the film present on the negative electrode surface, and the higher ionic conductivity of the film further increases the irreversible reaction. The reason may be that it was suppressed. However, when 1,3-PS is used alone as an additive as in Comparative Example 7, the effect of improving the capacity retention ratio is not so large.

[0342] The capacity retention rate after the cycle test in Examples 98-100 was higher than that in Comparative Example 16, and the capacity after the cycle test in Examples 101-103 to which 1,3-PS was added. The quantity retention is even better than in Example 98 100. A similar tendency was observed in Example 105 to which MMDS was added. This is because the addition of cyclic sulfonic acid ester such as 1,3-PS or MMDS further stabilizes the film present on the negative electrode surface, and further increases the irreversible reaction due to the higher ion conductivity of the film. Because it was suppressed Is considered as a reason. However, when 1,3-PS was used alone as an additive as in Comparative Example 17, the effect of improving the capacity retention rate was not so large.

[Verification of the effect of adding VC]

In the battery shown in Example 44, the capacity retention after the cycle test was further improved as compared with Example 43, that is, the cycle characteristics were improved by further adding VC to the electrolyte. Was confirmed. The reason for this is thought to be the same as the reason for the addition of 1,3-PS described above.

[0344] In the battery shown in Example 104, the capacity retention ratio after the cycle test was further improved as compared with Example 103, that is, the cycle characteristics were improved by further adding VC to the electrolytic solution. It was confirmed that. The reason for this is also considered to be the same as the above-mentioned reason for adding 1,3-PS.

[0345] (Verification of effect of change in concentration of additive in electrolyte solution)

From Examples 46-51, the capacity retention rate after 400 cycles tended to decrease at concentrations of compound No. 1 below 0.1% by mass and above 5.0% by mass. In addition, the rate of increase in resistance tended to increase. From these results, it was confirmed that the concentration of the compound represented by the general formula (1) in the electrolytic solution is preferably from 0.1% by mass to 5.0% by mass.

[0346] From Examples 106 to 111, the capacity retention rate after 400 cycles tended to decrease when the concentration of compound No. 1 was less than 0.1% by mass and more than 5.0% by mass. In addition, the resistance rise rate tended to increase. From these results, it was confirmed that the concentration of the compound represented by the general formula (1) in the electrolytic solution was preferably from 0.1% by mass to 5.0% by mass.

[0347] (Verification when using composite particles as negative electrode active material)

The capacity retention ratio and the resistance retention ratio after the cycle test in Examples 52 to 54 were higher than those in Comparative Example 9. From these results, it was confirmed that the same effect as in Example 1 was obtained in the case of the battery using the composite particles as the negative electrode active material.

[0348] The capacity retention ratio and the resistance retention ratio after the cycle test in Examples 112 to 114 were higher than those in Comparative Example 9. From this result, it was found that the electrode using composite particles as the negative electrode active material In the case of a pond, it was confirmed that the same effect as in Example 61 was obtained.

[0349] The capacity retention ratio and the resistance retention ratio after the cycle test in Example 128 were measured in Comparative Example 9 and

It is higher than 19. From this result, it was confirmed that the same effect as in Example 121 was obtained also in the case of the battery using the composite particles as the negative electrode active material.

[0350] (Verification when using composite particles and graphite particles as the negative electrode active material)

The capacity retention ratio and resistance retention ratio after the cycle test in Examples 55-57 were

It is higher than 0. From these results, it was confirmed that the same effect as in Example 1 was obtained in the case of the battery using the composite particles as the negative electrode active material.

[0351] The capacity retention ratio and the resistance retention ratio after the cycle test in Examples 115 to 117 were higher than those in Comparative Example 20. From these results, it was confirmed that the same effect as in Example 61 was obtained in the case of the battery using the composite particles as the negative electrode active material.

[0352] (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) were all good.

Example 61 (carbon material content: 50% by mass) and Examples 118 (5% by mass) and 119 (

(95% by mass) was confirmed to be good.

[0354] (Verification of effect by method of forming carbon material film)

It was confirmed that the results of Example 1 (coating method) and Example 60 (sputtering method) had good results and deviation.

[0355] The results of Example 61 (coating method) and Example 120 (sputtering method) were both confirmed to be good.

Claims

The scope of the claims

In a secondary battery including at least a positive electrode, a negative electrode, and an electrolyte,

A secondary battery, wherein the electrolytic solution contains at least an aprotic solvent in which an electrolyte is dissolved and a compound represented by the following general formula (1).

[Chemical 1]

14

Substituted or unsubstituted alkyl group having 15 carbon atoms, substituted or unsubstituted alkoxy group having 15 carbon atoms, substituted or unsubstituted fluoroalkyl group having 15 carbon atoms, polyfluoro group having 15 carbon atoms SO X (X is a substituted or unsubstituted C 1 -C 5

2 1 1

Alkyl group), -SY (Y is a substituted or unsubstituted alkyl group having 115 carbon atoms), CO

1 1

twenty three

A substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted fluoroalkyl group having 1 to 5 carbon atoms, C15 polyfluoroalkyl group, substituted or unsubstituted C15 fluoroalkoxy group, C15 polyfluoroalkoxy group, hydroxyl group, halogen atom, -NX X ( X and X are each independently a hydrogen atom,

2 3 2 3

Or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms), and one NY CONY Y (Y

2 3 4 2 1 Y is each independently a hydrogen atom or a substituted or unsubstituted

Four

Alkyl group), power Indicates the atom or group to be selected. ) [2] The element M ¹ (where M ¹ is selected from Si, Sn, Al, Pb, Ag, Ge and Sb), wherein the negative electrode absorbs and releases an alkali metal or an alkaline earth metal as a negative electrode active material. 2. The secondary battery according to claim 1, wherein the secondary battery comprises a metal or metalloid containing at least one element) 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] ratio of the element M ¹ and the element X, the element M ¹ in atomic ratio: element X = 19: 1-1: Secondary according to claim 3, wherein it is a 9 battery.

[6] The carbon material is graphite, amorphous carbon, carbon nanotube, carbon nanohorn.

The secondary battery according to any one of claims 2 to 5, wherein the secondary battery is at least one selected from carbon, fullerene, diamond-like carbon, soft carbon, hard carbon, and a mixture thereof.

[7] The secondary battery according to any one of claims 2 to 6, wherein the content of the carbon material with respect to the entire negative electrode active material is 5 to 95% by mass.

[8] The secondary battery according to any one of claims 2 to 7, wherein the negative electrode active material includes particles containing at least one of the metal or metalloid and the carbon material.

9. The secondary battery according to claim 8, wherein the particles are composite particles containing both the metal or metalloid and the carbon material.

10. 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.

11. 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.

12. The secondary battery according to claim 8, wherein the surface of the particles is coated with a carbon film.

13. The secondary battery according to claim 212, wherein the negative electrode active material is formed by a vacuum film forming method or a pressure welding method. 14. The secondary battery according to claim 13, wherein the vacuum film forming method is any one of vacuum evaporation, sputtering, and CVD.

15. The secondary battery according to claim 13, wherein the pressure welding method is a mechanofusion method or a mechanical milling method.

16. The secondary battery according to claim 215, wherein the negative electrode has a layer containing at least a part of the negative electrode active material and formed by a coating method or a vacuum film forming method. .

17. The negative electrode active material has a layered structure including a layer mainly composed of the metal or metalloid and a layer mainly composed of the carbon material. The rechargeable battery according to any one of the items 16.

[18] The method according to [217], wherein 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 based on the total mass of the electrolytic solution. The secondary battery according to any one of the above.

[19] The secondary battery according to any one of claims 2 to 18, wherein the electrolytic solution further comprises a cyclic monosulfonic acid ester represented by the following general formula (2).

20. The secondary battery according to claim 2, wherein the electrolytic solution further comprises a cyclic sulfonate having two sulfonyl groups represented by the following general formula (3). pond.

[Formula 3]

(3)

(However, in the above general formula (3), Q is an oxygen atom, a methylene group or a single bond, A is a substituted or unsubstituted alkylene group having 115 carbon atoms, a carbonyl group, a sulfinyl group, a carbon atom having 11 carbon atoms. In a polyfluoroalkylene group of 5, a substituted or unsubstituted fluoroalkylene group having 15 to 15 carbon atoms, or a substituted or unsubstituted alkylene group having 15 to 15 carbon atoms, at least one of the C-C bonds is C-C基 C-bonded groups, groups in which at least one of the C-C bonds in the C15 polyfluoroalkylene group is C_ C_C-bonded, and substituted or unsubstituted A group in which at least one of the C—C bonds in the fluoroalkylene group having 115 carbon atoms is a C_〇_C bond or a group selected from the group B is a substituted or unsubstituted carbon atom having 1 to 5 carbon atoms 5 alkylene groups, 11-carbon polyfluoroalkyl Indicating group, and substituted or unsubstituted full O b alkylene group having a carbon number of 1 one 5, a group selected from.)

21. The secondary battery according to claim 2, wherein the electrolyte further contains at least one of vinylene carbonate and a derivative thereof.

22. The secondary battery according to claim 22, wherein the electrolyte contains a lithium salt.

[23] The lithium salt power LiPF

6, LiBF

4, LiAsF

6, LiSbF

6, LiCIO

4, LiAlCl, and Li

Four

A group consisting of N (C F SO) (C F SO) (k and m are each independently 1 or 2) k 2k + l 2 m 2m + l 2

23. The secondary battery according to claim 22, wherein the secondary battery is at least one selected from lithium salts.

[24] The aprotic solvent is selected from cyclic carbonates, chain carbonates, and aliphatic carbonates. _23. The organic solvent according to claim 2, wherein the organic solvent is at least one organic solvent selected from the group consisting of carboxylic esters, _{monolatatatones} , cyclic ethers, chain ethers, and fluorinated derivatives thereof. The secondary battery according to any one of the above.

[25] The secondary battery according to any one of claims 224, wherein the secondary battery is covered with a laminate exterior body.

26. The secondary battery according to claim 1, wherein the negative electrode contains, as a negative electrode active material, an oxide capable of inserting and extracting an alkali metal or an alkaline earth metal and a carbon material.

[27] The oxide is, (the ^{Μ 2 Si, Sn, Al,} Pb, Ag, Ge, Sb, B, P, W Ti or we selected element and) Elemental Micromax ^2, characterized in that it comprises a 27. The secondary battery according to claim 26.

28. The secondary battery according to claim 27, 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.

29. The secondary battery according to claim 28, wherein the element X is an element selected from Fe, Ni, Cu, and Ti.

[30] The element ratio of M ² and the element X, the element M ² in atomic ratio: element X = 19: 1-1: Secondary according to claim 28 or 29, wherein it is a 9 battery.

31. 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.

[32] The method according to the above, wherein the metal contains an element selected from Fe, Ni, Cu and Ti.

31. The secondary battery according to 31.

[33] The carbon material is characterized by being 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 rechargeable battery according to any one of claims 26 to 32.

34. The secondary battery according to claim 26, wherein the content of the carbon material is 5 to 95% by mass based on the whole negative electrode active material.

35. 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 particle may be a composite particle containing both the oxide and the carbon material. 36. The secondary battery according to claim 35, wherein:

37. The secondary battery according to claim 36, wherein the composite particles have at least a part of the periphery of the oxide particles covered with the carbon material.

38. The secondary battery according to claim 36, wherein the composite particles have at least a part of the periphery of the particles of the carbon material covered with the oxide.

39. The secondary battery according to claim 35, wherein the surface of the particles is covered with a carbon film.

40. The secondary battery according to claim 26, wherein the negative electrode active material is formed by a vacuum film forming method or a pressure welding method.

41. The secondary battery according to claim 40, wherein the vacuum film forming method is any one of vacuum evaporation, sputtering, and CVD.

42. The secondary battery according to claim 40, wherein the pressure welding method is a mechanofusion method or a mechanical milling method.

43. The secondary according to claim 26, wherein the negative electrode has a layer containing at least a part of the negative electrode active material and formed by a coating method or a vacuum film forming method. battery.

44. The negative electrode active material according to claim 26, wherein the negative electrode active material has a layered structure including a layer mainly containing the oxide and a layer mainly containing the carbon material. 43. The secondary battery according to any one of 43.

45. The electrolytic solution according to claim 26, wherein 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 based on the total mass of the electrolytic solution. The rechargeable battery described in any one of 44.

46. The secondary battery according to claim 26, wherein the electrolytic solution further contains a cyclic monosulfonic acid ester represented by the following general formula (2).

[Formula 4]

47. The method according to claim 26, wherein the electrolytic solution further comprises a cyclic sulfonate having two sulfonyl groups represented by the following general formula (3). secondary

[Formula 5]

(However, in the above general formula (3), Q is an oxygen atom, a methylene group or a single bond, A is a substituted or unsubstituted alkylene group having 115 carbon atoms, a carbonyl group, a sulfinyl group, a carbon atom having 11 carbon atoms. In a polyfluoroalkylene group of 5, a substituted or unsubstituted fluoroalkylene group having 15 to 15 carbon atoms, and a substituted or unsubstituted alkylene group having 15 to 15 carbon atoms, at least one of the C-C bonds is C-C基 C-bonded groups, groups in which at least one of the C-C bonds in the C15 polyfluoroalkylene group is C_ C_C-bonded, and substituted or unsubstituted At least a C--C bond in a fluoroalkylene group having 1 to 5 carbon atoms One point indicates a group that has become a COC bond and a group that can be selected. B is a group selected from a substituted or unsubstituted alkylene group having 115 carbon atoms, a polyfluoroalkylene group having 115 carbon atoms, and a substituted or unsubstituted fluoroalkylene group having 115 carbon atoms Is shown. )

48. The secondary battery according to claim 26, wherein the electrolyte further contains at least one of vinylene carbonate and a derivative thereof.

49. The secondary battery according to claim 26, wherein the electrolyte contains a lithium salt.

[50] The lithium salt power LiPF

6, LiBF

4, LiAsF

6, LiSbF

6, LiCIO

4, LiAlCl, and Li

Four

50. The secondary battery according to claim 49, wherein the secondary battery is at least one selected from lithium salts.

[51] The aprotic solvent is, cyclic carbonates, chain carbonates, aliphatic Cal Bonn acid esters, _I one Rataton, cyclic ethers, from chain ethers and the group consisting of fluoride derivatives The secondary battery according to any one of claims 26 to 50, wherein the secondary battery is at least one selected from organic solvents.

[52] The secondary battery according to any one of [26] to [51], wherein the secondary battery is covered with a laminate exterior body.