JP6453611B2 - Lithium secondary battery - Google Patents

Description

  The present invention relates to a lithium secondary battery having good cycle characteristics and high-temperature storage characteristics.

  In recent years, along with the development of portable electronic devices such as mobile phones and notebook computers, and the practical application of electric vehicles, small and light lithium secondary batteries with high capacity have been required.

  In addition, lithium secondary batteries are required to improve various battery characteristics as well as to increase the capacity in accordance with the spread of applied devices.

  As one means for achieving improvement of the battery characteristics of such a lithium secondary battery, it is known to apply various additives to the nonaqueous electrolyte of the lithium secondary battery. For example, Patent Document 1 discloses a non-aqueous electrolysis containing a cyclic carbonate such as ethylene carbonate or propylene carbonate, and a cyclic acid anhydride having a side chain having 3 or more carbon atoms having a double bond or a triple bond at the end. A liquid is disclosed. By using this electrolytic solution, it is said that the electrochemical characteristics in a wide temperature range can be improved.

  Patent Document 2 discloses a non-aqueous electrolyte characterized by containing triallyl isocyanate and a compound such as a halogenated cyclic carbonate compound or a nitrile compound. By using this electrolytic solution, it is said that a battery with a good balance of overall performance can be obtained with respect to performance such as durability, capacity, resistance, and output characteristics.

  In addition, deterioration of characteristics of batteries derived from hydrogen fluoride (HF) generated by bringing moisture into the battery has been a problem. Patent Document 3 discloses a technique for improving cycle characteristics by using a specific sulfonic acid anhydride and controlling water contained in a non-aqueous electrolyte to 100 ppm or less. Furthermore, in Patent Document 4, the moisture content per unit volume of the battery separator provided with an insulating layer containing insulating inorganic fine particles is regulated to restrict moisture from being brought into the battery, and good reliability and safety are achieved. It is disclosed that a lithium secondary battery having excellent storage characteristics and special charge / discharge cycle characteristics can be provided.

International Publication No. 2013/058235 JP 2014-063733 A JP 2010-177025 A International Publication No. 2008/029922

  By the way, in recent years, in response to the demand for higher capacity of lithium secondary batteries, studies have been made to cope with this by increasing the upper limit voltage of charging compared to the conventional case. In this case, the battery is in a charged state. In particular, since various components are placed in a harsher environment than in the past, for example, there is a possibility that a technique capable of further improving the high-temperature storage characteristics in a battery environment may be required.

  This invention is made | formed in view of the said situation, The objective is to provide a lithium secondary battery with favorable cycling characteristics and high temperature storage characteristics.

  The lithium secondary battery of the present invention that has achieved the above object is a secondary battery comprising a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte, on at least one surface of the positive electrode, the negative electrode, and the separator. The inorganic oxide particle layer includes inorganic oxide particles and a binder, and allyl succinic anhydride in the nonaqueous electrolyte is 0.1 to 3% by mass, vinylene carbonate. Is a non-aqueous electrolyte with a concentration of 0.5 to 4% by mass.

  According to the present invention, it is possible to provide a lithium secondary battery having good cycle characteristics and high-temperature storage characteristics.

It is a fragmentary longitudinal cross-sectional view which represents typically an example of the lithium secondary battery of this invention. FIG. 2 is a perspective view of FIG. 1.

  In the lithium secondary battery of the present invention, for example, a solution (non-aqueous electrolyte) in which a lithium salt is dissolved in an organic solvent, which uses a non-aqueous electrolyte containing allyl succinic anhydride and vinylene carbonate, a positive electrode, An inorganic oxide particle layer is provided on at least one surface of the negative electrode and the separator.

  It is a common technique to provide an inorganic oxide particle layer having excellent heat resistance on a separator or electrode in order to prevent the positive electrode and the negative electrode from being short-circuited by thermal contraction of the separator and to improve the safety of the lithium secondary battery. However, the inorganic oxide particles generally have a property of storing moisture.

  When moisture is brought into the battery, it reacts with a fluorine compound (for example, fluorine derived from a lithium salt containing fluorine) in the battery to generate hydrogen fluoride (HF). In particular, this HF is likely to occur at high temperatures. This HF corrodes the internal parts of the battery and causes various battery characteristics to deteriorate. In particular, the deterioration of the positive electrode active material is caused by the transition metal element of the positive electrode active material being ionized and eluted into the non-aqueous electrolyte. It causes deterioration of cycle characteristics and gas generation. That is, when a heat-resistant layer using inorganic oxide particles that easily store moisture is provided, it contributes to improving the safety of the battery, but there is also a risk that HF is likely to be generated.

  Therefore, at the same time as providing the inorganic oxide particle layer, allyl succinic anhydride was contained in the non-aqueous electrolyte to prevent the generation of HF. Allyl succinic anhydride has the property of adsorbing water and can be brought into the battery and adsorbed the water dissolved in the non-aqueous electrolyte. Thereby, generation | occurrence | production of the hydrogen fluoride which is a reaction product of a water | moisture content and a fluorine compound can be suppressed in a battery. Therefore, even when an inorganic oxide particle layer is provided and moisture is easily taken into the battery, corrosion of the positive electrode active material by hydrogen fluoride can be suppressed, and cycle characteristics and high-temperature storage characteristics are improved.

  Vinylene carbonate (hereinafter referred to as VC) is very common as an electrolyte additive, and is a compound employed in many lithium secondary batteries. VC forms a film on the negative electrode surface and can prevent the negative electrode and the non-aqueous electrolyte from reacting excessively. However, as the upper limit voltage of the battery becomes higher (for example, 4.35 V or more) as the capacity increases, VC is oxidized on the surface of the positive electrode and becomes carbon dioxide, which causes swelling during high-temperature storage. However, if the content of VC in the non-aqueous electrolyte is reduced in order to avoid gas generation, a sufficient film cannot be formed on the negative electrode and cycle characteristics will deteriorate. In such a background, it has been clarified by the inventors of the present invention that high-temperature storage characteristics and cycle characteristics are improved by using VC and allyl succinic anhydride in combination.

  The reason for this is not clear, but is estimated as follows. As the charging upper limit voltage becomes higher, it approaches the oxidation potential of VC, so that VC easily reacts at the positive electrode and gas is generated. Furthermore, with VC alone, it is not possible to form a film that can withstand repeated Li insertion / extraction under high voltage and high temperature, the film is destroyed, and VC remaining in the electrolyte reacts on the exposed negative electrode surface. The electrolyte itself is consumed, and this causes the cycle characteristics to deteriorate.

  Therefore, allyl succinic anhydride and VC are both contained in the non-aqueous electrolyte. Both compounds are considered to form a film on the negative electrode surface, and can be used as a strong film that can easily pass Li ions and can withstand repeated charge and discharge when used in combination rather than a film of VC alone. As a result, it is possible to suppress the consumption of the electrolytic solution even in a harsh environment such as a high voltage and a high temperature, and to suppress deterioration in cycle characteristics.

  Furthermore, the reduction potential of allyl succinic anhydride on the negative electrode surface is close to VC, and when allyl succinic anhydride forms a film on the negative electrode, it reacts by entraining VC, allowing Li ions to pass through, and high voltage and high temperature resistance. A coating can be formed. Further, VC does not remain excessively in the non-aqueous electrolyte, and gas generation can be suppressed.

  In addition, as described above, the cycle characteristics when the allyl succinic anhydride and the inorganic oxide particle layer are provided and the cycle characteristics when both VC and allyl succinic anhydride are used simultaneously are synergistic. It has been made clear by the inventors of the present invention to bring about an effect.

  In order to obtain the above-described effect, the content of allyl succinic anhydride in the nonaqueous electrolyte is 0.1% by mass or more, preferably 0.3% by mass or more. If the amount of allyl succinic anhydride is too large, the interfacial resistance increases, so it is 3.0% by mass or less, preferably 2.0% by mass or less.

  Further, the content of VC in the non-aqueous electrolyte for obtaining the above-described effect is 0.5% by mass or more. Preferably it is 1.0 mass% or more. If the amount of VC is too large, the mixed film with allyl succinic anhydride becomes non-uniform, so that it is 4.0% by mass or less, preferably 3.0% by mass or less.

As long as the effects of the present invention are not impaired, compounds other than the compounds described above can be used as additives in the non-aqueous electrolyte.
For example, a phosphonoacetate compound represented by the following general formula (1) can be used. The phosphonoacetate compound is a component that forms a film on the negative electrode surface of the lithium secondary battery and suppresses the deterioration of the negative electrode active material and the nonaqueous electrolyte.

In the general formula (1) representing the phosphonoacetate compound, R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom (for example, , Alkyl group, alkenyl group, alkynyl group, etc.), and n is an integer of 0-6. That is, R ¹ , R ² and R ³ may be different from each other, or two or more may be the same.

  Specific examples of the phosphonoacetate compound represented by the general formula (1) include the following.

<Compound wherein n = 0 in the general formula (1)>
Trimethyl phosphonoformate, methyl diethyl phosphonoformate, methyl dipropyl phosphonoformate, methyl dibutyl phosphonoformate, triethyl phosphonoformate, ethyl dimethyl phosphonoformate, ethyl dipropyl phosphonoformate, ethyl Dibutyl phosphonoformate, tripropyl phosphonoformate, propyl dimethylphosphonoformate, propyl diethylphosphonoformate, propyl dibutylphosphonoformate, tributyl phosphonoformate, butyl dimethylphosphonoformate, butyl diethylphospho Noformate, butyl dipropylphosphonoformate, methyl bis (2,2,2-trifluoroethyl) phosphonoformate, ethyl bis (2 2,2-trifluoroethyl) phosphonoacetate formate, propyl bis (2,2,2-trifluoroethyl) phosphonoacetate formate, and butyl bis (2,2,2-trifluoroethyl) phosphonoacetate formate.

<Compound with n = 1 in the general formula (1)>
Trimethyl phosphonoacetate, methyl diethyl phosphonoacetate, methyl dipropyl phosphonoacetate, methyl dibutyl phosphonoacetate, triethyl phosphonoacetate, ethyl dimethylphosphonoacetate, ethyl dipropylphosphonoacetate, ethyldibutylphosphonoacetate, tripropyl Phosphonoacetate, propyl dimethylphosphonoacetate, propyl diethylphosphonoacetate, propyl dibutylphosphonoacetate, tributyl phosphonoacetate, butyldimethylphosphonoacetate, butyldiethylphosphonoacetate, butyldipropylphosphonoacetate, methylbis (2 , 2,2-trifluoroethyl) phosphonoacetate, ethyl bis (2,2,2-trifluoroethyl) phospho No acetate, propyl bis (2,2,2-trifluoroethyl) phosphonoacetate, butyl bis (2,2,2-trifluoroethyl) phosphonoacetate, allyl dimethylphosphonoacetate, allyl diethylphosphonoacetate, 2 -Propynyl (dimethylphosphono) acetate, 2-propynyl (diethylphosphono) acetate, etc.

<Compound wherein n = 2 in the general formula (1)>
Trimethyl-3-phosphonopropionate, methyl diethyl-3-phosphonopropionate, methyl dipropyl-3-phosphonopropionate, methyl dibutyl-3-phosphonopropionate, triethyl-3-phosphonopro Pionate, ethyl dimethyl-3-phosphonopropionate, ethyl dipropyl-3-phosphonopropionate, ethyl dibutyl 3-phosphonopropionate, tripropyl-3-phosphonopropionate, propyl dimethyl-3 -Phosphonopropionate, propyl diethyl-3-phosphonopropionate, propyl dibutyl 3-phosphonopropionate, tributyl-3-phosphonopropionate, butyl dimethyl-3-phosphonopropionate, butyl Diethyl-3-phosphonopropionate, butyl Propyl-3-phosphonopropionate, methyl bis (2,2,2-trifluoroethyl) -3-phosphonopropionate, ethyl bis (2,2,2-trifluoroethyl) -3-phosphono Propionate, propyl bis (2,2,2-trifluoroethyl) -3-phosphonopropionate, butyl bis (2,2,2-trifluoroethyl) -3-phosphonopropionate, and the like.

<Compound wherein n = 3 in the general formula (1)>
Trimethyl-4-phosphonobutyrate, methyl diethyl-4-phosphonobutyrate, methyl dipropyl-4-phosphonobutyrate, methyl dibutyl 4-phosphonobutyrate, triethyl-4-phosphonobutyrate, ethyl dimethyl- 4-phosphonobutyrate, ethyl dipropyl-4-phosphonobutyrate, ethyl dibutyl 4-phosphonobutyrate, tripropyl-4-phosphonobutyrate, propyl dimethyl-4-phosphonobutyrate, propyl diethyl-4 -Phosphonobutyrate, propyl dibutyl 4-phosphonobutyrate, tributyl-4-phosphonobutyrate, butyl dimethyl-4-phosphonobutyrate, butyl diethyl-4-phosphonobutyrate, butyl dipropyl-4-phospho Nob chelate etc.

  Among the above exemplified phosphonoacetate compounds, 2-propynyl (diethylphosphono) acetate (PDEA) and ethyl diethylphosphonoacetate (EDPA) are particularly preferable.

  The content of the phosphonoacetate compound represented by the general formula (1) in the non-aqueous electrolyte used for the lithium secondary battery is 0.5% by mass or more from the viewpoint of better ensuring the effect of the use. It is preferable that it is 1 mass% or more. However, if the content of the phosphonoacetate compound represented by the general formula (1) in the nonaqueous electrolyte is too large, the charge / discharge cycle characteristics of the battery may be deteriorated. Therefore, the content of the phosphonoacetate compound represented by the general formula (1) in the nonaqueous electrolyte used for the lithium secondary battery is preferably 30% by mass or less, and preferably 5% by mass or less. Is more preferable.

When any of R ¹ , R ² , and R ³ of the general formula (1) representing the phosphonoacetate compound contains an unsaturated bond, a carbon-carbon double bond or a carbon-carbon triple is formed on the negative electrode surface. It is presumed that a film is formed by polymerization by opening the bond. The film formed in this case is highly flexible because the constituent molecule (constituent polymer) has a flexible carbon-carbon bond as the main chain. When the lithium secondary battery is charged / discharged, the negative electrode active material expands and contracts accordingly, so that the entire negative electrode (negative electrode mixture layer) also changes in volume. However, when a film containing a component derived from a phosphonoacetate compound is formed on the surface of the negative electrode (negative electrode mixture layer), the film is rich in flexibility as described above. Following the change in volume of the negative electrode, cracks and cracks are less likely to occur, and thus the above-described effect of the coating containing a component derived from a phosphonoacetate compound can be sustained satisfactorily even when the battery is repeatedly charged and discharged. .

  Furthermore, you may make the nonaqueous electrolyte contain the compound which has a nitrile group in a molecule | numerator. The compound having a nitrile group in the molecule adsorbs on the surface of the positive electrode to form a film in the lithium secondary battery, and the non-ion of transition metal element ions from the positive electrode active material in a state charged at a high voltage. It has a function to suppress elution into the water electrolyte. Therefore, even if it uses by the method of charging by setting a high upper limit voltage by the effect | action by the compound which has a nitrile group in a molecule | numerator, it can be used stably.

  In addition, since the compound having a nitrile group in the molecule forms a film on the surface of the positive electrode, direct contact between the positive electrode and the non-aqueous electrolyte can be suppressed. Decomposition on the surface of the positive electrode and gas generation caused thereby can be suppressed. Therefore, it is possible to improve storage characteristics and charge / discharge cycle characteristics under a high temperature environment.

  Examples of the compound having a nitrile group in the molecule include a mononitrile compound having one nitrile group in the molecule, a dinitrile compound having two nitrile groups in the molecule, and a trinitrile compound having three nitrile groups in the molecule. Is mentioned. Among these, the above-mentioned actions (the action of suppressing the elution of ions of transition metal elements from the positive electrode active material by the film formation on the surface of the positive electrode and the action of suppressing the reaction between the positive electrode and the nonaqueous electrolyte component) are better. , Dinitrile compounds (that is, compounds having two nitrile groups in the molecule) are preferred, and are represented by the general formula NC-R-CN (wherein R is a linear or branched hydrocarbon chain having 1 to 10 carbon atoms). More preferred are dinitrile compounds. R in the general formula is more preferably a linear alkylene chain having 1 to 10 carbon atoms or a branched alkylene chain having 1 to 10 carbon atoms.

  Specific examples of the mononitrile compound include lauryl nitrile. Specific examples of the dinitrile compound represented by the general formula include, for example, malononitrile, succinonitrile, glutaronitrile, adiponitrile, 1,4-dicyanoheptane, 1,5-dicyanopentane, 1,6-dicyano. Hexane, 1,7-dicyanoheptane, 2,6-dicyanoheptane, 1,8-dicyanooctane, 2,7-dicyanooctane, 1,9-dicyanononane, 2,8-dicyanononane, 1,10-dicyanodecane, 1 , 6-dicyanodecane, 2,4-dimethylglutaronitrile and the like. As the compound having a nitrile group in the molecule, for example, only one of those exemplified above may be used, or two or more thereof may be used in combination. Among the exemplified compounds, adiponitrile is more preferable because it has a stronger effect of suppressing elution of transition metal element ions from the positive electrode active material.

  The content of the compound having a nitrile group in the molecule in the non-aqueous electrolyte used in the battery is preferably 0.1% by mass or more from the viewpoint of more effectively exerting the effect of the use of these compounds. More preferably, it is 2% by mass or more. However, if the amount of the compound having a nitrile group in the molecule is too large, for example, the storage characteristics of the battery are further improved, but the charge / discharge cycle characteristics may be deteriorated. Therefore, the content of the compound having a nitrile group in the molecule in the non-aqueous electrolyte used in the battery is preferably 5% by mass or less, and more preferably 4% by mass or less.

  1,3-dioxane may be contained in the nonaqueous electrolyte. When 1,3-dioxane is contained in a non-aqueous electrolyte together with a compound having a nitrile group in the molecule and a phosphonoacetate compound represented by the general formula (1), in a lithium secondary battery using this, And a component that forms a film on the negative electrode surface together with the phosphonoacetate compound and suppresses the deterioration of the negative electrode active material and the nonaqueous electrolyte.

  In addition, cyclic carbonates such as ethylene carbonate are generally used as solvents for non-aqueous electrolytes used in lithium secondary batteries, but by repeating charge and discharge of lithium secondary batteries, The nonaqueous electrolyte also deteriorates as the polymerization proceeds. However, in a non-aqueous electrolyte containing 1,3-dioxane, 1,3-dioxane is ring-opened and bonded to the radical-forming site of the cyclic carbonate even when a radical is generated in the cyclic carbonate and the polymer can be polymerized. For this reason, the polymerization reaction of the cyclic carbonate is stopped, and the deterioration of the nonaqueous electrolyte is suppressed.

  The content of 1,3-dioxane in the non-aqueous electrolyte used for the lithium secondary battery is preferably 0.1% by mass or more from the viewpoint of ensuring the above-mentioned effects by using the better. More preferably, it is 0.5 mass% or more. On the other hand, if the amount of 1,3-dioxane in the nonaqueous electrolyte is too large, the load characteristics and charge / discharge cycle characteristics of the battery may be degraded. Therefore, the content of 1,3-dioxane in the non-aqueous electrolyte used for the lithium secondary battery is preferably 5% by mass or less, and more preferably 2% by mass or less.

  In addition, it is preferable to use a non-aqueous electrolyte that also contains a halogen-substituted cyclic carbonate. The halogen-substituted cyclic carbonate acts on the negative electrode and has a function of suppressing the reaction between the negative electrode and the nonaqueous electrolyte component. Therefore, by using a non-aqueous electrolyte that also contains a halogen-substituted cyclic carbonate, a lithium secondary battery with better charge / discharge cycle characteristics can be obtained.

  As the halogen-substituted cyclic carbonate, a compound represented by the following general formula (2) can be used.

In the general formula (2), R ⁴ , R ⁵ , R ⁶ and R ⁷ represent hydrogen, a halogen element or an alkyl group having 1 to 10 carbon atoms, and a part or all of the hydrogen in the alkyl group is halogen. may be substituted with an ^element, at least one of R ^4, R 5, ^{R 6} and ^{R 7} are ^halogen, R ^4, R 5, ^{R 6} and ^{R 7} have different respective Two or more may be the same. When R ⁴ , R ⁵ , R ⁶ and R ⁷ are alkyl groups, the smaller the number of carbon atoms, the better. As the halogen element, fluorine is particularly preferable.

  Among the cyclic carbonates substituted with such a halogen element, 4-fluoro-1,3-dioxolan-2-one (FEC) is particularly preferable.

  The content of the halogen-substituted cyclic carbonate in the non-aqueous electrolyte used for the lithium secondary battery is preferably 0.1% by mass or more from the viewpoint of ensuring better the effect of the use, More preferably, it is at least mass%. However, if the content of the halogen-substituted cyclic carbonate in the non-aqueous electrolyte is too large, the effect of improving storage characteristics may be reduced. Therefore, the content of the halogen-substituted cyclic carbonate in the nonaqueous electrolyte used for the lithium secondary battery is preferably 10% by mass or less, and more preferably 5% by mass or less.

The lithium salt used for the non-aqueous electrolyte of the present invention includes those containing fluorine. For example, LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiSbF ₆ and other inorganic lithium salts, LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , Li ₂ C ₂ F ₄ (SO ₃ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , Examples thereof include organic lithium salts such as LiC (CF ₃ SO ₂ ) ₃ , LiC _n F _{2n + 1} SO ₃ (n ≧ 2), LiN (RfOSO ₂ ) ₂ [where Rf is a fluoroalkyl group]. Among them, highly versatile LiPF ₆ is used. In the present invention, other lithium salts are not limited, and are not particularly limited as long as they dissociate in a solvent to form Li ⁺ ions and hardly cause side reactions such as decomposition in a voltage range used as a battery. Absent. For example, an inorganic lithium salt of LiClO ₄ can be used.

  The total concentration of these lithium salts in the non-aqueous electrolyte is preferably 0.5 to 1.5 mol / l, more preferably 0.9 to 1.25 mol / l.

  The organic solvent used for the non-aqueous electrolyte is not particularly limited as long as it dissolves the lithium salt and does not cause a side reaction such as decomposition in a voltage range used as a battery. For example, cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; chain esters such as methyl propionate; cyclic esters such as γ-butyrolactone; dimethoxyethane; Chain ethers such as diethyl ether, 1,3-dioxolane, diglyme, triglyme and tetraglyme; cyclic ethers such as 1,4-dioxane, tetrahydrofuran and 2-methyltetrahydrofuran; acetonitrile, propionitrile, methoxypropionitrile and the like Nitriles; sulfites such as ethylene glycol sulfite; and the like. These may be used in combination of two or more. In order to obtain a battery with better characteristics, it is desirable to use a combination that can obtain high conductivity, such as a mixed solvent of ethylene carbonate and chain carbonate.

  In addition, non-aqueous electrolytes used for lithium secondary batteries include sulfonic acid esters, 1,3-, for the purpose of further improving charge / discharge cycle characteristics and improving safety such as high-temperature storage and prevention of overcharge. Additives (including these derivatives) such as propane sultone, diphenyl disulfide, cyclohexylbenzene, biphenyl, fluorobenzene, and t-butylbenzene may be added as appropriate.

  Further, as the non-aqueous electrolyte of the lithium secondary battery, a gel (gel electrolyte) obtained by adding a known gelling agent such as a polymer to the non-aqueous electrolyte (non-aqueous electrolyte) is used. You can also.

The lithium secondary battery of the present invention includes an inorganic oxide particle layer on at least one surface of a positive electrode, a negative electrode, and a separator.
The inorganic oxide particle layer is formed including, for example, inorganic oxide particles and a binder. The inorganic oxide particle layer may be formed on any one selected from a positive electrode, a negative electrode, and a separator and disposed between the positive electrode and the negative electrode. The inorganic oxide particle layer may be formed on the positive electrode and the separator, for example, and a plurality of inorganic oxide particle layers may be disposed between the positive electrode and the negative electrode. Furthermore, it does not matter on both sides, such as forming only on one side of the separator or on both sides of the positive electrode.

The inorganic oxide particles have electrical insulating properties, and shape changes such as deformation are not visually confirmed at least at 150 ° C. Specifically, such inorganic oxide particles include iron oxide, silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), BaTiO ₂ , boehmite, zirconia, magnesia, zeolite, apatite, kaolin. , Fine particles such as substances derived from mineral resources such as mullite, spinel, olivine and mica, or artificial products thereof.

  These inorganic oxide particles easily store moisture. However, as described above, by containing allyl succinic anhydride in the non-aqueous electrolyte, allyl succinic anhydride adsorbs the moisture brought in by the inorganic oxide particles, thereby suppressing the generation of HF and the deterioration of cycle characteristics. I can do it.

  As the inorganic oxide particles, those exemplified above may be used alone or in combination of two or more. Among the heat-resistant inorganic fine particles exemplified above, alumina, silica, and boehmite are preferable.

  The average particle diameter of the inorganic oxide particles is preferably 0.001 μm or more, more preferably 0.01 μm or more, and preferably 5 μm or less, more preferably 4 μm or less. The average particle diameter of the inorganic oxide particles is defined as, for example, the number average particle diameter measured by dispersing the inorganic oxide particles in a medium that does not dissolve, using a laser scattering particle size distribution analyzer “LA-920” manufactured by HORIBA. be able to.

  Moreover, as a form of the said inorganic oxide particle, it may have a shape close | similar to spherical shape, for example, and may have a plate-shaped shape.

  As the form of the plate-like particles, it is desirable that the aspect ratio is 5 or more, more preferably 10 or more, and 100 or less, more preferably 50 or less. The aspect ratio of the plate-like particles can be obtained, for example, by analyzing an image taken with a scanning electron microscope (SEM).

  The content of the inorganic oxide particles in the inorganic oxide particle layer is more preferably 60% by volume or more in the total volume of the constituent components of the inorganic oxide particle layer. By setting the content of the inorganic oxide particles in the inorganic oxide particle layer to the above-mentioned content, the mechanical strength of the inorganic oxide particle layer can be ensured, and the positive and negative electrodes are prevented from being short-circuited when the separator is thermally contracted. I can do it. Moreover, even when an inorganic oxide particle layer is provided on the separator, the inorganic oxide particles have the above-described content, so that the thermal contraction of the separator can be prevented by the inorganic oxide particles acting as a skeleton. It becomes possible to prevent a short circuit between the positive and negative electrodes.

  Furthermore, as a secondary effect, even when metal ions are eluted from the positive electrode active material whose stability is lowered under high voltage or high temperature, the function of the inorganic oxide particles to trap the metal ions suitably works. Can do. Therefore, the metal eluted on the negative electrode is prevented from depositing and causing a fine short circuit, and the high temperature storage characteristics are improved.

  The thickness of the inorganic oxide particle layer (when there are a plurality of inorganic oxide particle layers, the total thickness obtained by adding the thicknesses of the respective inorganic oxide particle layers) is preferably 1 μm or more and 5 μm or less. If it is this range, the short circuit prevention effect can be exhibited suitably.

  The binder used for the inorganic oxide particle layer is, for example, an ethylene-vinyl acetate copolymer (EVA, a vinyl acetate-derived structural unit of 20 to 35 mol%), an ethylene-ethyl acrylate copolymer (EEA), or the like. Ethylene-acrylic acid copolymer, fluororesin [polyvinylidene fluoride (PVDF), etc.], fluororubber, styrene-butadiene rubber (SBR), carboxymethylcellulose (CMC), hydroxyethylcellulose (HEC), polyvinyl alcohol (PVA), Examples include polyvinyl butyral (PVB), polyvinyl pyrrolidone (PVP), poly N-vinylacetamide, crosslinked acrylic resin, polyurethane, and epoxy resin. These organic binders may be used alone or in combination of two or more.

  Among the organic binders exemplified above, a heat-resistant resin having a heat resistance of 150 ° C. or higher is preferable, and a highly flexible material such as an ethylene-acrylic acid copolymer, a fluorine-based rubber, or SBR is particularly preferable. Specific examples of these include EVA “Evaflex Series” (trade name) manufactured by Mitsui DuPont Polychemical Co., Ltd., EVA manufactured by Nihon Unicar Co., Ltd., and EEA “Evaflex-EAA Series” manufactured by Mitsui DuPont Polychemical Co., Ltd. (trade name) ), EEA manufactured by Nihon Unicar Co., Ltd., Fluororubber “Daiel Latex Series” (trade name) manufactured by Daikin Industries, Ltd., SBR “TRD-2001” (trade name) manufactured by JSR Corporation, SBR “BM” manufactured by ZEON Corporation -400B "(trade name). A cross-linked acrylic resin (self-crosslinking acrylic resin) having a low glass transition temperature and having a structure in which butyl acrylate is a main component and is cross-linked is also preferable.

  When the organic binder is used, it may be used in the form of an emulsion dissolved or dispersed in a solvent of a composition (slurry or the like) for forming an inorganic oxide particle layer described later.

  As a method for producing the inorganic oxide particle layer of the present invention, for example, an inorganic oxide particle layer forming composition (slurry or the like) in which inorganic oxide particles and a binder are dispersed in an organic solvent or water is prepared. A method of forming an inorganic oxide particle layer by applying an organic solvent or water after drying is applied to at least one of a positive electrode, a negative electrode, and a separator. In addition, a solution in which an organic binder is uniformly dissolved in an organic solvent or an emulsion of an organic binder is previously mixed with inorganic oxide particles, and then this mixture is mixed with an organic solvent or water to form an inorganic oxide particle layer. The inorganic oxide particle layer of the present invention can also be produced using the composition for use.

  Further, the inorganic oxide particle layer forming composition is applied to a resin porous film mainly composed of a thermoplastic resin to produce a laminate of the resin porous film and the inorganic oxide particle layer. The body can also be used as a separator (laminated separator). In this case, the content of the inorganic oxide particles in the inorganic oxide particle layer is preferably 70% by volume or more in the total volume of the constituent components of the inorganic oxide particle layer. Thereby, it can be set as a battery with higher safety | security by the strength improvement effect, heat resistance improvement effect, etc. of separator itself.

  Moreover, when providing an inorganic oxide particle layer on a positive electrode and / or a negative electrode, it is also possible to make an inorganic oxide particle layer function as a separator.

  The lithium secondary battery of the present invention has a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator. The non-aqueous electrolyte may be used as the non-aqueous electrolyte, and the positive electrode, the negative electrode, and the separator As long as the inorganic oxide particle layer is provided on at least one surface, other configurations and structures are not particularly limited, and various configurations adopted in conventionally known lithium secondary batteries. And structure can be applied.

  As the positive electrode according to the lithium secondary battery, for example, one having a structure having a positive electrode mixture layer containing a positive electrode active material, a binder, a conductive additive and the like on one side or both sides of a current collector can be used.

The positive electrode active material, lithium cobalt composite oxide such as LiCoO _2; LiMnO _2, Li ₂ lithium manganese oxides such as MnO _3; lithium nickel composite oxide such as LiNiO _2; layered such _LiCo 1-x NiO ₂ Lithium-containing composite oxide having a structure; lithium-containing composite oxide having a spinel structure such as LiMn ₂ O ₄ , Li _4/3 Ti _5/3 O ₄ ; lithium-containing composite oxide having an olivine structure such as LiFePO ₄ ; One or two or more of lithium-containing composite oxides such as oxides having a basic composition and substituted with various elements can be used.

  Among these lithium-containing composite oxides, it is more preferable to use a lithium nickel cobalt manganese composite oxide represented by the following general composition formula (3) because of its larger capacity.

Li _{1 + s} M ¹ O ₂ (3)
[In the general composition formula (3), −0.3 ≦ s ≦ 0.3, and M ¹ is a group of three or more elements including at least Ni, Co, and Mn, and each of the elements constituting M ¹ 30 <a <65, 5 <b <35, and 15 <c <50, where the ratios (mol%) of Ni, Co, and Mn in the element are a, b, and c, respectively. ]

In the lithium nickel cobalt manganese composite oxide represented by the general composition formula (3), Ni is a component that contributes to an increase in the capacity of the lithium nickel cobalt manganese composite oxide, and the total number of elements in the element group M ¹ is 100 mol. %, The Ni ratio a is preferably over 30 mol%, more preferably 50 mol% or more. In addition, in the lithium nickel cobalt manganese composite oxide represented by the general composition formula (3), the total number of elements in the element group M ¹ is set to 100 mol from the viewpoint of satisfactorily securing the effect of containing an element other than Ni. %, The Ni ratio a is preferably less than 65 mol% and more preferably 60 mol% or less.

In the lithium nickel cobalt manganese composite oxide represented by the general composition formula (3), Co is a component that contributes to an increase in the capacity of the lithium nickel cobalt manganese composite oxide as well as Ni, and is filled in the positive electrode mixture layer. While it works to improve density, too much may cause an increase in cost and a decrease in safety. In addition to these reasons, all elements of the element group M ¹ in the general composition formula (3) representing the lithium nickel cobalt manganese composite oxide from the viewpoint of favorably securing the stabilizing effect of the average valence of Mn described later. When the number is 100 mol%, the Co ratio b is preferably more than 5 mol%, more preferably 20 mol% or more, and preferably less than 35 mol%, and 30 mol% or less. It is more preferable.

Furthermore, in a lithium-nickel-cobalt-manganese composite oxide, when the total number of elements in the element group ^{M 1} in the general formula (3) and 100 mol%, the ratio c of Mn, that is greater than 15 mol% preferably 20 mol% or more, more preferably less than 50 mol%, and even more preferably 30 mol% or less. By including Mn in the amount as described above in the lithium nickel cobalt manganese composite oxide, and making sure that Mn is present in the crystal lattice, the thermal stability of the lithium nickel cobalt manganese composite oxide can be improved. A highly safe battery can be configured.

  Furthermore, in the lithium nickel cobalt manganese composite oxide, Co acts together with Mn to suppress fluctuations in the valence of Mn due to Li doping and dedoping during battery charging / discharging. Therefore, the average valence of Mn can be stabilized at a value in the vicinity of tetravalence, and the reversibility of charge / discharge can be further enhanced. Therefore, by using such a lithium nickel cobalt manganese composite oxide, it becomes possible to constitute a battery having more excellent charge / discharge cycle characteristics.

In the lithium-nickel-cobalt-manganese composite oxide, the element group ^{M 1} is, Ni, may be composed only of Co and Mn, with these elements, Mg, Ti, Zr, Nb , Mo, W, Al, It may contain at least one element selected from the group consisting of Si, Ga, Ge, and Sn. However, when the total number of elements in the element group ^{M 1} was 100mol%, Mg, Ti, Zr , Nb, Mo, W, Al, Si, Ga, total proportion d of Ge and Sn are the following 5 mol% It is preferably 1 mol% or less. Elements other than Ni, Co, and Mn in the element group M ¹ may be uniformly distributed in the lithium nickel cobalt manganese composite oxide, or may be segregated on the particle surface or the like.

The lithium nickel cobalt manganese composite oxide having the above composition has a large true density of 4.55 to 4.95 g / cm ³ and is a material having a high volume energy density. The true density of the lithium nickel cobalt manganese composite oxide containing Mn in a certain range varies greatly depending on its composition. However, the structure is stabilized and the uniformity can be improved in the narrow composition range as described above. For example, it is considered to be a large value close to the true density of LiCoO ₂ . Moreover, the capacity | capacitance per mass of lithium nickel cobalt manganese complex oxide can be enlarged, and it can be set as the material excellent in reversibility.

The lithium nickel cobalt manganese composite oxide has a higher true density especially when the composition is close to the stoichiometric ratio. Specifically, in the general composition formula (3), −0.3 ≦ s It is preferable that ≦ 0.3, and the true density and reversibility can be improved by adjusting the value of s in this way. s is more preferably −0.05 or more and 0.05 or less. In this case, the true density of the lithium nickel cobalt manganese composite oxide is set to a higher value of 4.6 g / cm ³ or more. Can do.

The lithium nickel cobalt manganese composite oxide represented by the general composition formula (3) includes a Li-containing compound (such as lithium hydroxide), a Ni-containing compound (such as nickel sulfate), a Co-containing compound (such as cobalt sulfate), and a Mn-containing compound. compound (such as manganese sulfate), and the element group M compound containing other element contained in ¹ (oxides, hydroxides, sulfates, etc.) can be produced by, for example, mixing, calcining. Further, in synthesizing the lithium-nickel-cobalt-manganese composite oxide with a higher purity, a composite compound containing a plurality of elements included in the element group M ¹ (hydroxides, such as an oxide) and mixing the Li-containing compound It is preferable to fire.

  Firing conditions can be, for example, 800 to 1050 ° C. for 1 to 24 hours, but once heated to a temperature lower than the firing temperature (for example, 250 to 850 ° C.) and maintained at that temperature, preheating is performed. After that, it is preferable to raise the temperature to the firing temperature to advance the reaction. Although there is no restriction | limiting in particular about the time of preheating, Usually, what is necessary is just about 0.5 to 30 hours. The atmosphere during firing can be an atmosphere containing oxygen (that is, in the air), a mixed atmosphere of an inert gas (such as argon, helium, or nitrogen) and oxygen gas, or an oxygen gas atmosphere. The oxygen concentration (volume basis) is preferably 15% or more, and more preferably 18% or more.

  Moreover, the lithium cobalt complex oxide represented by the following general composition formula (4) can also be used for the positive electrode active material.

LiCo _1-z M ² _z O ₂ (4)
[In the general composition formula (4), 0 <z ≦ 0.1, and M ² is Mg, Al, Ti, Fe, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Sn, W, At least one element selected from the group consisting of B, P and Bi. ]

  In the general composition formula (4), z is more preferably 0.05 or less.

When the lithium nickel cobalt manganese composite oxide represented by the general composition formula (3) is used as the positive electrode active material, lithium cobaltate (LiCoO ₂ ) or lithium represented by the general composition formula (4) More preferably, a cobalt composite oxide is used in combination. The lithium cobalt oxide or the lithium cobalt composite oxide represented by the general composition formula (4) is more than the lithium nickel cobalt manganese composite oxide represented by the general composition formula (3). Since the capacity that increases when the battery is increased is large, the effect of increasing the capacity by increasing the end voltage when charging the battery becomes more remarkable.

  For the positive electrode active material, the lithium nickel cobalt manganese composite oxide represented by the general composition formula (3) and the lithium cobalt composite oxide represented by the general composition formula (4) may be used in combination. Particularly preferred. Like the lithium nickel cobalt manganese composite oxide represented by the general composition formula (3), the lithium cobalt composite oxide represented by the general composition formula (4) is under a higher voltage than the lithium cobalt oxide. Because the stability of the battery is good, use the battery more stably when the end voltage when charging the lithium secondary battery is set higher than the value used for normal batteries to increase the capacity. Will be able to.

  When the lithium nickel cobalt manganese composite oxide represented by the general composition formula (3) and the lithium cobalt oxide or the lithium cobalt composite oxide represented by the general composition formula (4) are used for the positive electrode active material The content of the lithium nickel cobalt manganese composite oxide represented by the general composition formula (3) in the total amount of the positive electrode active material is 5% by mass from the viewpoint of better ensuring the effect of increasing the capacity by its use. Preferably, it is preferably 10% by mass or more. In addition, since only the lithium nickel cobalt manganese composite oxide represented by the general composition formula (3) may be used as the positive electrode active material, it is represented by the general composition formula (3) in the total amount of the positive electrode active material. The upper limit of the preferred content of the lithium nickel cobalt manganese composite oxide is 100% by mass, but by using lithium cobaltate or the lithium cobalt composite oxide represented by the general composition formula (4) From the viewpoint of ensuring the above effects better, the content of the lithium nickel cobalt manganese composite oxide represented by the general composition formula (3) in the total amount of the positive electrode active material is preferably 80% by mass or less. .

  For example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), or the like is preferably used for the binder related to the positive electrode mixture layer. In addition, as the conductive auxiliary agent related to the positive electrode mixture layer, for example, graphite (graphite carbon material) such as natural graphite (flaky graphite), artificial graphite; acetylene black, ketjen black, channel black, furnace black, Carbon materials such as carbon black such as lamp black and thermal black; carbon fiber;

  For the positive electrode, for example, a paste-like or slurry-like positive electrode mixture-containing composition in which a positive electrode active material, a binder, a conductive auxiliary agent, and the like are dispersed in a solvent such as N-methyl-2-pyrrolidone (NMP) is prepared ( However, the binder may be dissolved in a solvent), and this is applied to one or both sides of the current collector, dried, and then subjected to a calendering process as necessary. However, the positive electrode is not limited to those manufactured by the above manufacturing method, and may be manufactured by other methods.

  Moreover, you may form the lead body for electrically connecting with the other member in a lithium secondary battery according to a conventional method to a positive electrode as needed.

  The thickness of the positive electrode mixture layer is preferably, for example, 10 to 100 μm per one side of the current collector. Moreover, as a composition of a positive mix layer, it is preferable that the quantity of a positive electrode active material is 60-95 mass%, for example, it is preferable that the quantity of a binder is 1-15 mass%, and the quantity of a conductive support agent. Is preferably 3 to 20% by mass.

  The positive electrode current collector may be the same as that used for the conventionally known positive electrodes of lithium secondary batteries. For example, an aluminum foil having a thickness of 8 to 30 μm is preferable.

  Furthermore, as described above, an inorganic oxide particle layer can be provided on the surface of the positive electrode. In that case, after preparing a positive electrode according to a conventional method, an inorganic oxide particle layer forming slurry can be applied and dried to form an inorganic oxide particle layer. In addition, an inorganic oxide particle layer prepared in advance can be laminated on the positive electrode.

  The negative electrode related to the lithium secondary battery has, for example, a negative electrode active material, a binder, and, if necessary, a negative electrode mixture layer including a negative electrode mixture containing a conductive auxiliary agent on one side or both sides of the current collector. A structure can be used.

  Examples of the negative electrode active material include graphite, pyrolytic carbons, cokes, glassy carbons, fired bodies of organic polymer compounds, mesocarbon microbeads, carbon fibers, activated carbon, and metals that can be alloyed with lithium (Si , Sn, etc.) or alloys thereof, oxides, etc., and one or more of these can be used.

Among the negative electrode active materials, in order to increase the capacity of the battery, in particular, a material containing Si and O as constituent elements (provided that the atomic ratio x of O to Si is 0.5 ≦ x ≦ 1.5 Hereinafter, the material is preferably referred to as “SiO _x ”.

The SiO _x may contain Si microcrystal or amorphous phase. In this case, the atomic ratio of Si and O is a ratio including Si microcrystal or amorphous phase Si. That is, SiO _x includes a structure in which Si (for example, microcrystalline Si) is dispersed in an amorphous SiO ₂ matrix, and this amorphous SiO ₂ is dispersed in the SiO ₂ matrix. It is sufficient that the atomic ratio x satisfies 0.5 ≦ x ≦ 1.5 in combination with Si. For example, in the case of a material in which Si is dispersed in an amorphous SiO ₂ matrix and the material has a molar ratio of SiO ₂ to Si of 1: 1, x = 1, so that the structural formula is represented by SiO. The In the case of a material having such a structure, for example, in X-ray diffraction analysis, a peak due to the presence of Si (microcrystalline Si) may not be observed, but when observed with a transmission electron microscope, the presence of fine Si Can be confirmed.

Then, SiO _x is preferably a complex complexed with carbon materials, for example, it is desirable that the surface of the SiO _x is coated with a carbon material. As described above, since SiO _x has poor conductivity, when using it as a negative electrode active material, from the viewpoint of securing good battery characteristics, a conductive material (conductive aid) is used, and SiO _x in the negative electrode is used. It is necessary to form an excellent conductive network by mixing and dispersing the material and the conductive material well. If complexes complexed with carbon material SiO _x, for example, simply than with a material obtained by mixing a conductive material such as SiO _x and the carbon material, good conductive network in the negative electrode Formed.

The complex of the SiO _x and the carbon material, as described above, other although the surface of the SiO _x coated with carbon material, such as granules of SiO _x and the carbon material can be cited.

In addition, since the composite in which the surface of SiO _x is coated with a carbon material is further combined with a conductive material (carbon material or the like), a better conductive network can be formed in the negative electrode. Therefore, it is possible to realize a lithium secondary battery with higher capacity and more excellent battery characteristics (for example, charge / discharge cycle characteristics). The complex of the SiO _x and the carbon material coated with a carbon material, for example, like granules the mixture was further granulated with SiO _x and the carbon material coated with a carbon material.

Further, as SiO _x whose surface is coated with a carbon material, the surface of a composite (for example, a granulated body) of SiO _x and a carbon material having a smaller specific resistance value is further coated with a carbon material. Those can also be preferably used. In a state where SiO _x and the carbon material are dispersed inside the granulated body, a better conductive network can be formed. Therefore, in a lithium secondary battery having a negative electrode containing SiO _x as a negative electrode active material, a heavy load Battery characteristics such as discharge characteristics can be further improved.

Preferred examples of the carbon material that can be used to form a composite with SiO _x include carbon materials such as low crystalline carbon, carbon nanotubes, and vapor grown carbon fibers.

The details of the carbon material include at least one selected from the group consisting of fibrous or coiled carbon materials, carbon black (including acetylene black and ketjen black), artificial graphite, graphitizable carbon, and non-graphitizable carbon. A seed material is preferred. Fibrous or coil-like carbon materials are preferable in that they easily form a conductive network and have a large surface area. Carbon black (including acetylene black and ketjen black), graphitizable carbon, and non-graphitizable carbon have high electrical conductivity and high liquid retention, and even if SiO _x particles expand and contract. This is preferable in that it has a property of easily maintaining contact with the particles.

Further, as will be described in detail later, when SiO _x is used as the negative electrode active material, it is preferable to use graphite together, but this graphite is used as a carbon material related to a composite of SiO _x and a carbon material. You can also. Graphite, like carbon black, has high electrical conductivity and high liquid retention, and also has the property of easily maintaining contact with the SiO _x particles even when they expand and contract. Therefore, it can be preferably used for forming a complex with SiO _x .

Among the carbon materials exemplified above, a fibrous carbon material is particularly preferable for use when the composite with SiO _x is a granulated body. Fibrous carbon material can follow the expansion and contraction of SiO _x with the charging and discharging of the battery due to the high shape is thin threadlike flexibility, also because bulk density is large, many and SiO _x particles It is because it can have a junction. Examples of fibrous carbon include polyacrylonitrile (PAN) -based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, and carbon nanotube, and any of these may be used.

The fibrous carbon material can also be formed on the surface of the SiO _x particles by, for example, a vapor phase method.

The specific resistance value of SiO _x is usually 10 ³ to 10 ⁷ kΩcm, while the specific resistance value of the carbon material exemplified above is usually 10 ^{−5 to} 10 kΩcm.

The composite of SiO _x and the carbon material may further have a material layer (a material layer containing non-graphitizable carbon) that covers the carbon material coating layer on the particle surface.

When a composite of SiO _x and a carbon material is used for the negative electrode, the ratio of SiO _x and the carbon material is based on SiO _x : 100 parts by mass from the viewpoint of satisfactorily exerting the effect of the composite with the carbon material. The carbon material is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. Further, in the composite, if the ratio of the carbon material to be combined with SiO _x is too large, it may lead to a decrease in the amount of SiO _x in the negative electrode mixture layer, and the effect of increasing the capacity may be reduced. SiO _x: relative to 100 parts by weight, the carbon material, and more preferably preferably not more than 50 parts by weight, more than 40 parts by weight.

The composite of the SiO _x and the carbon material can be obtained, for example, by the following method.

First, a manufacturing method in the case of combining SiO _x will be described. A dispersion liquid in which SiO _x is dispersed in a dispersion medium is prepared, and sprayed and dried to produce composite particles including a plurality of particles. For example, ethanol or the like can be used as the dispersion medium. It is appropriate to spray the dispersion in an atmosphere of 50 to 300 ° C. In addition to the above method, similar composite particles can be produced also by a granulation method by a mechanical method using a vibration type or planetary type ball mill or rod mill.

Incidentally, the SiO _x, in the case of manufacturing a granulated body with small carbon material resistivity value than SiO _x is adding the carbon material in the dispersion liquid of SiO _x are dispersed in a dispersion medium, the dispersion by using a liquid, by a similar method to the case of composite of SiO _x may be a composite particle (granule). Further, by granulation process according to the similar mechanical method, it is possible to produce a granular material of the SiO _x and the carbon material.

Next, when the surface of SiO _x particles (SiO _x composite particles or a granulated body of SiO _x and a carbon material) is coated with a carbon material to form a composite, for example, the SiO _x particles and the hydrocarbon-based material The gas is heated in the gas phase, and carbon generated by pyrolysis of the hydrocarbon-based gas is deposited on the surface of the particles. As described above, according to the vapor deposition (CVD) method, the hydrocarbon-based gas spreads to every corner of the composite particle, and the surface of the particle and the pores in the surface are thin and contain a conductive carbon material. Since a uniform film (carbon material coating layer) can be formed, the SiO _x particles can be imparted with good conductivity with a small amount of carbon material.

In the production of SiO _x coated with a carbon material, the processing temperature (atmosphere temperature) of the vapor deposition (CVD) method varies depending on the type of hydrocarbon gas, but usually 600 to 1200 ° C. is appropriate. Among these, the temperature is preferably 700 ° C. or higher, and more preferably 800 ° C. or higher. This is because the higher the treatment temperature, the less the remaining impurities, and the formation of a coating layer containing carbon having high conductivity.

  As the liquid source of the hydrocarbon-based gas, toluene, benzene, xylene, mesitylene and the like can be used, but toluene that is easy to handle is particularly preferable. A hydrocarbon-based gas can be obtained by vaporizing them (for example, bubbling with nitrogen gas). Moreover, methane gas, acetylene gas, etc. can also be used.

In addition, after the surface of SiO _x particles (SiO _x composite particles or a granulated body of SiO _x and a carbon material) is covered with a carbon material by a vapor deposition (CVD) method, a petroleum-based pitch or a coal-based pitch is used. At least one organic compound selected from the group consisting of a thermosetting resin and a condensate of naphthalene sulfonate and aldehydes is attached to a coating layer containing a carbon material, and then the organic compound is attached. The obtained particles may be fired.

Specifically, a dispersion liquid in which a SiO _x particle (SiO _x composite particle or a granulated body of SiO _x and a carbon material) coated with a carbon material and the organic compound are dispersed in a dispersion medium is prepared, The dispersion is sprayed and dried to form particles coated with the organic compound, and the particles coated with the organic compound are fired.

  An isotropic pitch can be used as the pitch, and a phenol resin, a furan resin, a furfural resin, or the like can be used as the thermosetting resin. As the condensate of naphthalene sulfonate and aldehydes, naphthalene sulfonic acid formaldehyde condensate can be used.

As a dispersion medium for dispersing the SiO _x particles coated with the carbon material and the organic compound, for example, water or alcohols (ethanol or the like) can be used. It is appropriate to spray the dispersion in an atmosphere of 50 to 300 ° C. The firing temperature is usually 600 to 1200 ° C., preferably 700 ° C. or higher, and more preferably 800 ° C. or higher. This is because the higher the processing temperature, the less the remaining impurities, and the formation of a coating layer containing a high-quality carbon material with high conductivity. However, the processing temperature needs to be below the melting point of SiO _x .

When using SiO _x for the negative electrode active material according to the lithium secondary battery of the present invention, it is preferable to use graphite as the negative electrode active material. By reducing the ratio of SiO _x in the negative electrode active material using graphite, the negative electrode (negative electrode mixture) associated with charging / discharging of the battery is suppressed as much as possible while suppressing the decrease in the capacity-enhancing effect due to the reduction of SiO _x. It is possible to suppress a change in volume of the layer) and to suppress a decrease in battery characteristics that may be caused by the volume change.

Examples of graphite used as the negative electrode active material together with SiO _x include natural graphite such as flaky graphite; graphitizable carbon such as pyrolytic carbons, mesophase carbon microbeads (MCMB), and carbon fibers at 2800 ° C. or more. Artificial graphite subjected to chemical treatment; and the like.

In the negative electrode according to the present invention, from the viewpoint of satisfactorily ensuring the effect of the high capacity by using a SiO _x, the content of SiO _x in the anode active material is 0.01 wt% or more It is preferably 3% by mass or more. Further, from the viewpoint of better avoiding the problem due to the volume change of the negative electrode due to charge / discharge, the content of SiO _x in the negative electrode active material is preferably 30% by mass or less, and 20% by mass or less. Is more preferable.

  Moreover, the same thing as what was illustrated previously as what can be used for a positive electrode can be used for the binder and conductive support agent of a negative electrode.

  For the negative electrode, for example, a negative electrode active material, a binder, and a conductive auxiliary agent used as necessary are prepared in a paste-like or slurry-like negative electrode mixture-containing composition in which a solvent such as NMP or water is dispersed. (However, the binder may be dissolved in a solvent), which is applied to one or both sides of the current collector, dried, and then subjected to a calendering process as necessary. However, the negative electrode is not limited to those manufactured by the above manufacturing method, and may be manufactured by other methods.

  Moreover, you may form in the negative electrode the lead body for electrically connecting with the other member in a lithium secondary battery according to a conventional method as needed.

  The thickness of the negative electrode mixture layer is preferably 10 to 100 μm per one surface of the current collector, for example. Moreover, as a composition of a negative mix layer, it is preferable that a negative electrode active material shall be 80.0-99.8 mass% and a binder shall be 0.1-10 mass%, for example. Furthermore, when making a negative mix layer contain a conductive support agent, it is preferable that the quantity of the conductive support agent in a negative mix layer shall be 0.1-10 mass%.

  As the current collector for the negative electrode, a foil made of copper or nickel, a punching metal, a net, an expanded metal, or the like can be used, but a copper foil is usually used. In the negative electrode current collector, when the thickness of the entire negative electrode is reduced in order to obtain a battery having a high energy density, the upper limit of the thickness is preferably 30 μm, and the lower limit is 5 μm in order to ensure mechanical strength. Is desirable.

  Furthermore, as described above, an inorganic oxide particle layer can be provided on the surface of the negative electrode. In that case, after preparing a negative electrode according to a conventional method, a slurry for forming an inorganic oxide particle layer can be applied and dried to form an inorganic oxide particle layer. In addition, an inorganic oxide particle layer prepared in advance can be laminated on the negative electrode.

The separator according to the lithium secondary battery has a property that the pores are closed at 80 ° C. or higher (more preferably 100 ° C. or higher) and 170 ° C. or lower (more preferably 150 ° C. or lower) (ie, shutdown function). It is preferable that a separator used in a normal lithium secondary battery, for example, a microporous membrane made of polyolefin such as polyethylene (PE) or polypropylene (PP) can be used. The microporous film constituting the separator may be, for example, one using only PE or one using PP, or a laminate of a PE microporous film and a PP microporous film. There may be.
Further, a separator integrated with such a conventional microporous membrane by laminating the inorganic oxide particle layer may be used. In that case, an inorganic oxide particle layer can be formed by applying a slurry for forming an inorganic oxide particle layer to a conventional microporous film and drying it. Moreover, the inorganic oxide particle layer produced previously can also be affixed on a separator, and can also be laminated | stacked.

  The thickness of the separator is preferably 6 to 30 μm (including the inorganic oxide particle layer when the inorganic oxide particle layer is provided on the separator surface), for example.

  The positive electrode, the negative electrode, and the separator are formed in the form of a laminated electrode body in which a separator is interposed between the positive electrode and the negative electrode, or a wound electrode body in which the separator is wound in a spiral shape. It can be used for the lithium battery of the invention.

  Examples of the form of the lithium secondary battery of the present invention include a cylindrical shape (such as a rectangular tube shape or a cylindrical shape) using a steel can or an aluminum can as an outer can. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.

The lithium secondary battery of the present invention can be used with the upper limit voltage for charging set to about 4.2 V as in the conventional lithium secondary battery, but the upper limit voltage for charging is set to 4.3 V or higher. Thus, it is possible to increase the capacity, and even when used at such a high voltage, high reliability and storage characteristics can be exhibited. In addition, it is preferable that the upper limit voltage of charge in the lithium secondary battery of this invention is 4.7V or less.

  Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention.

Example 1
<Preparation of positive electrode>
100 parts by mass of a positive electrode active material obtained by mixing LiCoO ₂ and Li _1.0 Ni _0.5 Co _0.2 Mn _0.3 O _{2 at} a ratio (mass ratio) of 8: 2, and 10 parts by mass of PVDF as a binder. 20 parts by weight of NMP solution contained at a concentration of 1%, 1 part by weight of artificial graphite and 1 part by weight of ketjen black, which are conductive assistants, are kneaded using a biaxial kneader, and NMP is added to adjust the viscosity. Thus, a positive electrode mixture-containing paste was prepared.

  After coating the positive electrode mixture-containing paste on both surfaces of an aluminum foil (positive electrode current collector) having a thickness of 15 μm, vacuum drying is performed at 120 ° C. for 12 hours to form a positive electrode mixture layer on both surfaces of the aluminum foil. did. Thereafter, press treatment was performed to adjust the thickness and density of the positive electrode mixture layer, and a nickel lead body was welded to the exposed portion of the aluminum foil to produce a strip-like positive electrode having a length of 375 mm and a width of 43 mm. . The positive electrode mixture layer in the obtained positive electrode had a thickness of 55 μm per one side.

<Production of negative electrode>
A composite in which the surface of SiO having an average particle diameter D50% of 8 μm, which is a negative electrode active material, is coated with a carbon material (the amount of the carbon material in the composite is 10% by mass), and graphite having an average particle diameter D50% of 16 μm A mixture in which the amount of the composite having the SiO surface coated with a carbon material is 3.75% by mass: 97.5 parts by mass, SBR as a binder: 1.5 parts by mass, and a thickener CMC: 1 part by mass of water was added and mixed to prepare a negative electrode mixture-containing paste.

  After applying the negative electrode mixture-containing paste to both sides of a copper foil (negative electrode current collector) having a thickness of 8 μm, vacuum drying is performed at 120 ° C. for 12 hours to form a negative electrode mixture layer on both sides of the copper foil. did. Thereafter, press treatment was performed to adjust the thickness and density of the negative electrode mixture layer, and a nickel lead body was welded to the exposed portion of the copper foil to produce a strip-shaped negative electrode having a length of 380 mm and a width of 44 mm. . The negative electrode mixture layer in the obtained negative electrode had a thickness of 65 μm per one surface.

<Preparation of non-aqueous electrolyte>
LiPF ₆ was dissolved in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) at a volume ratio of 3: 7 at a concentration of 1.1 mol / L, and an amount of 0.50% by mass of allyl succinic anhydride was obtained. , VC is 2.0% by mass, adiponitrile is 0.5% by mass, 1,3-dioxane is 1.0% by mass, and PDEA is 1.0% by mass. A nonaqueous electrolyte was prepared by adding FEC in an amount of 1.0% by mass.

<Preparation of inorganic oxide particle layer forming slurry>
To 5 kg of plate boehmite (average particle diameter 1 μm, aspect ratio 10), 5 kg of ion-exchanged water and 0.5 kg of a dispersant (aqueous polycarboxylic acid ammonium salt, solid content concentration 40% by mass) are added, and the internal volume is 20 L. Dispersion was prepared by crushing for 10 hours with a ball mill with 40 rotations / minute. When a part of the treated dispersion was vacuum dried at 120 ° C. and observed with a scanning electron microscope (SEM), the shape of boehmite was almost plate-like. The average particle size of the boehmite after the treatment was 1 μm.

  To 500 g of the above dispersion, 0.5 g of xanthan gum as a thickener and 17 g of resin binder dispersion (modified polybutyl acrylate, solid content 45% by mass) as a binder are added and stirred for 3 hours with a three-one motor to obtain a uniform inorganic A slurry for forming an oxide particle layer (solid content ratio 50% by mass) was prepared.

<Preparation of separator with inorganic oxide particle layer>
A PE microporous film (thickness 10 μm, porosity 40%, average pore diameter 0.08 μm, PE melting point 135 ° C.) was subjected to corona discharge treatment (discharge amount 40 W · min / m ² ), and this treated surface The inorganic oxide particle layer forming slurry was applied to a microgravure coater and dried to form an inorganic oxide particle layer having a thickness of 2 μm on one side of the separator to produce a separator with an inorganic oxide particle layer. .

<Battery assembly>
The strip-shaped positive electrode is overlapped with the strip-shaped negative electrode via the separator, wound in a spiral shape, and then pressed so as to be flattened to form a wound electrode body having a flat wound structure. The rotating body was fixed with an insulating tape made of polypropylene. Next, the wound electrode body is inserted into a prismatic battery case made of aluminum alloy having an outer dimension of 4.0 mm in thickness, 34 mm in width, and 50 mm in height, and the lead body is welded, and the lid made of aluminum alloy The plate was welded to the open end of the battery case. Thereafter, the non-aqueous electrolyte is injected from the inlet provided in the cover plate, and left for 1 hour, and then the inlet is sealed. The lithium secondary battery having the structure shown in FIG. Obtained.

  Here, the battery shown in FIGS. 1 and 2 will be described. FIG. 1 is a partial sectional view of the battery, and the positive electrode 1 and the negative electrode 2 are spirally wound via a separator 3 and then flattened. The flat wound electrode body 6 is pressurized and accommodated in a rectangular (square tube) battery case 4 together with a nonaqueous electrolyte. However, in FIG. 1, in order to avoid complication, a metal foil, a non-aqueous electrolyte, and the like as a current collector used for manufacturing the positive electrode 1 and the negative electrode 2 are not illustrated.

  The battery case 4 is made of an aluminum alloy and constitutes an outer package of the battery. The battery case 4 also serves as a positive electrode terminal. And the insulator 5 which consists of PE sheets is arrange | positioned at the bottom part of the battery case 4, and it connects to each one end of the positive electrode 1 and the negative electrode 2 from the flat wound electrode body 6 which consists of the positive electrode 1, the negative electrode 2, and the separator 3. The positive electrode lead body 7 and the negative electrode lead body 8 thus drawn are drawn out. A stainless steel terminal 11 is attached to a sealing lid plate 9 made of aluminum alloy for sealing the opening of the battery case 4 via a polypropylene insulating packing 10, and an insulator 12 is attached to the terminal 11. A stainless steel lead plate 13 is attached.

  And this cover plate 9 is inserted in the opening part of the battery case 4, and the opening part of the battery case 4 is sealed by welding the joint part of both, and the inside of the battery is sealed. Further, in the battery of FIG. 1, a non-aqueous electrolyte inlet 14 is provided in the lid plate 9, and the non-aqueous electrolyte inlet 14 is welded by, for example, laser welding with a sealing member inserted. The battery is sealed to ensure the battery hermeticity. Further, the lid plate 9 is provided with a cleavage vent 15 as a mechanism for discharging the internal gas to the outside when the temperature of the battery rises.

  In the battery of this Example 1, the outer can 5 and the cover plate 9 function as a positive electrode terminal by directly welding the positive electrode lead body 7 to the lid plate 9, and the negative electrode lead body 8 is welded to the lead plate 13, The terminal 11 functions as a negative electrode terminal by conducting the negative electrode lead body 8 and the terminal 11 through the lead plate 13, but depending on the material of the battery case 4, the sign may be reversed. There is also.

  FIG. 2 is a perspective view schematically showing the external appearance of the battery shown in FIG. 1. FIG. 2 is shown for the purpose of showing that the battery is a square battery. FIG. 1 schematically shows a battery, and only specific members of the battery are shown. Also in FIG. 1, the inner peripheral portion of the electrode body is not cross-sectional.

Example 2
An amount of 1.5% by mass of allyl succinic anhydride, an amount of VC of 1.0% by mass, an amount of adiponitrile of 0.5% by mass, and 1,3-dioxane of 1.0% by mass In the same manner as in Example 1, except that a non-aqueous electrolyte was prepared by adding PDEA in an amount of 1.0% by mass and FEC in an amount of 1.0% by mass, respectively. A secondary battery was prepared.

Example 3
An amount of 2.0% by mass of allyl succinic anhydride, an amount of VC of 0.5% by mass, an amount of adiponitrile of 0.5% by mass, and 1,3-dioxane of 1.0% by mass In the same manner as in Example 1, except that a non-aqueous electrolyte was prepared by adding PDEA in an amount of 1.0% by mass and FEC in an amount of 1.0% by mass, respectively. A secondary battery was prepared.

Example 4
An amount of 1.0% by mass of allyl succinic anhydride, an amount of VC of 2.5% by mass, an amount of adiponitrile of 0.5% by mass, and 1,3-dioxane of 1.0% by mass In the same manner as in Example 1, except that a non-aqueous electrolyte was prepared by adding PDEA in an amount of 1.0% by mass and FEC in an amount of 1.0% by mass, respectively. A secondary battery was prepared.

Example 5
An amount of 1.0% by mass of allyl succinic anhydride, an amount of VC of 4.0% by mass, an amount of adiponitrile of 0.5% by mass, and 1,3-dioxane of 1.0% by mass In the same manner as in Example 1, except that a non-aqueous electrolyte was prepared by adding PDEA in an amount of 1.0% by mass and FEC in an amount of 1.0% by mass, respectively. A secondary battery was prepared.

Example 6
An amount of 3.0% by mass of allyl succinic anhydride, an amount of VC of 1.0% by mass, an amount of adiponitrile of 0.5% by mass, and 1,3-dioxane of 1.0% by mass In the same manner as in Example 1, except that a non-aqueous electrolyte was prepared by adding PDEA in an amount of 1.0% by mass and FEC in an amount of 1.0% by mass, respectively. A secondary battery was prepared.

Example 7
An amount of 0.1% by mass of allyl succinic anhydride, an amount of VC of 4.0% by mass, an amount of adiponitrile of 0.5% by mass, and 1,3-dioxane of 1.0% by mass In the same manner as in Example 1, except that a non-aqueous electrolyte was prepared by adding PDEA in an amount of 1.0% by mass and FEC in an amount of 1.0% by mass, respectively. A secondary battery was prepared.

Example 8
A separator with an inorganic oxide particle layer was prepared in the same manner as in Example 1 except that the inorganic oxide particles were changed to titania having an average particle diameter of 0.2 μm.
A lithium secondary battery was produced in the same manner as in Example 1 except that the above separator was used.

Example 9
A separator with an inorganic oxide particle layer was prepared in the same manner as in Example 1 except that the inorganic oxide particles were changed to alumina fine particles having an average particle diameter of 0.5 μm.
A lithium secondary battery was produced in the same manner as in Example 1 except that the above separator was used.

Example 10
A separator with an inorganic oxide particle layer was prepared in the same manner as in Example 1 except that the inorganic oxide particles were changed to silica fine particles having an average particle diameter of 1.0 μm.
A lithium secondary battery was produced in the same manner as in Example 1 except that the above separator was used.

Example 11
The same inorganic oxide particle layer forming slurry as in Example 1 was applied to the same positive electrode surface as in Example 1 with a microgravure coater and dried to form an inorganic oxide particle layer having a thickness of 2 μm on both surfaces of the positive electrode. Then, a positive electrode with an inorganic oxide particle layer was produced.
Example 1 except that the positive electrode with the inorganic oxide particle layer and a microporous separator made of PE (thickness 12 μm, porosity 40%, average pore diameter 0.08 μm, PE melting point 135 ° C.) were used. Thus, a lithium secondary battery was prepared.

Example 12
A slurry for forming inorganic oxide particles was prepared in the same manner as in Example 1 except that the inorganic oxide particles were changed to titania having an average particle diameter of 0.2 μm.
The inorganic oxide particle layer forming slurry is applied to the same positive electrode surface as in Example 1 with a microgravure coater and dried to form inorganic oxide particle layers having a thickness of 2 μm on both surfaces of the positive electrode. A positive electrode with an inorganic oxide particle layer was produced.
Example 1 except that the positive electrode with the inorganic oxide particle layer and a microporous separator made of PE (thickness 12 μm, porosity 40%, average pore diameter 0.08 μm, PE melting point 135 ° C.) were used. Thus, a lithium secondary battery was prepared.

Example 13
The same inorganic oxide particle layer forming slurry as in Example 1 was applied to the negative electrode surface as in Example 1 with a microgravure coater and dried to form an inorganic oxide particle layer having a thickness of 2 μm on both surfaces of the negative electrode. Thus, a negative electrode with an inorganic oxide particle layer was produced.
Example 1 except that the negative electrode with an inorganic oxide particle layer and a microporous separator made of PE (thickness 12 μm, porosity 40%, average pore size 0.08 μm, PE melting point 135 ° C.) were used. Thus, a lithium secondary battery was prepared.

Example 14
An amount of 0.5% by mass of allyl succinic anhydride, an amount of VC of 2.5% by mass, an amount of adiponitrile of 0.5% by mass, and 1,3-dioxane of 1.0% by mass A lithium secondary battery was made in the same manner as in Example 1 except that a non-aqueous electrolyte was prepared by adding FEC in an amount of 1.0% by mass.

Example 15
An amount of 0.5% by weight of allyl succinic anhydride, an amount of VC of 2.5% by weight, an amount of adiponitrile of 0.5% by weight, and an amount of PDEA of 1.0% by weight, A lithium secondary battery was prepared in the same manner as in Example 1, except that a nonaqueous electrolyte was prepared by adding FEC in an amount of 1.0% by mass.

Example 16
An amount of 0.5% by mass of allyl succinic anhydride, an amount of VC of 2.5% by mass, an amount of 1,3-dioxane of 1.0% by mass, and PDEA of 1.0% by mass A lithium secondary battery was made in the same manner as in Example 1 except that a non-aqueous electrolyte was prepared by adding FEC in an amount of 1.0% by mass.

Example 17
An amount of 0.5% by mass of allyl succinic anhydride, an amount of VC of 2.5% by mass, an amount of 1,3-dioxane of 1.0% by mass, and PDEA of 1.0% by mass And a non-aqueous electrolyte was prepared by adding adiponitrile in an amount of 0.5% by mass.
A separator was prepared in the same manner as in Example 1 except that the thickness of the inorganic oxide particle layer of the separator was 3 μm.
A lithium secondary battery was produced in the same manner as in Example 1 except that the above nonaqueous electrolyte and the above separator were used.

Comparative Example 1
VC is 2.0% by mass, adiponitrile is 0.5% by mass, 1,3-dioxane is 1.0% by mass, and PDEA is 1.0% by mass. A nonaqueous electrolyte was prepared by adding FEC in an amount of 1.0% by mass (that is, without adding allyl succinic anhydride).
A lithium secondary as in Example 1 except that the above electrolyte was used and a microporous separator made of PE (thickness 12 μm, porosity 40%, average pore size 0.08 μm, PE melting point 135 ° C.) was used. A battery was created.

Comparative Example 2
VC is 2.0% by mass, adiponitrile is 0.5% by mass, 1,3-dioxane is 1.0% by mass, and PDEA is 1.0% by mass. A nonaqueous electrolyte was prepared by adding FEC in an amount of 1.0% by mass (that is, without adding allyl succinic anhydride). A lithium secondary battery was produced in the same manner as in Example 1 except that this nonaqueous electrolyte was used.

Comparative Example 3
An amount of 2.0% by mass of allyl succinic anhydride, an amount of 0.5% by mass of adiponitrile, an amount of 1.0% by mass of 1,3-dioxane, and 1.0% by mass of PDEA And non-aqueous electrolyte was prepared by adding FEC in an amount of 1.0% by mass (ie, without adding VC). A lithium secondary battery was produced in the same manner as in Example 1 except that this nonaqueous electrolyte was used.

Comparative Example 4
An amount of 0.1% by mass of allyl succinic anhydride, an amount of VC of 4.5% by mass, an amount of adiponitrile of 0.5% by mass, and 1,3-dioxane of 1.0% by mass A non-aqueous electrolyte was prepared by adding PDEA in an amount of 1.0% by mass and FEC in an amount of 1.0% by mass, respectively. A lithium secondary battery was produced in the same manner as in Example 1 except that this nonaqueous electrolyte was used.

Comparative Example 5
An amount of 3.1% by mass of allyl succinic anhydride, an amount of VC of 0.01% by mass, an amount of adiponitrile of 0.5% by mass, and 1,3-dioxane of 1.0% by mass A non-aqueous electrolyte was prepared by adding PDEA in an amount of 1.0% by mass and FEC in an amount of 1.0% by mass, respectively. A lithium secondary battery was produced in the same manner as in Example 1 except that this nonaqueous electrolyte was used.

Comparative Example 6
An amount of 2.0% by mass of allyl succinic anhydride, an amount of VC of 4.5% by mass, an amount of adiponitrile of 0.5% by mass, and 1,3-dioxane of 1.0% by mass A non-aqueous electrolyte was prepared by adding PDEA in an amount of 1.0% by mass and FEC in an amount of 1.0% by mass, respectively. A lithium secondary battery was produced in the same manner as in Example 1 except that this nonaqueous electrolyte was used.

Comparative Example 7
An amount of 3.1% by mass of allyl succinic anhydride, an amount of VC of 2.0% by mass, an amount of adiponitrile of 0.5% by mass, and 1,3-dioxane of 1.0% by mass A non-aqueous electrolyte was prepared by adding PDEA in an amount of 1.0% by mass and FEC in an amount of 1.0% by mass, respectively. A lithium secondary battery was produced in the same manner as in Example 1 except that this nonaqueous electrolyte was used.

Comparative Example 8
An amount of 0.5% by mass of allyl succinic anhydride, an amount of VC of 2.5% by mass, an amount of adiponitrile of 0.5% by mass, and 1,3-dioxane of 1.0% by mass A non-aqueous electrolyte was prepared by adding PDEA in an amount of 1.0% by mass and FEC in an amount of 1.0% by mass, respectively. A lithium secondary battery was produced in the same manner as in Example 1 except that this nonaqueous electrolyte was used.
Lithium was obtained in the same manner as in Example 1 except that the above nonaqueous electrolyte was used and a microporous separator made of PE (thickness 12 μm, porosity 40%, average pore diameter 0.08 μm, PE melting point 135 ° C.) was used. A secondary battery was prepared.

  The following cycle characteristic tests and high-temperature storage tests were performed on the lithium secondary batteries of the examples and comparative examples.

<Charge / discharge cycle characteristics evaluation>
The lithium secondary batteries of Examples and Comparative Examples were left in a constant temperature bath at 45 ° C. for 5 hours, and then each battery was charged with a constant current to 4.4 V at a current value of 0.5 C, and subsequently 4. The battery was charged at a constant voltage of 4 V (the total charging time of constant current charging and constant voltage charging was 2.5 hours), and then discharged at 2.75 V at a constant current of 0.2 C to obtain the initial discharge capacity. . Next, each battery was charged at a constant current of up to 4.4 V at a current value of 1 C at 45 ° C., and subsequently charged until a current value of 0.1 C was reached at a constant voltage of 4.4 V. A series of operations for discharging to a value of 3.0 V was taken as one cycle and this was repeated many times. Each battery was subjected to 500 cycles, and a constant current-constant voltage charge and a constant current discharge were performed under the same conditions as in the initial discharge capacity measurement, to determine a discharge capacity. A value obtained by dividing these discharge capacities by the initial discharge capacities was expressed as a percentage to calculate a 45 ° C. capacity retention rate.
Further, the room temperature capacity retention rate was calculated in the same manner as in the above method except that the temperature environment was 25 ° C.

<Storage test 1 high-temperature storage swelling>
About each lithium secondary battery of an Example and a comparative example, it carried out the constant current charge to 4.4V with the electric current value of 0.5C, and carried out the constant voltage charge at 4.4V subsequently. Thereafter, the thickness of the central part of the outer package was measured using a micrometer. (Total charging time of constant current charging and constant voltage charging was 2.5 hours) Each battery was placed in a thermostat kept at 85 ° C. and stored for 4 hours. Then, each battery was taken out from the thermostat and discharged to 2.75 V at 0.2 C after 2 hours. Thereafter, the battery was charged to 4.4V at 0.5C and then discharged to 2.75V at 0.2C. And the thickness of the center part of an exterior body was measured using the micrometer similarly to before storage.
The difference between the thickness of the outer package before storage and the thickness of the outer package after storage was divided by the thickness of the outer package before storage and expressed as a percentage.

<Storage test 2 capacity deterioration rate>
About each lithium secondary battery of an Example and a comparative example, it carried out the constant current charge to 4.4V with the electric current value of 0.5C, and carried out the constant voltage charge at 4.4V subsequently. (Total charging time of constant current charging and constant voltage charging is 2.5 hours) Each battery was placed in a thermostat kept at 85 ° C. and stored for 24 hours. Then, each battery was taken out from the thermostat and discharged to 2.75 V at 0.2 C after 2 hours. Thereafter, the battery was charged to 4.4 V at 0.5 C, and then discharged to 2.75 V at 0.2 C to obtain a recovery capacity. The storage capacity deterioration rate was obtained by dividing the recovery capacity after storage by the initial discharge capacity (discharge capacity before storage) and expressed as a percentage.

  The composition of the nonaqueous electrolyte additive used in each of the lithium secondary batteries of Examples and Comparative Examples is shown in Table 1, and the results of the capacity retention ratio and the storage test results are shown in Table 2.

  The present invention can be implemented in other forms without departing from the spirit of the present invention. The embodiments disclosed in the present application are examples, and the present invention is not limited to these embodiments. The scope of the present invention is construed in preference to the description of the appended claims rather than the description of the above specification, and all modifications within the scope equivalent to the claims are construed in the scope of the claims. included.

  The lithium secondary battery of the present invention can be used for the same applications as various applications to which conventionally known lithium secondary batteries are applied.

1 Positive electrode 2 Negative electrode 3 Separator

Claims (4)

A secondary battery comprising a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte,
The separator is a laminate of a porous film and a non-motor oxide particle layer,
The inorganic oxide particle layer includes inorganic oxide particles and a binder,
The inorganic oxide particle layer has a thickness of 1 μm to 5 μm ,
The non-aqueous electrolyte contains an allyl succinic anhydride, vinylene carbonate, and a lithium salt containing fluorine,
A lithium secondary battery using a non-aqueous electrolyte in which allyl succinic anhydride in the non-aqueous electrolyte is 0.1 to 3% by mass and vinylene carbonate is 0.5 to 4% by mass. Lithium salt including fluorine may be a lithium secondary battery according to claim 1 which is LiPF _6.  The lithium secondary battery according to claim 1, wherein the inorganic oxide particles are any one of alumina, silica, and boehmite. The lithium secondary battery according to claim 1, wherein the non-aqueous electrolyte further contains a phosphonoacetate compound represented by the following general formula (1).

In [Formula ^{(1), R 1, R} 2 and ^{R 3} are each independently a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom, n represents 0-6 Is an integer. ]

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