WO2005057715A1 - Accumulateur - Google Patents

Accumulateur Download PDF

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Publication number
WO2005057715A1
WO2005057715A1 PCT/JP2004/018715 JP2004018715W WO2005057715A1 WO 2005057715 A1 WO2005057715 A1 WO 2005057715A1 JP 2004018715 W JP2004018715 W JP 2004018715W WO 2005057715 A1 WO2005057715 A1 WO 2005057715A1
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Prior art keywords
negative electrode
group
carbon
secondary battery
electrode active
Prior art date
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PCT/JP2004/018715
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English (en)
Japanese (ja)
Inventor
Mariko Miyachi
Koji Utsugi
Yuki Kusachi
Hironori Yamamoto
Original Assignee
Nec Corporation
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Application filed by Nec Corporation filed Critical Nec Corporation
Priority to JP2005516241A priority Critical patent/JP4951969B2/ja
Publication of WO2005057715A1 publication Critical patent/WO2005057715A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a secondary battery.
  • 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.
  • 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.
  • a carbon material is used as the negative electrode material, its irreversible capacity needs to be reduced.
  • a lithium metal negative electrode it is necessary to solve the problems of reduction in charge / discharge efficiency and safety due to dendrite generation.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • aluminum reacts with a very small amount of water, the capacity may decrease rapidly when the cycle is repeated.
  • 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.
  • a lithium ion secondary battery that can use propylene carbonate can be provided.
  • cracks that occur in the solid electrolyte due to stress changes during the insertion and desorption of lithium ions sometimes lead to characteristic deterioration.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Patent Documents 9 and 10 disclose a method for producing a cyclic sulfonic acid ester having two sulfonyl groups
  • Non-Patent Documents 14 to 14 disclose a method for producing a chain disulfonic acid ester.
  • 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.
  • this additive 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.
  • 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.
  • 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.
  • Patent Document 13 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.
  • an electrode using only silicon absorbs an alkali metal or the like.
  • 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.
  • 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.
  • 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., ⁇ 64_69 (1968).
  • Non-Patent Document 4 Armyanskii Khimicheskii Zhurnal, 21, pp393-396 (1968).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • R and R are each independently a hydrogen atom
  • 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
  • R and R are each independently
  • 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. )
  • polyfluoroalkylene group polyfluoroalkyl group
  • polyfluoroalkoxy group are bonded to carbon atoms of the corresponding alkylene group, alkyl group, and alkoxy group, respectively.
  • ⁇ 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.
  • 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.
  • 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.
  • a group in which one SO — is introduced into these groups (eg, -OSO C
  • 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.
  • FIG. 1 is a schematic configuration diagram of a secondary battery according to the present invention.
  • metal containing element M 1 or metalloid is a schematic diagram showing a state of composite is coated with a carbon material.
  • FIG 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
  • FIG. 1 shows a schematic structure of an example of the battery according to the present invention.
  • the chain disulfonate compound (chain disulfonate) represented by the general formula (1) is contained in the electrolytic solution 15.
  • 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.
  • a porous film such as polyolefin such as polypropylene or polyethylene, or a fluororesin is preferably used.
  • LiMO LiMO (M is selected from Mn, Fe, Co, and a part thereof is other cations such as Mg, Al, Ti)
  • the layer 12 to be the positive electrode can be obtained by a method such as coating on the top.
  • 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.
  • 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 .
  • 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.
  • these elements may include a state of even good tool alloys contain respectively metals or semi-metallic state.
  • 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.
  • 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
  • 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.
  • a metal or semimetal and an oxide can be used in combination.
  • the above element M 1 is
  • M 1 is an element selected from Si, Sn, Al, Pb, Ag, Ge, and Sb
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • the element X contained in the negative electrode active material may be one or more.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a vacuum film forming method a vacuum evaporation method, a sputtering method, a CVD method, etc. can be used.
  • 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.
  • 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.
  • the “layer containing the main component” occupies 50% by mass or more of the entire material constituting the layer.
  • the main component of each layer accounts for 70% by mass or more.
  • 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 are produced by using a vacuum film forming method or a pressure welding method in addition to a usual production method.
  • a vacuum film forming method such as a CVD method, a pressure welding method such as a mechanical milling method ⁇ mechanofusion method, or a sol-gel method can be used.
  • a metal or metalloid containing the element M 1 S 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.
  • the metal or metalloid containing the elemental M 1 can be composited coated by the carbon material.
  • 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.
  • 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.
  • a CVD method or a carbon material deposition may be performed a carbon material coating.
  • 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.
  • 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.
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • PVDF chloride
  • 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.
  • 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.
  • 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.
  • a carbon material mainly composed of a metal or metalloid containing the element M 1 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.
  • the layer containing a composite material of a metal or metalloid and the carbon material containing the above element M 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.
  • 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 .
  • 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.
  • 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.
  • a coating method 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.
  • PVDF polyvinylidene phthaleolide
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • PVDF polyvinylidene fluoride
  • 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.
  • the oxide and the carbon material may be simply mixed in the form of particles.
  • the oxide 2c may be covered with the carbon material 2a to form a composite.
  • the carbon material 3a may be covered with the oxide 3c to form a composite.
  • 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.
  • 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.
  • the oxide can be coated with a carbon material film by, for example, a CVD method.
  • 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.
  • the above oxide can be coated with a carbon material to form a composite.
  • a pressure welding method such as mechanical milling / mechanofusion
  • 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.
  • the oxide film can be formed on the carbon material particles by, for example, a CVD method, and the composite film can be formed.
  • an oxide film can be formed on the carbon material particles by a sol-gel method to form a composite.
  • 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.
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • PVDF chloride
  • 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.
  • the oxide and the carbon material can be simultaneously formed into a film to form a composite film.
  • 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.
  • 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.
  • a film can be formed preferentially on a layer mainly composed of an oxide, and high conductivity and good vital characteristics can be expected.
  • 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.
  • this structure high conductivity and a cushioning effect against a volume change due to charge and discharge of the oxide can be expected.
  • 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.
  • 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.
  • a coating method 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.
  • PVDF polyvinylidene phthaleolide
  • 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).
  • PVDF polyvinylidene fluoride
  • 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.
  • the electrolytic solution 15 has at least an electrolyte, an aprotic solvent and an additive.
  • lithium salt As the electrolyte, in the case of a lithium secondary battery, a lithium salt is used, and this is dissolved in an aprotic solvent.
  • lithium salts lithium imide salts, LiPF, LiAsF, LiAICl, Li
  • LiPF and LiBF are preferred. These may be used alone or in combination.
  • High energy density can be achieved by including these lithium salts.
  • the aprotic electrolytic solution may include cyclic carbonates, chain carbonates, aliphatic carboxylic acid esters, ⁇ -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 ⁇ -petit ratatone, and derivatives thereof
  • Cyclic ethers tetrahydrofuran, 2-methyltetrahydrofuran, and derivatives thereof
  • Chain ethers 1,2-diethoxytan (DEE), ethoxymethoxyethane ( ⁇ ), 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
  • a chain disulfonic acid ester represented by the general formula (1) is used as the additive.
  • R and R are each independently a hydrogen atom
  • 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
  • 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
  • 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.
  • the preferable molecular structure of R and R in the general formula (1) is a reaction occurring on an electrode.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the compounds represented by the general formula (1) may be used alone or in combination of two or more.
  • at least one compound having an active methylene group ie, R and
  • 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.
  • 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
  • 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.
  • Examples of the cyclic monosulfonic acid ester include compounds represented by the following general formula (2).
  • n is an integer of 0 or more and 2 or less.
  • 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
  • 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
  • a polyfluoroalkyl group having 115 carbon atoms a trifluoromethyl group is preferable.
  • 1,3_propane sultone (1,3_PS), ⁇ -trifluoromethyl- ⁇ -sultone, j3-trifluoromethylinone, ⁇ -sultone, ⁇ -trifluoromethylinole 1 ⁇ -sultone, 1 methinole 1 ⁇ _snoretone, 1 j-di (trifnorolelomethinole) 1 ⁇ _snoreton, 1 h, Hichiji (trif noreolomethinole) 1 ⁇ -sultone, 1d Gamma-sultone, Tafluoropropyl- ⁇ -sultone, 1,4-butansnoretone (1,4-BS), etc.
  • 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).
  • 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.
  • the power S that mainly reacts with a certain part of the negative electrode surface and Compound No.
  • 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.
  • Examples of the cyclic sulfonic acid ester having two sulfonyl groups include a compound represented by the following 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_ ⁇ _C bond, and a group selected
  • 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
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 1090% by mass of the total mass of the compounds of the general formulas (1), (2) and (3) is preferable. ,.
  • 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.
  • the effect can be obtained by adding 0.05% by mass and 3.0% by mass in 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.
  • 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
  • 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.
  • a desired electrolyte can be obtained.
  • the shape of the secondary battery according to the present invention is not particularly limited, and examples thereof include a cylindrical shape, a square shape, a coin shape, and a laminate shape.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • 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.
  • 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.
  • the negative electrode active material is in the form of particles
  • the ratio of carbon material particles having an average particle diameter of 10 ⁇ m: 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.
  • 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.
  • 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 ⁇ 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.
  • 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.
  • 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]: ⁇ 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.
  • a prismatic secondary battery exemplified in the column 1-31, 52 60, 61 91, and 112-143, and]: ⁇ Rows 1-3, 9-13, 19, and 20
  • cylindrical secondary batteries Examples 46-51 and 106 111, and Comparative Examples 8 and 18
  • aluminum laminated film secondary batteries Examples 32 to 45 and 92 to 105, and Comparative Examples 417 and 14 to 117
  • the laminated film used was a polypropylene resin (sealing layer, thickness 70 / im), polyethylene terephthalate (20 / im), aluminum (50 ⁇ ), 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.
  • 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)
  • 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.
  • 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.
  • 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.
  • the layer containing the negative electrode active material was prepared using Pb having an average particle size of 10 ⁇ as a negative electrode active material other than the carbon material. Other conditions were the same as in Example 1.
  • the layer containing the negative electrode active material was prepared using Ag having an average particle size of 10 ⁇ as a negative electrode active material other than the carbon material. Other conditions were the same as in Example 1.
  • 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.
  • 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.
  • Compound No. 2 was used as an additive. Other conditions were the same as in Example 1.
  • Compound No. 3 was used as an additive. Other conditions were the same as in Example 1.
  • Compound No. 4 was used as an additive. Other conditions were the same as in Example 1.
  • Compound No. 6 was used as an additive. Other conditions were the same as in Example 1.
  • Compound No. 9 was used as an additive. Other conditions were the same as in Example 1.
  • Compound No. 10 was used as an additive. Other conditions were the same as in Example 1.
  • Compound No. 15 was used as an additive. Other conditions were the same as in Example 1.
  • Compound No. 16 was used as an additive. Other conditions were the same as in Example 1.
  • Compound No. 19 was used as an additive. Other conditions were the same as in Example 1.
  • Example 20 The layer containing the negative electrode active material was produced using Si having an average particle size of 10 ⁇ 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.
  • 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.
  • 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.
  • the layer containing the negative electrode active material was produced using Si having an average particle size of 10 ⁇ 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.
  • 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.
  • 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.
  • 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 ⁇ as a negative electrode active material other than the carbon material. Other conditions were the same as in Example 22.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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 ⁇ and Ni particles corresponding to element X having an average particle size of 10 ⁇ .
  • Si—A1 alloy particles having an average particle size of 10 ⁇
  • Ni particles corresponding to element X having an average particle size of 10 ⁇ .
  • 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 ⁇ m 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)
  • o.1 containing 0.5% by mass was used.
  • 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.
  • 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.
  • 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.
  • 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.
  • the additives used were 0.5% by mass of the compound ⁇ ⁇ 1, 3% by mass of 1,3_PS, and 1% by mass of VC. Other conditions were the same as in Example 38.
  • 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.
  • Compound No. 1 was used in an amount of 0.1% by mass. Other conditions were the same as in Example 46.
  • Example 51 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)
  • 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 ⁇ m 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
  • 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 ⁇ m and Sn particles having an average particle size of 1 ⁇ m by mechanical milling. Other conditions were the same as in Example 52.
  • the layer containing the negative electrode active material is a composite particle obtained by combining graphite particles with an average particle size of 10 ⁇ m 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
  • 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.
  • the layer containing the negative electrode active material is a composite particle obtained by combining graphite particles with an average particle size of 10 ⁇ m 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.
  • the content of the carbon material was set to 5% by mass. Other conditions were the same as in Example 1.
  • the content of the carbon material was set to 95% by mass. Other conditions were the same as in Example 1.
  • 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.
  • the layer containing the negative electrode active material was formed by sputtering Sn ⁇ as a negative electrode active material other than the carbon material. Other conditions were the same as in Example 61.
  • the layer containing the negative electrode active material was sputtered with Sn ⁇ as the negative electrode active material other than the carbon material.
  • 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.
  • the layer containing the negative electrode active material is a particle obtained by mixing Fe O particles having an average particle size of 10 ⁇ 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.
  • W O was sputtered as the negative electrode active material other than the carbon material.
  • 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.
  • Compound No. 2 was used as an additive. Other conditions were the same as in Example 61.
  • Compound No. 3 was used as an additive. Other conditions were the same as in Example 61.
  • Compound No. 4 was used as an additive. Other conditions were the same as in Example 61.
  • Compound No. 6 was used as an additive. Other conditions were the same as in Example 61.
  • Compound No. 9 was used as an additive. Other conditions were the same as in Example 61.
  • Compound No. 10 was used as an additive. Other conditions were the same as in Example 61.
  • Compound No. 15 was used as an additive. Other conditions were the same as in Example 61.
  • Compound No. 16 was used as an additive. Other conditions were the same as in Example 61.
  • Compound No. 19 was used as an additive. Other conditions were the same as in Example 61.
  • Example 80 The layer containing the negative electrode active material was formed using Si ⁇ having an average particle size of 10 ⁇ 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.
  • 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 61.
  • the layer containing the negative electrode active material was prepared 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 61.
  • the layer containing the negative electrode active material was formed using Si ⁇ having an average particle size of 10 ⁇ 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.
  • the layer containing the negative electrode active material was formed by sputtering Sn ⁇ as a negative electrode active material other than the carbon material. Other conditions were the same as in Example 82.
  • the layer containing the negative electrode active material was sputtered with Sn ⁇ as the negative electrode active material other than the carbon material.
  • Example 85 (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 ⁇ and BO particles having an average particle size of 10 / im as a negative electrode active material other than the carbon material.
  • 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.
  • W O was sputtered as the negative electrode active material other than the carbon material.
  • the layer containing the negative electrode active material was prepared using Li Ti O having an average particle size of 10 ⁇ as the negative electrode active material other than the carbon material. Other conditions were the same as in Example 82.
  • the layer containing the negative electrode active material was prepared by depositing Si ⁇ 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.
  • No. 1 containing 0.5% by mass was used.
  • 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.
  • the layer containing the negative electrode active material is formed by mechanical milling Sn-- particles with an average particle size of 10 ⁇ and Ni particles corresponding to element X with an average particle size of 10 ⁇ m as the negative electrode active material other than the carbon material.
  • a material containing 0.5% by mass of the product No. 1 was used.
  • 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 ⁇ as a negative electrode active material other than the carbon material by vapor deposition. Other conditions were the same as in Example 98.
  • the layer containing the negative electrode active material was prepared by depositing Si ⁇ 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Compound No. 1 was used in an amount of 0.1% by mass. Other conditions were the same as in Example 106.
  • Example 106 As an additive, 0.75% by mass of Compound No. 1 was used. Other conditions were the same as in Example 106.
  • Example 110 As an additive, 3% by mass of Compound No. 1 was used. Other conditions were the same as in Example 106. (Example 110)
  • compound No. 1 was used in an amount of 5% by mass.
  • Other conditions were the same as in Example 106.
  • 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 ⁇ m 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.
  • 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 ⁇ m and Sn 2 O particles having an average particle diameter of 1 ⁇ m by mechanical milling.
  • the other conditions were the same as in Example 112.
  • 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 ⁇ m and Ni particles having an average particle size of 1 ⁇ m, and graphite particles having an average particle size of 10 ⁇ m.
  • the layer containing the negative electrode active material was composed of graphite particles with an average particle size of 10 ⁇ m 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
  • the layer containing the negative electrode active material is a composite obtained by combining graphite particles with an average particle size of 10 ⁇ m and SnO particles with an average particle size of 1 ⁇ m by mechanical milling, and then carbon coating by CVD. It was prepared using particles. Other conditions were the same as in Example 115.
  • the content of the carbon material was set to 5% by mass. Other conditions were the same as in Example 61.
  • the content of the carbon material was set to 95% by mass. Other conditions were the same as in Example 61.
  • 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.
  • 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 ⁇ . (S source number: 0 atom number: 2: 1). Other conditions were the same as in Example 1.
  • the layer containing the negative electrode active material is composed of a mixture of Si, Si ⁇ , and Li
  • the layer containing the negative electrode active material contains Sn, Sn ⁇ , and Li as the negative electrode active material other than the carbon material.
  • the layer containing the negative electrode active material was prepared by mixing Si having an average particle size of 1 ⁇ m and SiO having an average particle size of 1 ⁇ m 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.
  • the layer containing the negative electrode active material has an average particle diameter of 1 ⁇ m as a negative electrode active material other than the carbon material.
  • Compound No. 2 was used as an additive. Other conditions were the same as in Example 127.
  • Compound No. 3 was used as an additive. Other conditions were the same as in Example 127.
  • Compound No. 4 was used as an additive. Other conditions were the same as in Example 127.
  • Compound No. 6 was used as an additive. Other conditions were the same as in Example 127.
  • Compound No. 9 was used as an additive. Other conditions were the same as in Example 127.
  • Compound No. 10 was used as an additive. Other conditions were the same as in Example 127.
  • Compound No. 15 was used as an additive. Other conditions were the same as in Example 127.
  • Compound No. 16 was used as an additive. Other conditions were the same as in Example 127.
  • Compound No. 19 was used as an additive. Other conditions were the same as in Example 127.
  • the layer containing the negative electrode active material is composed of a mixture of Si, Si ⁇ , and Li
  • the layer containing the negative electrode active material contains Sn, Sn ⁇ , and Li as the negative electrode active material other than the carbon material.
  • the layer containing the negative electrode active material was prepared by mixing Si having an average particle size of 1 ⁇ m and SiO having an average particle size of 1 ⁇ m 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 1 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 9 81.6 1.36
  • Example 10 83.5 1.27
  • Example 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
  • 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 72 86.4 1.54
  • 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 85 80.1 1.95
  • Example 86 81.6
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • Example 38-40 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.
  • 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.
  • 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.
  • Example 104 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Example 121 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.
  • Example 1 carbon material content: 50% by mass
  • Example 61 carbon material content: 50% by mass
  • Examples 118 5% by mass
  • 119 carbon material content: 50% by mass
  • Example 1 coating method
  • Example 60 sputtering method
  • Example 61 coating method
  • Example 120 sputtering method

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Abstract

L'invention porte sur un accumulateur au lithium possédant d'excellentes caractéristiques de densité d'énergie et de force électromotrice, de durée de vie utile et de stabilité au stockage. L'invention concerne un accumulateur qui comprend au moins une électrode positive, une électrode négative et une solution électrolytique, l'électrode négative contenant un métal, un métalloïde ou un oxyde qui adsorbe/désorbe un métal alcalin ou un métal de terre alcaline, et un matériau carboné comme matière active de l'électrode négative, la solution électrolytique contenant un solvant non protéique dans lequel est dissout au moins un électrolyte, et un composé disulfone à chaîne.
PCT/JP2004/018715 2003-12-15 2004-12-15 Accumulateur WO2005057715A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005516241A JP4951969B2 (ja) 2003-12-15 2004-12-15 二次電池

Applications Claiming Priority (6)

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JP2003416516 2003-12-15
JP2003-416516 2003-12-15
JP2004-317298 2004-10-29
JP2004317298 2004-10-29
JP2004317280 2004-10-29
JP2004-317280 2004-10-29

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WO2005057715A1 true WO2005057715A1 (fr) 2005-06-23

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JP (1) JP4951969B2 (fr)
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JP2007165108A (ja) * 2005-12-14 2007-06-28 Hitachi Maxell Ltd 非水電解液二次電池
JP2007329010A (ja) * 2006-06-07 2007-12-20 Sumitomo Electric Ind Ltd リチウム二次電池用電極及びその製造方法
JP2008153118A (ja) * 2006-12-19 2008-07-03 Nec Tokin Corp 非水電解液およびそれを用いた非水電解液二次電池
JP2009032693A (ja) * 2007-07-27 2009-02-12 Samsung Sdi Co Ltd Ｓｉ／Ｃ複合物、これを含むアノード活物質及びリチウム電池
EP2051318A1 (fr) * 2007-02-02 2009-04-22 Panasonic Corporation Electrode de pile au lithium et procédé de fabrication de l'électrode de pile au lithium
WO2010053200A1 (fr) * 2008-11-10 2010-05-14 株式会社エクォス・リサーチ Électrode positive pour batterie secondaire, batterie secondaire l'utilisant, collecteur, et batterie utilisant le collecteur
JP2010282920A (ja) * 2009-06-08 2010-12-16 Kobe Steel Ltd リチウムイオン二次電池用負極材、および、その製造方法、ならびに、リチウムイオン二次電池
JP2011071084A (ja) * 2009-01-19 2011-04-07 Equos Research Co Ltd 二次電池用正極及び二次電池
JP2011071085A (ja) * 2009-01-19 2011-04-07 Equos Research Co Ltd 二次電池用正極及び二次電池
JP2012033346A (ja) * 2010-07-29 2012-02-16 Nec Energy Devices Ltd 非プロトン性電解液二次電池
US20120177988A1 (en) * 2006-04-27 2012-07-12 Mitsubishi Chemical Corporation Non-aqueous liquid electrolyte and non-aqueous liquid electrolyte secondary battery
JP5304961B1 (ja) * 2013-02-22 2013-10-02 大日本印刷株式会社 マグネシウムイオン二次電池用負極板、及びマグネシウムイオン二次電池、および電池パック
US8551655B2 (en) 2010-07-07 2013-10-08 Samsung Sdi Co., Ltd. Negative active material for secondary lithium battery and secondary lithium battery
JP2014127313A (ja) * 2012-12-26 2014-07-07 Toyota Motor Corp 非水電解液二次電池および該電池の製造方法
US20140199601A1 (en) * 2011-07-07 2014-07-17 Sumitomo Seika Chemicals Co., Ltd. Additive for nonaqueous electrolyte, nonaqueous electrolyte, and electricity storage device
JP2014521196A (ja) * 2012-04-26 2014-08-25 ▲寧▼波杉杉新材料科技有限公司 高性能リチウムイオン電池における多孔質フィルムシリコン負極材料及びその製造方法
WO2016035396A1 (fr) * 2014-09-01 2016-03-10 日立オートモティブシステムズ株式会社 Batterie secondaire au lithium-ion
JPWO2015129266A1 (ja) * 2014-02-25 2017-03-30 新日鐵住金株式会社 複合粒子、負極及び電池
CN106688132A (zh) * 2014-07-22 2017-05-17 瑞克锐斯株式会社 硅二次电池
JPWO2016098214A1 (ja) * 2014-12-17 2017-11-02 日産自動車株式会社 電気デバイス用負極活物質、およびこれを用いた電気デバイス
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WO2019163967A1 (fr) * 2018-02-23 2019-08-29 国立研究開発法人産業技術総合研究所 Corps multicouche et son procédé de production
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JPWO2015129266A1 (ja) * 2014-02-25 2017-03-30 新日鐵住金株式会社 複合粒子、負極及び電池
US10263280B2 (en) 2014-03-28 2019-04-16 Evonik Degussa Gmbh 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymers and use thereof
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