JP2012138335A - Nonaqueous electrolyte secondary battery and nonaqueous electrolyte, battery pack, electronic device, electric vehicle, power storage device, and power system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a nonaqueous electrolyte secondary battery, in which gas generation caused when used in a high-temperature environment can be suppressed and cycle characteristics can be also improved, and a nonaqueous electrolyte; and a battery pack, an electronic apparatus, an electric vehicle, an electricity storage device and an electric power system which include the nonaqueous electrolyte secondary battery.SOLUTION: An electrolyte is a gelatinous electrolyte including an electrolytic solution and a polymer compound holding the electrolytic solution. The electrolytic solution includes a cyclic alkylene carbonate and a dinitrile compound represented by formula (1), and the content of the cyclic alkylene carbonate is 80 mass% or more relative to the total mass of the electrolytic solution. Formula (1) NC-(CH)-CN (In the formula, n represents an integer of 1 or more.)

Description

  The present technology relates to a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte, a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system. More specifically, for example, a non-aqueous electrolyte secondary battery using a non-aqueous electrolyte containing a non-aqueous electrolyte containing a non-aqueous solvent and an electrolyte salt, and a battery pack, electronic device, electric vehicle, power storage device, and The power system.

  In recent years, portable electronic devices such as a camera-integrated VTR (Video Tape Recorder), a mobile phone, or a laptop computer have become widespread, and there is a strong demand for miniaturization, weight reduction, and long life. Accordingly, as a power source, development of a battery, in particular, a secondary battery that is lightweight and capable of obtaining a high energy density is in progress.

  Among them, secondary batteries (so-called lithium ion secondary batteries) that use lithium (Li) occlusion and release for charge / discharge reactions are highly expected because they can obtain higher energy density than lead batteries and nickel cadmium batteries. Yes. This lithium ion secondary battery includes an electrolyte that is an ion conductive medium together with a positive electrode and a negative electrode.

  In order to improve various performances of secondary batteries, diligent development is underway. For example, a laminated battery using a laminated film such as an aluminum laminated film as an exterior member can increase the energy density because it is lightweight. In a laminate type battery, a polymer compound is contained together with an electrolytic solution as an electrolyte. In such a laminate-type polymer battery, when the polymer compound is swollen by the electrolytic solution, the deformation of the laminate-type battery can be suppressed. In particular, the gel polymer is obtained by swelling and polymerizing the polymer compound by the electrolyte solution. Gel-type electrolyte batteries using the are widely used.

  By the way, in the conventional lithium ion secondary battery that operates at a maximum of 4.2 V, the positive electrode active material such as lithium cobaltate used for the positive electrode only uses about 60% of its theoretical capacity. Absent. For this reason, it is theoretically possible to utilize the remaining capacity by further increasing the charging voltage. In fact, it is known that high energy density can be realized by setting the voltage during charging to 4.25 V or more. (For example, see Patent Document 1)

  Usually, in lithium ion secondary batteries, lithium cobaltate is used for the positive electrode and a carbon material is used for the negative electrode, and the operating voltage is used in the range of 4.2V to 2.5V. In the unit cell, the terminal voltage can be increased to 4.2 V largely due to excellent electrochemical stability such as a non-aqueous electrolyte material and a separator.

  However, when charging and discharging are performed at an operating voltage of 4.25 V or higher in a lithium ion secondary battery, more lithium is released from the positive electrode as the charging progresses. For this reason, the positive electrode is placed in a thermally and electrically unstable state, and undesirable side reactions such as decomposition of the electrolytic solution become more prominent. The problem of being damaged arises.

  In an electrolytic solution used for a laminate-type battery, since the laminate exterior is soft and easily swells in a high-temperature environment, a cyclic carbonate having a high boiling point is contained in an amount of 80% by mass or more. (For example, refer to Patent Document 2) In addition, Patent Document 3 discloses a non-aqueous electrolyte secondary battery using an electrolytic solution containing γ-butyrolactone having a high boiling point and a high dielectric constant, similar to the cyclic carbonate. It is disclosed.

International Publication No. 03/019713 Pamphlet JP 2001-167797 A JP 2000-235868 A JP-A-10-214640

  However, in a battery in which the charging voltage is set to 4.25 V or more, the oxidizing atmosphere in the vicinity of the positive electrode surface is strengthened. As a result, when a conventional electrolyte is used, the cell is deformed due to gas generation particularly in a high temperature environment. there were. In addition, this problem becomes more prominent because the reaction is promoted as the charging voltage becomes higher, and the suppression by the conventional electrolytic solution using the above-described cyclic carbonate or γ-butyrolactone is not sufficient.

  Further, if the deformation is large, it becomes easy to short-circuit inside, and it does not function as a battery. As disclosed in Patent Document 4, the strength up to short-circuiting is increased by applying ceramics to the electrode surface, but the impregnating property of the electrolytic solution into the electrode is lowered, and the characteristics are lowered.

  The present technology has been made in view of such problems, and the purpose thereof is to suppress gas generation accompanying use in a high-temperature environment and improve cycle characteristics even when the charging voltage is set to 4.25 V or higher. An object of the present invention is to provide a nonaqueous electrolyte secondary battery and a nonaqueous electrolyte that can be produced, and a battery pack, electronic device, electric vehicle, power storage device, and electric power system using the same.

In order to solve the above-described problem, the present technology includes a positive electrode, a negative electrode, and a non-aqueous electrolyte including a non-aqueous electrolyte solution containing a non-aqueous solvent and an electrolyte salt, and fully charged per pair of the positive electrode and the negative electrode. The open circuit voltage in the state is set in the range of 4.25 V or more and 4.50 V or less, and the non-aqueous solvent includes cyclic alkylene carbonate and a dinitrile compound represented by the formula (1), and cyclic alkylene carbonate The content of is a nonaqueous electrolyte secondary battery that is 80% by mass or more with respect to the total mass of the nonaqueous electrolyte.
Formula (1)
NC- (CH _{2) n} -CN
(In the formula, n is an integer of 1 or more.)

The present technology includes a nonaqueous electrolytic solution containing a nonaqueous solvent and an electrolyte salt, and the nonaqueous solvent includes a cyclic alkylene carbonate and a dinitrile compound represented by the formula (1), and the content of the cyclic alkylene carbonate Is a non-aqueous electrolyte that is 80% by mass or more based on the total mass of the non-aqueous electrolyte.
Formula (1)
NC- (CH _{2) n} -CN
(In the formula, n is an integer of 1 or more.)

  In the present technology, the nonaqueous electrolytic solution contains 80% by mass or more of cyclic alkylene carbonate and the dinitrile compound represented by the formula (1), thereby suppressing gas generation accompanying use in a high temperature environment. At the same time, the cycle characteristics can be improved.

  Furthermore, the battery pack, the electronic device, the electric vehicle, the power storage device, and the power system according to the present technology include the nonaqueous electrolyte secondary battery described above.

  According to the present technology, it is possible to suppress gas generation accompanying use in a high temperature environment and improve cycle characteristics.

It is a disassembled perspective view which shows the structural example of the nonaqueous electrolyte battery by embodiment of this technique. It is sectional drawing along the II line of the winding electrode body in FIG. It is a block diagram which shows the structural example of the battery pack by embodiment of this technique. It is the schematic which shows the example applied to the electrical storage system for houses using the nonaqueous electrolyte battery of this technique. It is a schematic diagram showing roughly an example of composition of a hybrid vehicle which adopts a series hybrid system to which this art is applied.

Hereinafter, embodiments of the present technology will be described with reference to the drawings. The description will be given in the following order.
1. First embodiment (electrolyte)
2. Second Embodiment (First Example of Nonaqueous Electrolyte Battery)
3. Third embodiment (second example of nonaqueous electrolyte battery)
4). Fourth Embodiment (Third Example of Nonaqueous Electrolyte Battery)
5. Fifth embodiment (example of battery pack using non-aqueous electrolyte battery)
6). Sixth embodiment (an example of a power storage system using a nonaqueous electrolyte battery)
7). Other embodiment (modification)

1. First embodiment (electrolyte)
The electrolyte according to the first embodiment of the present technology will be described. The electrolyte according to the first embodiment of the present technology is a non-aqueous electrolyte containing an ion conductive non-aqueous solvent, for example, a non-aqueous electrolyte that is a liquid electrolyte. This nonaqueous electrolytic solution contains a nonaqueous solvent and an electrolyte salt. The non-aqueous solvent contains a nitrile compound and a cyclic alkylene ester. The electrolyte according to the first embodiment of the present technology is used in an electrochemical device such as a nonaqueous electrolyte battery.

(Nitrile compound)
The nonaqueous electrolytic solution contains a hydrocarbon compound having two nitrile groups, such as a dinitrile compound represented by the formula (1), as a nonaqueous solvent. When the non-aqueous electrolyte contains the dinitrile compound represented by the formula (1), the dinitrile compound represented by the formula (1) may be contained in one kind or in two or more kinds. .

Formula (1)
NC- (CH _{2) n} -CN
(In the formula, n is an integer of 1 or more.)

  In addition, as a hydrocarbon compound having a nitrile group related to the present technology, for example, in Japanese Patent Application Laid-Open No. 07-176322, charging with a voltage exceeding 4.2 V by adding an organic compound having two or more cyano groups. A technique for suppressing the decomposition of the electrolytic solution is disclosed. However, this technique is not preferable because it uses a chain carbonate which is a low-boiling solvent and cannot improve the problem in a high temperature environment.

  Further, for example, Japanese Patent Application Laid-Open No. 2004-179146 discloses a technique for containing a nitrile compound and an S═O group-containing compound in a nonaqueous electrolytic solution. Accordingly, it has been proposed that a protective coating for suppressing corrosion is formed on the metal surface of a battery can or the like, and that the storage characteristics in a charged state are improved by a corrosion prevention effect. However, there is no mention of high voltage conditions in this technique.

  Further, for example, in Japanese Patent Application Laid-Open No. 2010-165653, in a non-aqueous electrolyte, at least one of a chain saturated hydrocarbon dinitrile compound having a nitrile group bonded to both ends, a cyclic carbonate, a cyclic ester, and a chain carbonate. A technique of including one is disclosed. However, in this technique, the composition of the cyclic carbonate for the purpose of improving characteristics under a high temperature environment as in the present technique is not specified.

  The dinitrile compound represented by the formula (1) is advantageous in suppressing gas generation as the boiling point of the nitrile compound itself increases as the number of carbon atoms of the hydrocarbon group increases. On the other hand, when the number of carbon atoms of the hydrocarbon group in the dinitrile compound represented by the formula (1) is increased, the concentration of the nitrile group is relatively decreased, so that the conductivity of the electrolyte cannot be maintained. Therefore, n in Formula (1) is preferably 2 or more and 6 or less.

  More specifically, examples of the dinitrile compound represented by the formula (1) include, for example, malononitrile in which n in the formula (1) is 1, succinonitrile in which n in the formula (1) is 2, Glutaronitrile in which n in formula (1) is 3, adiponitrile in which n is 4 in formula (1), pimelonitrile in which n in formula (1) is 5, n in formula (1) is 6 A certain suberonitrile, an azeronitrile in which n in the formula (1) is 7, sebacononitrile (n = 8) in which n is 8 in the formula (1), an undecanedinitrile in which n is 9 in the formula (1), a formula (1) Dinitrile compounds such as dodecanedinitrile in which n is 10 may be mentioned. Among these, dinitrile compounds such as succinonitrile, adiponitrile, suberonitrile, and sebaconitrile are preferable. This is because it is easily available and a high effect can be obtained. These dinitrile compounds may be used alone or in combination of two or more. In addition, the dinitrile compound represented by Formula (1) is not limited to the dinitrile compound specifically illustrated.

(Nitrile compound content)
The content of the dinitrile compound represented by the formula (1) is preferably 0.1% by mass or more and 5% by mass or less, and 0.5% by mass or more and 3% by mass with respect to the total mass of the nonaqueous electrolytic solution. % Or less is more preferable. If the content of the dinitrile compound represented by formula (1) is excessively small in the non-aqueous electrolyte, the effect on the active sites on the positive and negative electrodes is not sufficient, and side reactions, that is, gas generation can be suppressed. Can not. On the other hand, when the content of the nitrile compound is excessively large, the resistance of the nonaqueous electrolytic solution becomes too large, and thus the discharge capacity and the cycle characteristics tend to be deteriorated.

  Similar to the active sites on the positive and negative electrodes, the dinitrile compound represented by the formula (1) coordinates with the supporting salt in the electrolyte to promote the dissociation of ions, and as a result, the conductivity is improved. Therefore, it is preferable to increase the amount in a range not impeding the cycle characteristics in proportion to the molar concentration of the electrolyte salt to be used. However, it is not preferable to increase the amount exceeding the molar concentration of the nitrile compound that can coordinate to the active material or the electrolyte salt because battery characteristics such as cycle characteristics are deteriorated.

(Cyclic alkylene carbonate)
The nonaqueous electrolytic solution contains a high dielectric constant solvent having a relative dielectric constant of 30 or more as a main solvent of the nonaqueous solvent together with the dinitrile compound represented by the formula (1). This is because the number of lithium ions can be increased. An example of such a high dielectric constant solvent is cyclic alkylene carbonate.

  Cyclic alkylene carbonate is a cyclic carbonate having no carbon-carbon multiple bond and containing no halogen. Specific examples thereof include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2, 3 -Butylene carbonate, tert-butyl ethylene carbonate, trimethylene carbonate and the like. Among these, it is preferable to use ethylene carbonate and propylene carbonate as the main solvent from the viewpoint of stability and viscosity. When cyclic alkylene carbonate is used as the non-aqueous solvent, one kind may be used alone, or a plurality of kinds may be mixed and used.

(Content of cyclic alkylene carbonate)
The content of the cyclic alkylene carbonate contained in the nonaqueous electrolytic solution is 80% by mass or more and more preferably 80% by mass or more and 95% by mass or less with respect to the total mass of the nonaqueous electrolytic solution. If it is in the said range, expansion | swelling of a battery can be suppressed and it can be set as favorable cycling characteristics.

  When the cyclic alkylene carbonate contains ethylene carbonate, the ratio of the mass of the ethylene carbonate to the total mass of the cyclic alkylene carbonate is preferably 20% or more and 60% or less, and 30% or more and 50% or less. Is more preferable, and 30% or more and 40% or less is particularly preferable. When the content of ethylene carbonate exceeds 60%, the high-temperature storage characteristics tend to deteriorate, and when it is less than 20%, the battery capacity including cycle characteristics tends to deteriorate.

  When the cyclic alkylene carbonate contains other cyclic alkylene carbonate other than ethylene carbonate, the ratio of the mass of the other cyclic alkylene carbonate to the total mass of the cyclic alkylene carbonate is 40% or more and 80% or less. preferable. As other cyclic alkylene carbonate, it is preferable to use propylene carbonate, butylene carbonate, trimethylene carbonate or the like. These may be used individually by 1 type, and may mix and use multiple types.

(Other high dielectric constant solvents)
The nonaqueous electrolytic solution may contain a high dielectric constant solvent other than the exemplified high dielectric constant solvent as the nonaqueous solvent. Examples of other high dielectric constant solvents include cyclic carbonates having carbon-carbon multiple bonds such as vinylene carbonate and vinyl ethylene carbonate, chloroethylene carbonate, 4-fluoro-1,3-dioxolan-2-one (fluoroethylene). Carbonate), trans-4,5-difluoro-fluoro-1,3-dioxolan-2-one (difluoroethylene carbonate), halogenated cyclic carbonates such as trifluoromethylethylene carbonate, γ-butyrolactone and γ-valerolactone, etc. Lactones, lactams such as N-methyl-2-pyrrolidone, cyclic carbamates such as N-methyl-2-oxazolidinone, and sulfone compounds such as tetramethylene sulfone.

  Among these, it is preferable to use a cyclic carbonate having a carbon-carbon multiple bond, and vinylene carbonate, vinyl ethylene carbonate and the like are particularly preferable. The content of the cyclic carbonate having a carbon-carbon multiple bond in the non-aqueous electrolyte is preferably 0.5% by mass or more and 5% by mass or less with respect to the total mass of the non-aqueous electrolyte. Further, it is preferable to use a halogenated cyclic carbonate, and particularly, fluoroethylene carbonate, difluoroethylene carbonate, and the like are preferable. The content of the halogenated cyclic carbonate in the non-aqueous electrolyte is preferably in the range of 0.5% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte. Further, lactone is preferably used, and γ-butyrolactone is particularly preferably used. The lactone content in the non-aqueous electrolyte is preferably 0.5% by mass or more and 5% by mass or less with respect to the total mass of the non-aqueous electrolyte. Said other high dielectric constant solvent may be used individually by 1 type, and may mix and use multiple types.

(Low viscosity solvent)
The nonaqueous electrolytic solution may contain a low viscosity solvent having a viscosity of 1 mPa · s or less as a nonaqueous solvent. The low viscosity solvent is preferably used by mixing with a high dielectric constant solvent. This is because high ion conductivity can be obtained. The ratio (mass ratio) of the low-viscosity solvent to the high-dielectric-constant solvent is preferably in the range of high-dielectric-constant solvent: low-viscosity solvent = 85: 15 to 100: 0. It is because a higher effect can be obtained in the discharge capacity and the like while maintaining the high temperature storage characteristics by being within this range.

  Examples of the low-viscosity solvent include chain carbonates such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and methyl propyl carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, and trimethyl. Chain carboxylic acid esters such as methyl acetate and ethyl trimethylacetate, chain amides such as N, N-dimethylacetamide, chain carbamic acid esters such as methyl N, N-diethylcarbamate and ethyl N, N-diethylcarbamate And ethers such as 1,2-dimethoxyethane, tetrahydrofuran, tetrahydropyran and 1,3-dioxolane. These low-viscosity solvents may be used alone or in combination of two or more.

(Electrolyte salt)
The electrolyte salt contains, for example, one or more light metal salts such as a lithium salt. As this lithium salt, for example, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium tetraphenylborate (LiB (C ₆ H ₅ ) ₄ ), Lithium methanesulfonate (LiCH ₃ SO ₃ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), lithium tetrachloroaluminate (LiAlCl ₄ ), dilithium hexafluorosilicate (Li ₂ SiF ₆ ), lithium chloride ( LiCl) or lithium bromide (LiBr). Among these, at least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, and lithium hexafluoroarsenate is preferable, and lithium hexafluorophosphate is more preferable. This is because the resistance of the electrolyte decreases.

  The electrolyte according to the first embodiment of the present technology preferably further includes a polymer compound that swells with a non-aqueous electrolyte and serves as a holding body that holds the non-aqueous electrolyte. Thereby, the non-aqueous electrolyte is held by the polymer compound, and the non-aqueous electrolyte and the polymer compound are integrated to form a gel electrolyte. And by including the high molecular compound which swells with a non-aqueous electrolyte, high ionic conductivity can be obtained, and while the outstanding charging / discharging efficiency can be obtained, the leakage of a battery can be prevented.

  When a polymer compound is added to a non-aqueous electrolyte and used, the content of the polymer compound relative to the total amount of the non-aqueous electrolyte and the polymer compound depends on the molecular weight of the polymer compound used, etc. It is preferable to be within the range of 0.1% by mass or more and 10% by mass or less. If the amount used is too large, the viscosity becomes too high, resulting in difficulty in the process, and the ratio of the non-aqueous electrolyte is decreased, the ionic conductivity is decreased, and the battery characteristics such as the rate characteristics tend to be decreased. On the other hand, if the amount is too small, the retention of the non-aqueous electrolyte may be reduced, resulting in a problem of liquid leakage. If it is the said range, higher charging / discharging efficiency will be obtained. Moreover, when apply | coating and using a polymer compound on both surfaces of the separator mentioned later, it is preferable to make mass ratio of a nonaqueous electrolyte solution and a polymer compound into the range of 50: 1-10: 1. It is because higher charging / discharging efficiency is obtained by setting it within this range.

  As the polymer compound that holds the non-aqueous electrolyte, it is preferable to use an alkylene oxide polymer having an alkylene oxide unit, a fluorine polymer such as polyvinylidene fluoride or a copolymer thereof, and the like. The copolymer of polyvinylidene fluoride is a copolymer of vinylidene fluoride and other monomers, such as a copolymer of vinylidene fluoride and hexafluoropropylene, a copolymer of chlorotrifluoroethylene, etc. Can be mentioned.

  As a method for forming a gel electrolyte, it can be obtained by immersing the non-aqueous electrolyte in a polymer such as an isocyanate cross-linked product of polyalkylene oxide. (1) Contains a polymerizable gelling agent A gel electrolyte is formed by subjecting a non-aqueous electrolyte to a polymerization treatment such as ultraviolet curing or thermosetting, or (2) cooling a polymer compound dissolved in a non-aqueous electrolyte at a high temperature to room temperature. A method of gelling a gel electrolyte precursor, such as the method of

  In the case of the method (1) using a non-aqueous electrolyte containing a polymerizable gelling agent, examples of the polymerizable gelling agent include unsaturated double bonds such as acryloyl group, methacryloyl group, vinyl group and allyl group. What you have. Specifically, acrylic acid, methyl acrylate, ethyl acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, ethoxyethoxyethyl acrylate, polyethylene glycol monoacrylate, ethoxyethyl methacrylate, methoxyethyl methacrylate, ethoxyethoxyethyl methacrylate, polyethylene glycol mono Methacrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, allyl acrylate, acrylonitrile, N-vinyl pyrrolidone, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol Diacrylate, diethylene glycol Dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyalkylene glycol diacrylate, polyalkylene glycol dimethacrylate, etc. can be used, and trimethylolpropane alkoxylate triacrylate, pentaerythritol alkoxylate Trifunctional monomers such as triacrylate, tetrafunctional or higher functional monomers such as pentaerythritol alkoxylate tetraacrylate and ditrimethylolpropane alkoxylate tetraacrylate can also be used. Among these, oxyalkylene glycol compounds having an acryloyl group or a methacryloyl group are preferable.

  On the other hand, in the case of the method (2) in which a gel-like electrolyte is formed by cooling a polymer compound dissolved in a non-aqueous electrolyte at a high temperature to room temperature, such a polymer compound includes non-aqueous electrolysis. Any material can be used as long as it forms a gel with respect to the liquid and is stable as a battery material. For example, a polymer having a ring such as polyvinyl pyridine and poly-N-vinyl pyrrolidone; polymethyl methacrylate , Acrylic derivative polymers such as polyethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyacrylic acid, polymethacrylic acid polyacrylamide; fluorine resins such as polyvinyl fluoride and polyvinylidene fluoride; CN group-containing polymers such as polyacrylonitrile and polyvinylidene cyanide; polyvinyl acetate Polyvinyl alcohol polymers such as polyvinyl alcohol; polyvinyl chloride, and halogen-containing polymers such as polyvinylidene chloride. In addition, a mixture such as the above-described polymer compound, a modified body, a derivative, a random copolymer, an alternating copolymer, a graft copolymer, a block copolymer, and the like can be used. The weight average molecular weight of these polymer compounds is preferably in the range of 10,000 to 5,000,000. When the molecular weight is low, it is difficult to form a gel, and when the molecular weight is high, the viscosity becomes too high and handling becomes difficult. As the gel electrolyte, it is also possible to use a completely solid electrolyte formed by the polymer compound and the electrolyte salt.

The gel electrolyte preferably contains ceramic powder. For example, in a battery in which a gel electrolyte is disposed between a positive electrode and a negative electrode, the mechanical strength of the gel electrolyte is improved, and current short circuit due to contact between both electrodes is less likely to occur. As the ceramic powder, at least one selected from the group consisting of Al ₂ O ₃ , ZrO, TiO ₂ and MgO ₂ can be used.

  The average particle size of the ceramic powder is preferably 0.1 μm or more and 2.5 μm or less, and the mass ratio of the ceramic powder and the polymer compound is preferably ceramic powder / polymer compound = 1/1 or more and 5/1 or less. . This is because the intended strength can be obtained while suppressing the deterioration of the battery characteristics.

2. Second Embodiment (Configuration of Nonaqueous Electrolyte Battery)
A nonaqueous electrolyte battery according to a second embodiment of the present technology will be described. FIG. 1 illustrates an exploded perspective configuration of a nonaqueous electrolyte battery according to a second embodiment of the present technology. FIG. 2 is a cross-sectional view taken along line II of the spirally wound electrode body 30 illustrated in FIG. Is shown enlarged. This nonaqueous electrolyte battery is, for example, a nonaqueous electrolyte secondary battery that can be charged and discharged.

  In this nonaqueous electrolyte battery, a wound electrode body 30 to which a positive electrode lead 31 and a negative electrode lead 32 are attached is mainly housed in a film-like exterior member 40. The battery structure using the film-shaped exterior member 40 is called a laminate type.

  For example, the positive electrode lead 31 and the negative electrode lead 32 are led out in the same direction from the inside of the exterior member 40 toward the outside. The positive electrode lead 31 is made of, for example, a metal material such as aluminum, and the negative electrode lead 32 is made of, for example, a metal material such as copper, nickel, or stainless steel. These metal materials are, for example, in a thin plate shape or a mesh shape.

  The exterior member 40 is made of, for example, an aluminum laminated film in which a nylon film, an aluminum foil, and a polyethylene film are bonded together in this order. The exterior member 40 has, for example, a structure in which outer edges of two rectangular aluminum laminate films are bonded to each other by fusion or an adhesive so that the polyethylene film faces the wound electrode body 30. ing.

  An adhesive film 41 is inserted between the exterior member 40 and the positive electrode lead 31 and the negative electrode lead 32 to prevent intrusion of outside air. The adhesion film 41 is made of a material having adhesion to the positive electrode lead 31 and the negative electrode lead 32. Examples of such a material include polyolefin resins such as polyethylene, polypropylene, modified polyethylene, and modified polypropylene.

  In addition, the exterior member 40 may be composed of a laminated film having another laminated structure instead of the above-described aluminum laminated film, or may be composed of a polymer film such as polypropylene or a metal film.

  FIG. 2 shows a cross-sectional configuration along line II of the spirally wound electrode body 30 shown in FIG. The wound electrode body 30 is obtained by laminating and winding a positive electrode 33 and a negative electrode 34 via a separator 35 and an electrolyte 36, and an outermost peripheral portion thereof is protected by a protective tape 37.

  In the nonaqueous electrolyte secondary battery according to the second embodiment of the present technology, the electrochemical equivalent of the negative electrode material capable of inserting and extracting lithium is larger than the electrochemical equivalent of the positive electrode 21. The lithium metal may not be deposited on the negative electrode 22 during the charging.

  Further, in the nonaqueous electrolyte secondary battery according to the second embodiment of the present technology, the open circuit voltage (that is, the battery voltage) in the fully charged state per pair of the positive electrode 33 and the negative electrode 34 may be 4.20 V or less. It may be designed to be higher than 4.20V, and preferably in the range of 4.25V to 4.50V. By making the battery voltage higher than 4.20V, the amount of lithium released per unit mass is increased even with the same positive electrode active material than the battery with an open circuit voltage of 4.20V at the time of full charge. Accordingly, the amounts of the positive electrode active material and the negative electrode active material are adjusted. As a result, a high energy density can be obtained.

(Positive electrode)
In the positive electrode 33, for example, a positive electrode active material layer 33B is provided on both surfaces of a positive electrode current collector 33A having a pair of surfaces. However, the positive electrode active material layer 33B may be provided only on one surface of the positive electrode current collector 33A. As the positive electrode current collector 33A, for example, a metal foil such as an aluminum (Al) foil, a nickel (Ni) foil, or a stainless steel (SUS) foil can be used.

  The positive electrode active material layer 33B includes one or more positive electrode materials capable of inserting and extracting lithium as a positive electrode active material, and a binder, a conductive agent, and the like as necessary. Other materials may be included.

As a positive electrode material capable of inserting and extracting lithium, for example, a lithium transition metal composite oxide containing lithium and a transition metal is preferable. This is because a high voltage can be generated and a high energy density can be obtained. Examples of the lithium transition metal composite oxide include those represented by the general formula Li _x MO ₂ . M contains one or more transition metal elements, and preferably contains at least one of cobalt and nickel, for example. x varies depending on the charge / discharge state of the battery and is usually a value in the range of 0.05 ≦ x ≦ 1.10. Specific examples of such a lithium transition metal composite oxide include LiCoO _{2 and} LiNiO ₂ .

Furthermore, examples of the lithium transition metal composite compound include a lithium composite oxide having a spinel structure, and more specifically, Li _d Mn ₂ O ₄ (d≈1).

Furthermore, examples of the positive electrode material capable of inserting and extracting lithium include lithium composite phosphates having an olivine type structure, more specifically, LieFePO ₄ (e≈1). .

  Furthermore, as a positive electrode material capable of inserting and extracting lithium, for example, a lithium composite oxide having a layered rock salt type structure represented by formula (A), formula (B), or formula (C), formula ( Examples thereof include a lithium composite oxide having a spinel structure shown in D) or a lithium composite phosphate having an olivine structure shown in Formula (E).

Li _f Mn _(1-gh) Ni _g M1 _h O _(2-j) F _k (A)
(In the formula, M1 is cobalt (Co), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu ), Zinc (Zn), zirconium (Zr), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W). g, h, j and k are 0.8 ≦ f ≦ 1.2, 0 <g <0.5, 0 ≦ h ≦ 0.5, g + h <1, −0.1 ≦ j ≦ 0.2, (The value is in the range of 0 ≦ k ≦ 0.1. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of f represents a value in a fully discharged state.)

Li _m Ni _(1-n) M2 _n O _(2-p) F _q (B)
(In the formula, M2 represents cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), at least one selected from the group consisting of m, n, p and q are values within the range of 0.8 ≦ m ≦ 1.2, 0.005 ≦ n ≦ 0.5, −0.1 ≦ p ≦ 0.2, 0 ≦ q ≦ 0.1. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of m represents a value in a fully discharged state.)

Li _r Co _(1-s) M3 _s O _{(2-t) Fu} (C)
(In the formula, M3 represents nickel (Ni), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), at least one kind. s, t, and u are values within the ranges of 0.8 ≦ r ≦ 1.2, 0 ≦ s <0.5, −0.1 ≦ t ≦ 0.2, and 0 ≦ u ≦ 0.1. (Note that the composition of lithium varies depending on the state of charge and discharge, and the value of r represents the value in a fully discharged state.)

Li _v Mn _2-w M4 _w O _x F _y (D)
(In the formula, M4 is cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr) and tungsten (W), at least one selected from the group consisting of v, w, x, and y are values within the range of 0.9 ≦ v ≦ 1.1, 0 ≦ w ≦ 0.6, 3.7 ≦ x ≦ 4.1, and 0 ≦ y ≦ 0.1. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of v represents the value in a fully discharged state.)

Li _z M5PO ₄ (E)
(Wherein M5 is cobalt (Co), manganese (Mn), iron (Fe), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V ), Niobium (Nb), copper (Cu), zinc (Zn), molybdenum (Mo), calcium (Ca), strontium (Sr), tungsten (W) and zirconium (Zr) Z is a value in a range of 0.9 ≦ z ≦ 1.1, wherein the composition of lithium varies depending on the state of charge and discharge, and the value of z represents a value in a complete discharge state. )

  The positive electrode material comprises at least a part of the surface of the central part with core particles containing lithium composite oxide containing lithium and at least one member selected from the group consisting of cobalt, nickel and manganese as a central part. It is preferable that a surface layer containing a compound containing phosphorus and at least one member selected from the group consisting of nickel, cobalt, manganese, iron, aluminum, magnesium and zinc is provided. That is, this positive electrode material contains a lithium composite oxide, and includes, on the surface, phosphorus and at least one member selected from the group consisting of nickel, cobalt, manganese, iron, aluminum, magnesium and zinc as a covering element. It is out. Thereby, this positive electrode material can obtain a high energy density, and can improve the chemical stability or the reactivity in the input / output of lithium ions.

  The surface layer may contain other elements in addition to the covering elements described above. Examples of other elements include lithium, oxygen (O), and elements constituting a lithium composite oxide. Although the compound which comprises a surface layer may be 1 type, it may contain 2 or more types. More preferable as the covering element is phosphorus and at least one of manganese, magnesium and aluminum. This is because higher characteristics can be obtained. When aluminum is included as the covering element, the atomic ratio of phosphorus to aluminum (P / Al) on the surface is preferably 0.3 or more, and more preferably 0.35 or more and 12.7 or less. This is because a sufficient effect cannot be obtained when the atomic ratio is small, and the improvement effect is saturated when the atomic ratio is large.

  The content of the covering element is preferably higher on the surface than on the inside, and the covering element is preferably present so as to decrease from the surface toward the inside. This is because a higher effect can be obtained. The amount of the surface layer is preferably in the range of 0.2% by mass or more and 5% by mass or less with respect to the mass of the lithium composite oxide contained in the central part. If the amount is small, a sufficient effect cannot be obtained, and if the amount is too large, the capacity decreases. Furthermore, the suitable covering amount of the covering element in the surface layer differs depending on the kind of the covering element. When the covering element contains, for example, phosphorus and manganese, 0.2 mol% or more and 6.0 mol with respect to the lithium composite oxide. % Or less, and when phosphorus and magnesium are included, it is preferably 0.2 mol% or more and 4.0 mol% or less. Or when phosphorus and aluminum are included as a covering element, it is preferable that the covering element containing phosphorus and aluminum is 0.2 mol% or more and 6.0 mol% or less in total with respect to lithium complex oxide. In either case, if the amount is small, sufficient effects cannot be obtained, and if the amount is too large, the capacity decreases.

  Other positive electrode materials capable of inserting and extracting lithium include oxides such as titanium oxide, vanadium oxide or manganese dioxide, disulfides such as titanium disulfide or molybdenum sulfide, and niobium selenide. Or a conductive polymer such as sulfur, polyaniline or polythiophene. Of course, the positive electrode material capable of inserting and extracting lithium may be other than the above. Further, two or more kinds of the series of positive electrode materials described above may be mixed in any combination.

(Binder)
Examples of the binder include synthetic rubber such as styrene butadiene rubber, fluorine rubber or ethylene propylene diene, a polymer material such as polyvinylidene fluoride, cellulose such as carboxymethyl cellulose, and the like. These may be single and multiple types may be mixed.

(Conductive agent)
Examples of the conductive agent include carbon materials such as graphite and carbon black. These may be used alone or in combination of two or more.

(Negative electrode)
The negative electrode 34 is obtained by providing a negative electrode active material layer 34B on both surfaces of a negative electrode current collector 34A having a pair of surfaces. However, the negative electrode active material layer 34B may be provided only on one surface of the negative electrode current collector 34A. As the negative electrode current collector 34A, for example, a metal foil such as a copper (Cu) foil, a nickel foil, or a stainless steel foil can be used.

  The negative electrode active material layer 34B includes one or more negative electrode materials capable of inserting and extracting lithium as a negative electrode active material, and a binder, a conductive agent, and the like as necessary. Other materials may be included. At this time, the chargeable capacity of the negative electrode material capable of inserting and extracting lithium is preferably larger than the discharge capacity of the positive electrode 33. The details regarding the binder and the conductive agent are the same as those of the positive electrode 33.

  Examples of the negative electrode material capable of occluding and releasing lithium include graphite, non-graphitizable carbon, graphitizable carbon, pyrolytic carbons, cokes, glassy carbons, and fired organic polymer compounds And carbon materials such as carbon fiber or activated carbon. Among these, examples of coke include pitch coke, needle coke, and petroleum coke. An organic polymer compound fired body refers to a carbonized material obtained by firing a polymer material such as phenol resin or furan resin at an appropriate temperature, and part of it is non-graphitizable carbon or graphitizable carbon. Some are classified as: Examples of the polymer material include polyacetylene and polypyrrole. These carbon materials are preferable because the change in crystal structure that occurs during charge and discharge is very small, a high charge and discharge capacity can be obtained, and good cycle characteristics can be obtained. In particular, graphite is preferable because it has a high electrochemical equivalent and can provide a high energy density. Further, non-graphitizable carbon is preferable because excellent characteristics can be obtained. Furthermore, a battery having a low charge / discharge potential, specifically, a battery having a charge / discharge potential close to that of lithium metal is preferable because a high energy density of the battery can be easily realized.

  Examples of the negative electrode material capable of inserting and extracting lithium include materials capable of inserting and extracting lithium and containing at least one of a metal element and a metalloid element as a constituent element. This is because a high energy density can be obtained by using such a material. In particular, the use with a carbon material is more preferable because a high energy density can be obtained and excellent cycle characteristics can be obtained. The negative electrode material may be a single element, alloy, or compound of a metal element or a metalloid element, or may have at least a part of one or more of these phases. In the present technology, the alloy includes an alloy including one or more metal elements and one or more metalloid elements in addition to an alloy composed of two or more metal elements. Moreover, the nonmetallic element may be included. Some of the structures include a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or a mixture of two or more of them.

  Examples of the metal element or metalloid element constituting the negative electrode material include magnesium (Mg), boron (B), aluminum (Al), gallium (Ga), indium (In), silicon (Si), and germanium (Ge). ), Tin (Sn), lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd) ) Or platinum (Pt). These may be crystalline or amorphous.

  Among these, as the negative electrode material, a material containing a 4B group metal element or semimetal element in the short-period type periodic table as a constituent element is preferable, and at least one of silicon (Si) and tin (Sn) is particularly preferable. It is included as an element. This is because silicon (Si) and tin (Sn) have a large ability to occlude and release lithium (Li), and a high energy density can be obtained.

  As an alloy of tin (Sn), for example, as a second constituent element other than tin (Sn), silicon (Si), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb), and chromium (Cr) The thing containing at least 1 sort is mentioned. As an alloy of silicon (Si), for example, as a second constituent element other than silicon (Si), tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb), and chromium (Cr). The thing containing 1 type is mentioned.

  Examples of the tin (Sn) compound or silicon (Si) compound include those containing oxygen (O) or carbon (C), and in addition to tin (Sn) or silicon (Si), Two constituent elements may be included.

Examples of the negative electrode material capable of inserting and extracting lithium further include other metal compounds or polymer materials. Examples of other metal compounds include oxides such as MnO ₂ , V ₂ O ₅ , and V ₆ O ₁₃ , sulfides such as NiS and MoS, and lithium nitrides such as LiN ₃ , and polymer materials include polyacetylene. , Polyaniline or polypyrrole.

(Electrolytes)
The electrolyte 36 is a gel electrolyte that includes a nonaqueous electrolytic solution containing a nonaqueous solvent and an electrolyte salt, and a polymer compound that holds the nonaqueous electrolytic solution. The details of the non-aqueous electrolyte and the polymer compound are the same as those in the first embodiment, and thus detailed description thereof is omitted.

(Separator)
The separator 35 separates the positive electrode 33 and the negative electrode 34 and allows lithium ions to pass through while preventing a short circuit of current due to contact between both electrodes. For example, it is composed of a porous film made of a polyolefin-based material such as polyethylene (PE) or polypropylene (PP). The separator may have a structure in which two or more porous films are laminated. In addition, a separator in which a porous resin layer such as polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE) is formed on a porous film made of a polyolefin-based material may be used.

  In addition, you may impregnate the non-aqueous electrolyte in the separator 35 of the form which used the porous polyolefin film and the gel electrolyte together. That is, it is possible to use the separator 35 in which a polymer compound for holding the nonaqueous electrolytic solution is deposited on the surface. By using such a separator 35, an electrolyte 36 is formed on the surface of the separator 35 when the separator 35 is impregnated with a non-aqueous electrolyte later in the battery manufacturing process. At this time, the nonaqueous electrolytic solution has the configuration described in the first embodiment. In the present technology, the gel electrolyte described in the first embodiment may be used as a layer for separating the positive electrode 33 and the negative electrode 34 without using the separator 35.

(Method for producing non-aqueous electrolyte battery)
This nonaqueous electrolyte battery is manufactured, for example, by the following three types of manufacturing methods (first to third manufacturing methods).

(First manufacturing method)
In the first manufacturing method, first, the positive electrode 33 and the negative electrode 34 are manufactured as follows.

  A positive electrode material, a binder, and a conductive agent are mixed to prepare a positive electrode mixture, and the positive electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to prepare a mixed solution. Next, this positive electrode mixture slurry is applied to the positive electrode current collector 33A and dried, and then compression molded by a roll press or the like to form the positive electrode active material layer 33B, whereby the positive electrode 33 is obtained.

  A negative electrode material and a binder are mixed to prepare a negative electrode mixture, and the negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to obtain a negative electrode mixture slurry. Next, after applying this negative electrode mixture slurry to the negative electrode current collector 34A and drying the solvent, the negative electrode active material layer 34B is formed by compression molding using a roll press or the like, and the negative electrode 34 is obtained.

  Next, first, a precursor solution containing the nonaqueous electrolytic solution described in the first embodiment and a solvent is prepared. Thereafter, the precursor solution is applied to the respective surfaces of the positive electrode 33 and the negative electrode 34, and then the solvent is volatilized to form a gel electrolyte that becomes the electrolyte 36. Subsequently, the positive electrode lead 31 and the negative electrode lead 32 are attached to the positive electrode current collector 33A and the negative electrode current collector 34A, respectively. Here, the positive electrode lead 31 and the negative electrode lead 32 may be attached to the positive electrode current collector 33 and the negative electrode current collector 34 before the electrolyte 36 is formed.

  Subsequently, the positive electrode 33 and the negative electrode 34 provided with the electrolyte 36 are stacked via the separator 35 and then wound in the longitudinal direction, and a protective tape 37 is adhered to the outermost peripheral portion to form the wound electrode body 30. To do. Finally, for example, after sandwiching the wound electrode body 30 between two film-like exterior members 40, the outer edges of the exterior member 40 are bonded together by heat fusion or the like and sealed under reduced pressure, The wound electrode body 30 is enclosed. At this time, the adhesion film 41 is inserted between the positive electrode lead 31 and the negative electrode lead 32 and the exterior member 40. Thereby, a nonaqueous electrolyte battery is completed.

(Second manufacturing method)
In the second manufacturing method, first, the positive electrode lead 31 and the negative electrode lead 32 are attached to the positive electrode current collector 33A and the negative electrode current collector 34A, respectively. And the positive electrode 33 and the negative electrode 34 are laminated | stacked via the separator 35, Then, it winds in a longitudinal direction, The protective tape 37 is adhere | attached on the outermost periphery part, and the winding electrode body 30 is formed. Subsequently, after sandwiching the wound electrode body 30 between the two film-shaped exterior members 40, the remaining outer peripheral edge portion excluding the outer peripheral edge portion on one side is adhered by heat fusion or the like, thereby forming a bag shape. The wound electrode body 30 is housed inside the exterior member 40.

  Subsequently, the non-aqueous electrolyte described in the first embodiment, a monomer that is a raw material of the polymer compound that holds the non-aqueous electrolyte, a polymerization initiator, and a polymerization inhibitor as necessary An electrolyte composition containing other materials is prepared and injected into the bag-shaped exterior member 40. Finally, the opening of the exterior member 40 is sealed by thermal fusion or the like, and the monomer is thermally polymerized to obtain a polymer compound, thereby forming a gel electrolyte that becomes the electrolyte 36. Thereby, a nonaqueous electrolyte battery is completed.

(Third production method)
In the third manufacturing method, first, a polymer compound for holding the nonaqueous electrolytic solution is applied to both surfaces of the separator 35. Examples of the polymer compound applied to the separator 35 include a polymer containing vinylidene fluoride as a component, that is, a homopolymer, a copolymer, a multi-component copolymer, and the like. Specifically, polyvinylidene fluoride, binary copolymers containing vinylidene fluoride and hexafluoropropylene as components, and ternary copolymers containing vinylidene fluoride, hexafluoropropylene and chlorotrifluoroethylene as components. Such as coalescence. The polymer compound may contain one or more other polymer compounds together with the polymer containing vinylidene fluoride as a component.

  Next, the positive electrode lead 31 and the negative electrode lead 32 are attached to the positive electrode current collector 33A and the negative electrode current collector 34A, respectively. And the positive electrode 33 and the negative electrode 34 are laminated | stacked via the separator 35, Then, it winds in a longitudinal direction, The protective tape 37 is adhere | attached on the outermost periphery part, the wound electrode body 30 is formed, A bag-shaped exterior member 40 inside. Thereafter, the non-aqueous electrolyte described in the first embodiment is injected into the exterior member 40, and the opening of the exterior member 40 is sealed by thermal fusion or the like. Finally, the exterior member 40 is heated while applying a load, and the separator 35 is brought into close contact with the positive electrode 33 and the negative electrode 34 through the polymer compound. Thus, the polymer compound is impregnated with the non-aqueous electrolyte, and a gel electrolyte that becomes the electrolyte 36 is formed, thereby completing the non-aqueous electrolyte battery.

  In the third manufacturing method, the swelling of the nonaqueous electrolyte battery is suppressed as compared with the first manufacturing method. Further, in the third manufacturing method, compared with the second manufacturing method, there are almost no monomers, solvents or the like as raw materials for the polymer compound remaining in the electrolyte 36, and the formation process of the polymer compound is well controlled. Therefore, sufficient adhesion is obtained between the positive electrode 33, the negative electrode 34, the separator 35, and the electrolyte 36. For this reason, it is more preferable to use the third manufacturing method.

  In the nonaqueous electrolyte battery according to the second embodiment of the present technology, the nonaqueous electrolyte constituting the electrolyte 36 includes a cyclic alkylene carbonate and a dinitrile compound represented by the formula (1), and the cyclic alkylene carbonate. The content of is set to 80% by mass or more with respect to the total mass of the nonaqueous electrolytic solution. With this configuration, even if the open circuit voltage in the fully charged state per pair of positive and negative electrodes is set in the range of 4.25V to 4.50V, gas generation during high-temperature storage is suppressed, battery swelling, etc. It is possible to suppress deformation and improve cycle characteristics.

3. Third Embodiment A nonaqueous electrolyte battery according to a third embodiment of the present technology will be described. The nonaqueous electrolyte battery according to the third embodiment of the present technology is the same as that of the second embodiment except that ceramic powder is added to the electrolyte 36 of the second embodiment. Therefore, in the following, the configuration will be described in detail with a focus on differences from the second embodiment.

(Electrolytes)
In the nonaqueous electrolyte battery according to the third embodiment of the present technology, the electrolyte 36 contains ceramic powder. That is, the electrolyte 36 is a gel electrolyte that includes a nonaqueous electrolyte solution containing a nonaqueous solvent and an electrolyte salt and a polymer compound that holds the nonaqueous electrolyte solution, and ceramic powder contains the gel electrolyte. Has been.

  By including ceramic powder in the electrolyte 36, the mechanical strength of the electrolyte 36 is improved, and a short circuit of current is less likely to occur due to contact between the positive electrode 33 and the negative electrode 34.

  On the other hand, when ceramic powder is contained in the electrolyte 36, the conductivity of the electrolyte 36 tends to decrease. On the other hand, since the electrolyte 36 contains the dinitrile compound represented by the formula (1), the dinitrile compound represented by the formula (1) is supported in the electrolyte in the same manner as the active points on the positive and negative electrodes. It can also coordinate with the salt to promote ion dissociation and improve the conductivity of the electrolyte 36. In other words, the dinitrile compound represented by the formula (1) contained in the electrolyte 36 can compensate for the decrease in electrical conductivity by containing the ceramic powder in the electrolyte 36.

  It is more preferable to increase the amount of the dinitrile compound represented by the formula (1) in the non-aqueous electrolyte in proportion to the molar concentration of the electrolyte salt to be used in a range that does not disturb the cycle characteristics. However, it is not preferable to increase the amount exceeding the molar concentration of the nitrile compound that can coordinate with the active material or the electrolyte salt because the battery characteristics such as the cycle are deteriorated. From the above viewpoint, the content of the dinitrile compound represented by the formula (1) in the non-aqueous electrolyte is 0.5% by mass or more and 5% by mass or less with respect to the total mass of the non-aqueous electrolyte. Is preferable, and it is more preferable that they are 1 mass% or more and 3 mass% or less.

  As a range in which the dinitrile compound does not interfere with battery characteristics such as cycle characteristics, the mass percentage of the content of the dinitrile compound represented by the formula (1) with respect to the content of the electrolyte salt in the nonaqueous electrolytic solution ([mass of dinitrile compound / The mass of the electrolyte salt] × 100 [%]) is preferably 6.0% to 36%, more preferably 8.0% to 30%, and more preferably 8.0% to 25%. It is particularly preferred that Within this range, gas generation during high-temperature storage can be effectively suppressed without interfering with battery characteristics such as cycle characteristics.

  The nonaqueous electrolyte battery according to the third embodiment of the present technology has the same effect as that of the second embodiment.

4). Fourth Embodiment A nonaqueous electrolyte battery according to a fourth embodiment of the present technology will be described. The nonaqueous electrolyte battery according to the fourth embodiment of the present technology is replaced with the nonaqueous electrolyte battery according to the first embodiment in which the nonaqueous electrolytic solution is held in a polymer compound (electrolyte 36). The non-aqueous electrolyte battery is the same as the non-aqueous electrolyte battery according to the second embodiment except that the non-aqueous electrolyte is used as it is. Therefore, in the following, the configuration will be described in detail with a focus on differences from the second embodiment.

(Configuration of non-aqueous electrolyte battery)
In the nonaqueous electrolyte battery according to the fourth embodiment of the present technology, a nonaqueous electrolyte is used instead of the gel electrolyte 36. Therefore, the wound electrode body 30 has a configuration in which the electrolyte 36 is omitted, and the separator 35 is impregnated with the nonaqueous electrolytic solution.

(Method for producing non-aqueous electrolyte battery)
This nonaqueous electrolyte battery is manufactured as follows, for example.

  First, for example, a positive electrode active material, a binder, and a conductive agent are mixed to prepare a positive electrode mixture, and dispersed in a solvent such as N-methyl-2-pyrrolidone to prepare a positive electrode mixture slurry. Next, this positive electrode mixture slurry is applied to both sides, dried and compression molded to form the positive electrode active material layer 33B, and the positive electrode 33 is produced. Next, for example, the positive electrode lead 31 is joined to the positive electrode current collector 33A by, for example, ultrasonic welding or spot welding.

  Further, for example, a negative electrode material and a binder are mixed to prepare a negative electrode mixture, and dispersed in a solvent such as N-methyl-2-pyrrolidone to prepare a negative electrode mixture slurry. Next, the negative electrode mixture slurry is applied to both surfaces of the negative electrode current collector 34A, dried, and compression molded to form the negative electrode active material layer 34B, whereby the negative electrode 34 is produced. Next, for example, the negative electrode lead 32 is joined to the negative electrode current collector 34A by, for example, ultrasonic welding or spot welding.

  Subsequently, after winding the positive electrode 33 and the negative electrode 34 through the separator 35 and sandwiching them inside the exterior member 40, the nonaqueous electrolyte according to the first embodiment is injected into the exterior member 40, The exterior member 40 is sealed. Thereby, the nonaqueous electrolyte battery shown in FIGS. 1 and 2 is obtained.

  The nonaqueous electrolyte battery according to the fourth embodiment of the present technology has the same effect as that of the second embodiment.

5. Fifth embodiment (example of battery pack)
FIG. 3 is a block diagram illustrating an example of a circuit configuration when a nonaqueous electrolyte secondary battery (hereinafter, appropriately referred to as a secondary battery) of the present technology is applied to a battery pack. The battery pack includes a switch unit 304 including an assembled battery 301, an exterior, a charge control switch 302a, and a discharge control switch 303a, a current detection resistor 307, a temperature detection element 308, and a control unit 310.

  In addition, the battery pack includes a positive electrode terminal 321 and a negative electrode terminal 322. During charging, the positive electrode terminal 321 and the negative electrode terminal 322 are connected to the positive electrode terminal and the negative electrode terminal of the charger, respectively, and charging is performed. Further, when the electronic device is used, the positive electrode terminal 321 and the negative electrode terminal 322 are connected to the positive electrode terminal and the negative electrode terminal of the electronic device, respectively, and discharge is performed.

  The assembled battery 301 is formed by connecting a plurality of secondary batteries 301a in series and / or in parallel. The secondary battery 301a is a secondary battery of the present technology. In addition, in FIG. 3, the case where the six secondary batteries 301a are connected to 2 parallel 3 series (2P3S) is shown as an example, but otherwise n parallel m series (n and m are integers) Any connection method may be used.

  The switch unit 304 includes a charge control switch 302a and a diode 302b, and a discharge control switch 303a and a diode 303b, and is controlled by the control unit 310. The diode 302b has a reverse polarity with respect to the charging current flowing from the positive terminal 321 in the direction of the assembled battery 301 and the forward polarity with respect to the discharging current flowing from the negative terminal 322 in the direction of the assembled battery 301. The diode 303b has a forward polarity with respect to the charging current and a reverse polarity with respect to the discharging current. In the example, the switch portion is provided on the + side, but may be provided on the − side.

  The charge control switch 302 a is turned off when the battery voltage becomes the overcharge detection voltage, and is controlled by the charge / discharge control unit so that the charge current does not flow in the current path of the assembled battery 301. After the charge control switch is turned off, only discharging is possible through the diode 302b. Further, it is turned off when a large current flows during charging, and is controlled by the control unit 310 so that the charging current flowing in the current path of the assembled battery 301 is cut off.

  The discharge control switch 303a is turned off when the battery voltage becomes the overdischarge detection voltage, and is controlled by the control unit 310 so that the discharge current does not flow through the current path of the assembled battery 301. After the discharge control switch 303a is turned off, only charging is possible via the diode 303b. Further, it is turned off when a large current flows during discharging, and is controlled by the control unit 310 so as to cut off the discharging current flowing in the current path of the assembled battery 301.

  The temperature detection element 308 is, for example, a thermistor, is provided in the vicinity of the assembled battery 301, measures the temperature of the 301 assembled battery 301, and supplies the measured temperature to the control unit 310. The voltage detection unit 311 measures the voltage of the assembled battery 301 and each secondary battery 301a constituting the assembled battery 301, performs A / D conversion on the measured voltage, and supplies the voltage to the control unit 310. The current measurement unit 313 measures the current using the current detection resistor 307 and supplies this measurement current to the control unit 310.

  The switch control unit 314 controls the charge control switch 302a and the discharge control switch 303a of the switch unit 304 based on the voltage and current input from the voltage detection unit 311 and the current measurement unit 313. The switch control unit 314 sends a control signal to the switch unit 304 when any voltage of the secondary battery 301a falls below the overcharge detection voltage or overdischarge detection voltage, or when a large current flows suddenly. By sending, overcharge, overdischarge, and overcurrent charge / discharge are prevented.

  Here, for example, when the secondary battery is a lithium ion secondary battery, the overcharge detection voltage is determined to be 4.20 V ± 0.05 V, for example, and the overdischarge detection voltage is determined to be 2.4 V ± 0.1 V, for example. .

  As the charge / discharge switch, for example, a semiconductor switch such as a MOSFET can be used. In this case, the parasitic diode of the MOSFET functions as the diodes 302b and 303b. When a P-channel FET is used as the charge / discharge switch, the switch control unit 314 supplies control signals DO and CO to the gates of the charge control switch 302a and the discharge control switch 303a, respectively. When the charge control switch 302a and the discharge control switch 303a are P-channel type, they are turned on by a gate potential that is lower than the source potential by a predetermined value or more. That is, in normal charging and discharging operations, the control signals CO and DO are set to the low level, and the charging control switch 302a and the discharging control switch 303a are turned on.

  For example, during overcharge or overdischarge, the control signals CO and DO are set to a high level, and the charge control switch 302a and the discharge control switch 303b are turned off.

  The memory 317 includes a RAM and a ROM, and includes, for example, an EPROM (Erasable Programmable Read Only Memory) that is a nonvolatile memory. In the memory 317, the numerical value calculated by the control unit 310, the internal resistance value of the battery in the initial state of each secondary battery 301a measured in the manufacturing process, and the like are stored in advance, and can be rewritten as appropriate. . (Also, by storing the full charge capacity of the secondary battery 301a, for example, the remaining capacity can be calculated together with the control unit 310.

  The temperature detection unit 318 measures the temperature using the temperature detection element 308, performs charge / discharge control during abnormal heat generation, and performs correction in the calculation of the remaining capacity.

6). Sixth Embodiment The nonaqueous electrolyte battery of the present technology and the battery pack using the same described above can be used for mounting or supplying power to devices such as electronic devices, electric vehicles, and power storage devices, for example. .

  Examples of electronic devices include notebook computers, PDAs (personal digital assistants), mobile phones, cordless phones, video movies, digital still cameras, electronic books, electronic dictionaries, music players, radios, headphones, game consoles, navigation systems, Memory cards, pacemakers, hearing aids, power tools, electric shavers, refrigerators, air conditioners, TVs, stereos, water heaters, microwave ovens, dishwashers, washing machines, dryers, lighting equipment, toys, medical equipment, robots, road conditioners, traffic lights Etc.

  Moreover, examples of the electric vehicle include a railway vehicle, a golf cart, an electric cart, an electric vehicle (including a hybrid vehicle), and the like, and these are used as a driving power source or an auxiliary power source.

  Examples of the power storage device include a power storage power source for buildings such as houses or power generation facilities.

  Below, the specific example of the electrical storage system using the electrical storage apparatus to which the nonaqueous electrolyte battery of this technique mentioned above is applied among the application examples mentioned above is demonstrated.

  This power storage system has the following configuration, for example. The first power storage system is a power storage system in which a power storage device is charged by a power generation device that generates power from renewable energy. The second power storage system is a power storage system that includes a power storage device and supplies power to an electronic device connected to the power storage device. The third power storage system is an electronic device that receives power supply from the power storage device. These power storage systems are implemented as a system for efficiently supplying power in cooperation with an external power supply network.

  Further, the fourth power storage system includes an electric vehicle having a conversion device that receives power supplied from the power storage device and converts the power into a driving force of the vehicle, and a control device that performs information processing related to vehicle control based on information related to the power storage device. It is. The fifth power storage system is a power system that includes a power information transmission / reception unit that transmits / receives signals to / from other devices via a network, and performs charge / discharge control of the power storage device described above based on information received by the transmission / reception unit. . The sixth power storage system is a power system that receives power from the power storage device described above or supplies power from the power generation device or the power network to the power storage device. Hereinafter, the power storage system will be described.

(6-1) Residential Power Storage System as an Application Example An example in which a power storage device using a nonaqueous electrolyte battery of the present technology is applied to a residential power storage system will be described with reference to FIG. For example, in the power storage system 100 for the house 101, electric power is stored from the centralized power system 102 such as the thermal power generation 102a, the nuclear power generation 102b, and the hydroelectric power generation 102c through the power network 109, the information network 112, the smart meter 107, the power hub 108, and the like. Supplied to the device 103. At the same time, power is supplied to the power storage device 103 from an independent power source such as the home power generation device 104. The electric power supplied to the power storage device 103 is stored. Electric power used in the house 101 is fed using the power storage device 103. The same power storage system can be used not only for the house 101 but also for buildings.

  The house 101 is provided with a power generation device 104, a power consumption device 105, a power storage device 103, a control device 110 that controls each device, a smart meter 107, and a sensor 111 that acquires various types of information. Each device is connected by a power network 109 and an information network 112. As the power generation device 104, a solar cell, a fuel cell, or the like is used, and the generated power is supplied to the power consumption device 105 and / or the power storage device 103. The power consuming device 105 is a refrigerator 105a, an air conditioner 105b, a television receiver 105c, a bath 105d, and the like. Furthermore, the electric power consumption device 105 includes an electric vehicle 106. The electric vehicle 106 is an electric vehicle 106a, a hybrid car 106b, and an electric motorcycle 106c.

  The nonaqueous electrolyte battery of the present technology is applied to the power storage device 103. The nonaqueous electrolyte battery of the present technology may be constituted by, for example, the above-described lithium ion secondary battery. The smart meter 107 has a function of measuring the usage amount of commercial power and transmitting the measured usage amount to an electric power company. The power network 109 may be any one or a combination of DC power supply, AC power supply, and non-contact power supply.

  The various sensors 111 are, for example, human sensors, illuminance sensors, object detection sensors, power consumption sensors, vibration sensors, contact sensors, temperature sensors, infrared sensors, and the like. Information acquired by various sensors 111 is transmitted to the control device 110. Based on the information from the sensor 111, the weather condition, the human condition, etc. can be grasped, and the power consumption device 105 can be automatically controlled to minimize the energy consumption. Furthermore, the control device 110 can transmit information regarding the house 101 to an external power company or the like via the Internet.

  The power hub 108 performs processing such as branching of power lines and DC / AC conversion. Communication methods of the information network 112 connected to the control device 110 include a method using a communication interface such as UART (Universal Asynchronous Receiver-Transceiver), wireless communication such as Bluetooth, ZigBee, and Wi-Fi. There is a method of using a sensor network according to the standard. The Bluetooth method is applied to multimedia communication and can perform one-to-many connection communication. ZigBee uses the physical layer of IEEE (Institute of Electrical and Electronics Engineers) 802.15.4. IEEE 802.15.4 is the name of a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.

  The control device 110 is connected to an external server 113. The server 113 may be managed by any one of the house 101, the power company, and the service provider. The information transmitted and received by the server 113 is, for example, information related to power consumption information, life pattern information, power charges, weather information, natural disaster information, and power transactions. These pieces of information may be transmitted / received from a power consuming device (for example, a television receiver) in the home, or may be transmitted / received from a device outside the home (for example, a mobile phone). Such information may be displayed on a device having a display function, such as a television receiver, a mobile phone, or a PDA (Personal Digital Assistants).

  A control device 110 that controls each unit includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), and the like, and is stored in the power storage device 103 in this example. The control device 110 is connected to the power storage device 103, the home power generation device 104, the power consumption device 105, the various sensors 111, the server 113 and the information network 112, and adjusts, for example, the amount of commercial power used and the amount of power generation. It has a function. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.

  As described above, the electric power can be stored not only in the centralized power system 102 such as the thermal power 102a, the nuclear power 102b, and the hydraulic power 102c but also in the power generation device 104 (solar power generation, wind power generation) in the power storage device 103. it can. Therefore, even if the generated power of the home power generation device 104 fluctuates, it is possible to perform control such that the amount of power to be sent to the outside is constant or discharge is performed as necessary. For example, the electric power obtained by solar power generation is stored in the power storage device 103, and midnight power with a low charge is stored in the power storage device 103 at night, and the power stored by the power storage device 103 is discharged during a high daytime charge. You can also use it.

  In this example, the control device 110 is stored in the power storage device 103. However, the control device 110 may be stored in the smart meter 107, or may be configured independently. Furthermore, the power storage system 100 may be used for a plurality of homes in an apartment house, or may be used for a plurality of detached houses.

(6-2) Power Storage System in Vehicle as Application Example An example in which the present technology is applied to a power storage system for a vehicle will be described with reference to FIG. FIG. 5 schematically shows an example of the configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied. A series hybrid system is a car that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power once stored in a battery.

  The hybrid vehicle 200 includes an engine 201, a generator 202, a power driving force conversion device 203, driving wheels 204a, driving wheels 204b, wheels 205a, wheels 205b, a battery 208, a vehicle control device 209, various sensors 210, and a charging port 211. Is installed. The nonaqueous electrolyte battery of the present technology described above is applied to the battery 208.

  The hybrid vehicle 200 runs using the power driving force conversion device 203 as a power source. An example of the power driving force conversion device 203 is a motor. The electric power / driving force converter 203 is operated by the electric power of the battery 208, and the rotational force of the electric power / driving force converter 203 is transmitted to the driving wheels 204a and 204b. In addition, by using a direct current-alternating current (DC-AC) or reverse conversion (AC-DC conversion) where necessary, the power driving force conversion device 203 can be applied to either an alternating current motor or a direct current motor. The various sensors 210 control the engine speed via the vehicle control device 209 and control the opening (throttle opening) of a throttle valve (not shown). The various sensors 210 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.

  The rotational force of the engine 201 is transmitted to the generator 202, and the electric power generated by the generator 202 by the rotational force can be stored in the battery 208.

  When the hybrid vehicle 200 decelerates by a braking mechanism (not shown), the resistance force at the time of deceleration is applied as a rotational force to the power driving force conversion device 203, and the regenerative electric power generated by the power driving force conversion device 203 by this rotational force is used as the battery 208. Accumulated in.

  The battery 208 can be connected to a power source external to the hybrid vehicle 200 to receive power supply from the external power source using the charging port 211 as an input port and store the received power.

  Although not shown, an information processing device that performs information processing related to vehicle control based on information related to the secondary battery may be provided. As such an information processing apparatus, for example, there is an information processing apparatus that displays a battery remaining amount based on information on the remaining amount of the battery.

  In addition, the above demonstrated as an example the series hybrid vehicle which drive | works with a motor using the electric power generated with the generator driven by an engine, or the electric power once stored in the battery. However, the present technology is also effective for a parallel hybrid vehicle in which the engine and motor outputs are both driving sources, and the system is switched between the three modes of driving with only the engine, driving with the motor, and engine and motor. Applicable. Furthermore, the present technology can be effectively applied to a so-called electric vehicle that travels only by a drive motor without using an engine.

Specific examples of the present technology will be described in detail, but the present technology is not limited thereto.
The dinitrile compounds used in the following examples and comparative examples are as follows.
A: malononitrile B: succinonitrile C: glutaronitrile D: adiponitrile E: suberonitrile F: sebacononitrile G: dodecandinitrile

<Example 1-1>
The laminate type secondary battery shown in FIG. 1 and FIG. 2 was produced by using the following procedure using MCMB (mesocarbon microbeads) -based graphite as a negative electrode active material.

First, 94 parts by mass of lithium cobaltate (LiCoO ₂ ) as a positive electrode active material, 3 parts by mass of graphite as a conductive agent, and 3 parts by mass of polyvinylidene fluoride (PVdF) as a binder were uniformly mixed to form N-methyl. Pyrrolidone was added to obtain a positive electrode mixture slurry.

Next, the obtained positive electrode mixture slurry was uniformly applied on both surfaces of a 10 μm thick aluminum foil serving as a positive electrode current collector, and dried to form a positive electrode mixture layer of 16 mg / cm ² per side. This was cut into a shape having a width of 50 mm and a length of 300 mm to produce a positive electrode.

  Further, 97 parts by mass of MCMB (mesocarbon microbeads) graphite as a negative electrode active material and 3 parts by mass of PVdF as a binder were mixed homogeneously, and N-methylpyrrolidone was added to obtain a negative electrode mixture slurry.

Next, the obtained negative electrode mixture slurry was uniformly applied on both sides of a 10 μm thick copper foil serving as a negative electrode current collector, and dried to form a negative electrode mixture layer of 10 mg / cm ² per side. This was cut into a shape having a width of 50 mm and a length of 300 mm to prepare a negative electrode.

  An electrolyte solution having an electrolyte composition (EC / PC / VC / A / electrolyte salt = 45.275 mass% / 45.275 mass% / 1 mass% / 0.05 mass% / 8.4 mass%) is as follows: It was prepared as follows. First, 0.6 mol / kg (8.4 mass%) of lithium hexafluorophosphate was dissolved in a main solvent mixed with ethylene carbonate (EC) / propylene carbonate (PC) = 1/1 (mass ratio). Vinylene carbonate (VC) was mixed at 1% by mass and Compound A was mixed at 0.05% by mass, thereby obtaining an electrolytic solution.

  After winding the positive electrode and the negative electrode through a separator made of a microporous polyethylene film having a thickness of 9 μm, after putting it in a bag-like exterior member made of an aluminum laminate film, 2 g of an electrolyte solution was injected, The bag was heat-sealed to produce a laminated battery of Example 1-1.

<Example 1-2 to Example 1-8>
A laminate-type battery was produced in the same manner as in Example 1-1 except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 1 when the electrolytic solution was prepared. .

<Example 1-9 to Example 1-13>
A laminate-type battery was produced in the same manner as in Example 1-1 except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 1 when the electrolytic solution was prepared. .

<Example 1-14 to Example 1-15>
Instead of vinylene carbonate (VC), an electrolytic solution composition using fluoroethylene carbonate (FEC) or difluoroethylene carbonate (DFEC) was used. That is, a laminate type battery was prepared in the same manner as in Example 1-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 1 when the electrolytic solution was prepared. Produced.

<Example 1-16 to Example 1-19>
A laminate-type battery was produced in the same manner as in Example 1-1 except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 1 when the electrolytic solution was prepared. .

<Example 1-20 to Example 1-21>
A laminate-type battery was produced in the same manner as in Example 1-1 except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 1 when the electrolytic solution was prepared. .

<Example 1-22 to Example 1-23>
A laminate-type battery was produced in the same manner as in Example 1-1 except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 1 when the electrolytic solution was prepared. .

<Comparative Example 1-1>
The electrolyte solution composition was not added with a nitrile compound. That is, a laminate type battery was prepared in the same manner as in Example 1-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 1 when the electrolytic solution was prepared. Produced.

<Comparative Example 1-2>
The electrolyte solution composition was such that vinylene carbonate (VC) and a nitrile compound were not added. That is, a laminate type battery was prepared in the same manner as in Example 1-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 1 when the electrolytic solution was prepared. Produced.

<Comparative Example 1-3>
The amount of Chemical A was increased, and the amounts of ethylene carbonate (EC) and propylene carbonate (PC) as main solvents were decreased accordingly. That is, a laminate type battery was prepared in the same manner as in Example 1-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 1 when the electrolytic solution was prepared. Produced.

<Comparative Example 1-4>
Ethyl methyl carbonate (EMC), which is a chain carbonate, was added, and ethylene carbonate (EC) and propylene carbonate (PC) were reduced accordingly. That is, a laminate type battery was prepared in the same manner as in Example 1-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 1 when the electrolytic solution was prepared. Produced.

<Example 1-24 to Example 1-28, Comparative Example 1-5 to Comparative Example 1-8>
In preparing the electrolytic solution, the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were set as shown in Table 1, and Example 1-1 was used except that the upper limit voltage for charging was set to 4.30 V. Similarly, a laminate type battery was produced.

<Example 1-29 to Example 1-33, Comparative Example 1-9 to Comparative Example 1-12>
In the preparation of the electrolytic solution, the composition of the main solvent, the composition of the other solvents, and the composition of the chemical A were as shown in Table 1, and Example 1-1 and the point other than that the upper limit voltage for charging was set to 4.35 V Similarly, a laminate type battery was produced.

(Evaluation)
The following evaluation was performed for each laminated battery of Example 1-1 to Example 1-33 and Comparative Example 1-1 to Comparative Example 1-12.

(Initial capacity and high temperature cycle test)
First, each battery was charged and discharged for 2 cycles at a current of 0.2 C in an atmosphere of 23 ° C., and the discharge capacity at the second cycle was measured. Subsequently, 300 cycles of charge and discharge were repeated in an atmosphere at 23 ° C., and the discharge capacity maintenance rate (cycle maintenance rate) at 300 cycles with respect to the discharge capacity at the second cycle was calculated as (discharge capacity at 300th cycle / 2nd cycle). (Discharge capacity) × 100 (%). As charging / discharging conditions, constant current and constant voltage charging was performed at a current of 0.2 C to the upper limit voltage described in Table 1, and further charging was performed until the current value reached 0.05 C at a constant voltage at the upper limit voltage. A constant current was discharged at a current of 2 C to a final voltage of 3.0 V. This “0.2 C” is a current value at which the theoretical capacity can be discharged in 5 hours.

(Measures swelling when stored at high temperature)
Each battery after the initial capacity measurement was charged in a 23 ° C. atmosphere for 3 hours with the voltage shown in Table 1 as the upper limit, then stored in a 90 ° C. constant temperature bath for 4 hours in the charged state, and the battery thickness after storage The increase rate of the cell thickness during high temperature storage (change in cell thickness during high temperature storage) was determined from the difference between the battery thickness and the battery thickness before storage.

  The evaluation results are shown in Table 1.

  Table 1 shows the following. In Example 1-1 to Example 1-23, the electrolyte solution contains 80% by mass or more of cyclic alkylene carbonate and contains a dinitrile compound represented by the formula (1) such as Chemical Formula A. Both the swollenness characteristics and the cycle characteristics during storage could be made favorable.

  On the other hand, Comparative Example 1-1 contains 80% by mass or more of cyclic alkylene carbonate in the electrolytic solution, but does not contain the dinitrile compound represented by the formula (1) like Chemical A. Compared to 1-1 to Example 1-8, both the swollenness characteristics and cycle characteristics during high-temperature storage could not be improved. In particular, in Comparative Example 1-1, the swelling characteristics during high-temperature storage deteriorated compared to Examples 1-1 to 1-8. Similarly, Comparative Example 1-2 contains 80% by mass or more of cyclic alkylene carbonate in the electrolytic solution, but does not contain the dinitrile compound represented by Formula (1), so Examples 1-9 to Compared to Example 1-13, both the swollenness characteristics and cycle characteristics during high-temperature storage could not be improved. In particular, in Comparative Example 1-2, the swollenness characteristics during high-temperature storage deteriorated compared to Examples 1-9 to 1-13.

  In Comparative Example 1-3, although the dinitrile compound represented by Formula (1) is contained in the electrolytic solution, the content of cyclic alkylene carbonate is less than 80% by mass. Compared with 1-8, both the swelling characteristics during high temperature storage and the cycle characteristics during high temperature storage could not be made favorable. In particular, in Comparative Example 1-3, the cycle characteristics were deteriorated as compared with Examples 1-1 to 1-8.

  Moreover, according to Example 1-1 to Example 1-8, when the content of the compound represented by the formula (1) in the electrolytic solution was 3% by mass or less, the cycle characteristics were better. . According to Examples 1-14 to 1-15, since the electrolyte contains fluoroethylene carbonate (FEC) and difluoroethylene carbonate (DFEC), both swelling characteristics and cycle characteristics during high-temperature storage are included. Was able to improve. According to Examples 1-16 to 1-19, as the ratio of the mass of EC to the total mass of cyclic alkylene carbonate in the electrolytic solution increases, cycle characteristics are improved, and the total mass of cyclic alkylene carbonate is increased. As the proportion of EC mass decreased, the swelling characteristics during high temperature storage improved. According to Examples 1-20 to 1-21, by including ethyl methyl carbonate (EMC), which is a chain-like alkylene carbonate, in the electrolytic solution, while maintaining the swollenness characteristics during high temperature storage, the cycle The characteristics could be improved further.

  In Examples 1-24 to 1-28, the electrolytic solution contains 80% by mass or more of cyclic alkylene carbonate and contains a dinitrile compound represented by the formula (1), so that the charging voltage is 4.30V. When set to, both the swelling characteristics and cycle characteristics during high temperature storage could be made favorable. In Examples 1-29 to 1-33, the electrolytic solution contains 80% by mass or more of cyclic alkylene carbonate and the dinitrile compound represented by the formula (1), so that the charging voltage is 4.35V. When set to, both the swelling characteristics and cycle characteristics during high temperature storage could be made favorable.

  Compared with the case where the charging voltage was set to 4.25 V, the degree of effect using the electrolytic solution of the present technology was larger when the charging voltage was set to 4.30 V and 4.35 V. Therefore, it was confirmed that the electrolytic solution composition of the present technology is more effective as the upper limit voltage of the battery exceeds 4.2 V and can significantly improve the swollenness characteristics during high temperature storage.

<Example 2-1>
A laminated battery was produced in the same manner as Example 1-29.

<Example 2-2 to Example 2-6>
A laminate type battery was produced in the same manner as in Example 3-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of the chemical compound A were as shown in Table 2 when adjusting the electrolytic solution. .

<Example 2-7 to Example 2-12>
A laminate type battery was produced in the same manner as in Example 2-1 to Example 2-6, except that Chemical Formula A was changed to Chemical Formula B when the electrolytic solution was prepared.

<Example 2-13 to Example 2-18>
A laminate type battery was produced in the same manner as in Example 2-1 to Example 2-6, except that Chemical Formula A was changed to Chemical Formula C when the electrolytic solution was prepared.

<Example 2-19 to Example 2-24>
A laminate type battery was produced in the same manner as in Example 2-1 to Example 2-6, except that Chemical Formula A was changed to Chemical Formula D when the electrolytic solution was prepared.

<Example 2-25 to Example 2-30>
A laminate type battery was produced in the same manner as in Example 2-1 to Example 2-6, except that Chemical Formula A was changed to Chemical Formula E when the electrolytic solution was prepared.

<Example 2-31 to Example 2-36>
A laminate type battery was produced in the same manner as in Example 2-1 to Example 2-6, except that Chemical A was changed to Chemical F during the preparation of the electrolytic solution.

<Example 2-37 to Example 2-42>
A laminate type battery was produced in the same manner as in Example 2-1 to Example 2-6, except that Chemical A was changed to Chemical G when the electrolytic solution was prepared.

(Evaluation)
For the laminated batteries of Example 2-1 to Example 2-42, the initial capacity, the high-temperature cycle test, and the swelling during high-temperature storage were measured in the same manner as in Example 1-29. The evaluation results are shown in Table 2.

  Table 2 shows the following. In the electrolytic solution, the cyclic alkylene carbonate is contained in an amount of 80% by mass or more, and in addition to chemical A, a dinitrile compound represented by the formula (1) such as chemical B to chemical G is contained. Both the swollenness characteristic and the cycle characteristic could be made favorable.

<Example 3-1>
Example 2-1 except that the thickness of the separator made of polyethylene film was 7 μm, and both sides were coated with 2 μm of polyvinylidene fluoride, which is a polymer material for holding the electrolytic solution, as the separator. Similarly, a laminate type battery was produced.

<Example 3-2 to Example 3-7>
A laminate type battery was produced in the same manner as in Example 3-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of the chemical compound A were as shown in Table 3 when the electrolytic solution was prepared. .

<Example 3-8 to Example 3-14>
A laminate type battery was produced in the same manner as in Example 3-1 to Example 3-7, except that Chemical Formula A was changed to Chemical Formula B when the electrolytic solution was prepared.

<Example 3-15 to Example 3-20>
A laminate type battery was produced in the same manner as in Example 3-1 to Example 3-7, except that the chemical A was changed to the chemical C during the preparation of the electrolytic solution.

<Example 3-21 to Example 3-27>
A laminate type battery was produced in the same manner as Example 3-1 to Example 3-7, except that Chemical Formula A was changed to Chemical Formula D when the electrolytic solution was prepared.

<Example 3-28 to Example 3-33>
A laminate type battery was produced in the same manner as Example 3-1 to Example 3-7, except that Chemical Formula A was changed to Chemical Formula E when the electrolytic solution was prepared.

<Example 3-34 to Example 3-39>
A laminate type battery was produced in the same manner as in Example 3-1 to Example 3-7, except that Chemical A was changed to Chemical F during the preparation of the electrolytic solution.

<Example 3-40 to Example 3-45>
A laminate type battery was produced in the same manner as in Example 3-1 to Example 3-7, except that Chemical A was changed to Chemical G during the preparation of the electrolytic solution.

<Comparative Example 3-1>
The electrolyte solution composition was not added with a nitrile compound. That is, a laminate type battery was prepared in the same manner as in Example 3-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 3 when preparing the electrolytic solution. Produced.

<Comparative Example 3-2>
The electrolyte solution composition was such that vinylene carbonate (VC) and a nitrile compound were not added. That is, a laminate type battery was prepared in the same manner as in Example 3-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 3 when preparing the electrolytic solution. Produced.

<Comparative Example 3-3>
The amount of electrolysis A was increased, and the amounts of ethylene carbonate (EC) and propylene carbonate (PC) as main solvents were decreased accordingly. That is, a laminate type battery was prepared in the same manner as in Example 3-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 3 when preparing the electrolytic solution. Produced.

<Comparative Example 3-4>
Ethyl methyl carbonate (EMC), which is a chain carbonate, was added, and ethylene carbonate (EC) and propylene carbonate (PC) were reduced accordingly. That is, a laminate type battery was prepared in the same manner as in Example 3-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 3 when preparing the electrolytic solution. Produced.

(Evaluation)
The following evaluation was performed for each laminated battery of Example 3-1 to Example 3-45 and Comparative Example 3-1 to Comparative Example 3-4.

(Initial capacity and high temperature cycle test)
First, each battery was charged and discharged for 2 cycles at a current of 0.2 C in an atmosphere of 23 ° C., and the discharge capacity at the second cycle was measured. Subsequently, 300 cycles of charge and discharge were repeated in an atmosphere at 23 ° C., and the discharge capacity maintenance rate (cycle maintenance rate) at 300 cycles with respect to the discharge capacity at the second cycle was calculated as (discharge capacity at 300th cycle / 2nd cycle). (Discharge capacity) × 100 (%). As charging / discharging conditions, constant current and constant voltage charging was performed at a current of 0.2 C to the upper limit voltage described in Table 3, and further charging was performed until the current value reached 0.05 C at a constant voltage at the upper limit voltage. A constant current was discharged at a current of 2 C to a final voltage of 3.0 V. This “0.2 C” is a current value at which the theoretical capacity can be discharged in 5 hours.

(Measures swelling when stored at high temperature)
Each battery after the initial capacity measurement was charged in a 23 ° C. atmosphere for 3 hours with the voltage shown in Table 3 as the upper limit, and then stored in a 90 ° C. constant temperature bath for 4 hours in the charged state. The increase rate of the cell thickness during high temperature storage (change in cell thickness during high temperature storage) was determined from the difference between the battery thickness and the battery thickness before storage.

(Measurement of discharge load characteristics)
For each battery after the initial capacity measurement, after charging for 3 hours with a current of 1 C with the voltage shown in Table 3 as the upper limit, the discharge capacity when discharging at constant current to a final voltage of 3.0 V with a current of 0.2 C (0 .2C discharge capacity). Next, after charging under the same conditions, a discharge capacity (3C discharge capacity) when a constant current discharge is performed at a current of 3C to a final voltage of 3.0 V is measured, and load characteristics are expressed as (3C discharge capacity / 0.2C (Discharge capacity) × 100 (%). “0.2 C” is a current value at which the theoretical capacity can be discharged in 5 hours, and “3C” is a current value at which the theoretical capacity can be discharged in 20 minutes.

(Measurement of conductivity of gel electrolyte)
A gel electrolyte was prepared by dissolving 10 parts by mass of polyvinylidene fluoride in 90 parts by mass of the electrolytic solution having the composition shown in Table 3, and the electrical conductivity of this gel electrolyte at 23 ° C. was measured.

  The evaluation results are shown in Table 3.

  Table 3 shows the following. In a laminate type battery in which polyvinylidene fluoride, which is a polymer material for holding an electrolyte solution, is applied to a separator, a laminate type battery using a separator made of only polyethylene as in Example 2-1 to Example 2-42 Compared to the above, the swollenness characteristics and cycle characteristics were improved. This is presumably because the positive electrode / separator / negative electrode are adhered to each other so that gas is less likely to be generated during storage and the distance between the electrodes can be maintained even after repeated charge / discharge.

<Example 4-1 to Example 4-45>
The thickness of the separator made of polyethylene film is 7 μm, and 2 μm each of mixed materials containing the same amount of polyvinylidene fluoride as a polymer material for holding the electrolyte and Al ₂ O ₃ as ceramic powder on both sides A laminate type battery was produced in the same manner as Example 3-1 to Example 3-45 except that the coated material was used as a separator.

<Comparative Example 4-1>
The electrolyte solution composition was not added with a nitrile compound. That is, a laminate type battery was prepared in the same manner as in Example 4-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 4 when preparing the electrolytic solution. Produced.

<Comparative Example 4-2>
The electrolyte solution composition was such that vinylene carbonate (VC) and a nitrile compound were not added. That is, a laminate type battery was prepared in the same manner as in Example 4-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 4 when preparing the electrolytic solution. Produced.

<Comparative Example 4-3>
The amount of electrolysis A was increased, and the amounts of ethylene carbonate (EC) and propylene carbonate (PC) as main solvents were decreased accordingly. That is, a laminate type battery was prepared in the same manner as in Example 4-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 4 when preparing the electrolytic solution. Produced.

<Comparative Example 4-4>
Ethyl methyl carbonate (EMC), which is a chain carbonate, was added, and ethylene carbonate (EC) and propylene carbonate (PC) were reduced accordingly. That is, a laminate type battery was prepared in the same manner as in Example 4-1, except that the composition of the main solvent, the composition of the other solvents, and the composition of Chemical Formula A were as shown in Table 4 when preparing the electrolytic solution. Produced.

(Evaluation)
For each of the laminate type batteries of Example 4-1 to Example 4-45 and Comparative Example 4-1 to Comparative Example 4-4, in the same manner as in Example 3-1, the initial capacity and the high-temperature cycle test, at the time of high-temperature storage The measurement of the swelling and the discharge load characteristic were performed. Moreover, the electrical conductivity measurement of the gel electrolyte was performed as follows.

(Measurement of conductivity of gel electrolyte)
Gel form in which 10 parts by mass of polyvinylidene fluoride is dissolved in 90 parts by mass of the electrolytic solution having the composition shown in Table 4, and Al ₂ O ₃ is added in the same mass part (10 parts by mass) as polyvinylidene fluoride as ceramic powder. An electrolyte was prepared. The electrical conductivity of this gel electrolyte at 23 ° C. was measured.

  The evaluation results are shown in Table 4.

Table 4 shows the following. In a laminate type battery in which polyvinylidene fluoride, which is a polymer material for holding an electrolytic solution, is added to a separator and applied with Al ₂ O ₃ which is ceramic powder, as in Example 2-1 to Example 2-42 As compared with a laminate type battery using a polyethylene-only separator, the swelling characteristics and cycle characteristics were improved. This is presumably because the positive electrode / separator / negative electrode are adhered to each other so that gas is less likely to be generated during storage and the distance between the electrodes can be maintained even after repeated charge / discharge. In addition, it is considered that Al ₂ O ₃ is present at the electrode interface, thereby suppressing side reactions during charging and discharging.

Further, due to the influence of the Al ₂ O ₃ added, the conductivity of the electrolyte is reduced (e.g., comparing the reference and Comparative Example 3-1 and Comparative Example 4-1), Example 4-1 Example 4-45 Then, the electrical conductivity was improved by containing the nitrile compound represented by the formula (1) in the electrolytic solution, and the decrease in electrical conductivity due to the addition of Al ₂ O ₃ could be compensated.

<Example 5-1 to Example 5-35>
Table 5 shows the composition of the main solvent, the composition of the other solvents, the compositions of Chemical Formula B, Chemical Formula D, Chemical Formula E, and the concentration of lithium hexafluorophosphate (salt concentration) during the preparation of the electrolytic solution. Except for the above, each laminate type battery was produced in the same manner as in Example 4-1.

(Evaluation)
For each of the laminate type batteries of Example 5-1 to Example 5-35, the initial capacity and the high temperature cycle test, the measurement of swelling during storage at high temperature, and the measurement of discharge load characteristics were performed in the same manner as in Example 3-1. It was. Moreover, the electrical conductivity measurement of the gel electrolyte was performed as follows.

(Measurement of conductivity of gel electrolyte)
Gel form in which 10 parts by mass of polyvinylidene fluoride is dissolved in 90 parts by mass of the electrolytic solution having the composition shown in Table 5, and Al ₂ O ₃ is added in the same mass part (10 parts by mass) as polyvinylidene fluoride as ceramic powder. An electrolyte was prepared. The electrical conductivity of this gel electrolyte at 23 ° C. was measured.

  The evaluation results are shown in Table 5.

  As shown in Table 5, the mass percentage of the dinitrile compound content relative to the electrolyte salt content ([dinitrile compound mass / electrolyte salt mass] × 100 [%]) is 6.0% or more and 36% or less. The conductivity could be increased without interfering with the cycle characteristics and load characteristics. On the other hand, as shown in Example 4-11 and Example 4-24 in Table 4, when the mass percentage was too large, the load characteristics deteriorated.

7). Other embodiment (modification)
The present technology is not limited to the above-described embodiments of the present technology, and various modifications and applications are possible without departing from the scope of the present technology. For example, in the above-described embodiments and examples, the nonaqueous electrolyte battery having a winding structure has been described as a specific example, but the present invention is not limited to this. For example, the present technology is similarly applied to a non-aqueous electrolyte battery having a battery element in which one or a plurality of positive electrodes and negative electrodes are stacked and folded, or one or more positive and negative electrodes are stacked. Can be applied to.

  Moreover, although the above-mentioned embodiment and Example demonstrated the case where a film-shaped exterior member was used, you may use the exterior member of a can. In that case, the shape may be any shape such as a cylindrical shape, a square shape, a coin shape, or a button shape.

  Furthermore, in the above-described embodiments and examples, the case where lithium is used for the electrode reaction has been described, but other alkali metals such as sodium (Na) or potassium (K), or alkaline earth such as magnesium or calcium (Ca). The present technology can also be applied to the case where other light metals such as a similar metal or aluminum are used, and similar effects can be obtained. Further, lithium metal may be used as the negative electrode active material.

The present technology may take the following configurations.
[1]
A positive electrode;
A negative electrode,
A non-aqueous electrolyte including a non-aqueous electrolyte containing a non-aqueous solvent and an electrolyte salt,
The open circuit voltage in a fully charged state per pair of positive electrode and negative electrode is set within a range of 4.25V to 4.50V,
The non-aqueous solvent is
Cyclic alkylene carbonate;
A dinitrile compound represented by formula (1),
The non-aqueous electrolyte secondary battery in which the content of the cyclic alkylene carbonate is 80% by mass or more based on the total mass of the non-aqueous electrolyte.
Formula (1)
NC- (CH _{2) n} -CN
(In the formula, n is an integer of 1 or more.)
[2]
The nonaqueous electrolyte secondary battery according to [1], wherein the nonaqueous electrolyte is a gel electrolyte further including a polymer compound that holds the nonaqueous electrolyte.
[3]
The non-aqueous electrolyte secondary battery according to [2], wherein the gel electrolyte contains ceramic powder.
[4]
The non-aqueous electrolyte secondary battery according to any one of [1] to [3], wherein the cyclic alkylene carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and 1,2-butylene carbonate.
[5]
The cyclic alkylene carbonate includes ethylene carbonate and another cyclic alkylene carbonate other than the ethylene carbonate,
The nonaqueous electrolyte secondary battery according to any one of [1] to [4], wherein a ratio of the mass of the ethylene carbonate to the total mass of the cyclic alkylene carbonate is 20% or more and 60% or less.
[6]
The non-aqueous electrolyte secondary battery according to any one of [3] to [5], wherein the ceramic powder is at least one selected from the group consisting of Al ₂ O ₃ , ZrO, TiO ₂ , and MgO ₂ .
[7]
The non-aqueous electrolyte secondary battery according to any one of [1] to [6], wherein n, which indicates the number of hydrocarbon groups in the formula (1), is 1 or more and 6 or less.
[8]
The non-aqueous electrolyte secondary battery according to any one of [1] to [7], wherein the content of the cyclic carbonate is 80% by mass to 95% by mass with respect to the total mass of the non-aqueous electrolyte. .
[9]
The content of the dinitrile compound represented by the above formula (1) is from 0.1% by mass to 5.0% by mass with respect to the total mass of the non-aqueous electrolyte. The nonaqueous electrolyte secondary battery according to any one of the above.
[10]
The mass percentage of the content of the electrolyte salt relative to the content of the ditolyl compound represented by the above formula (1) ([dinitrile compound mass / electrolyte salt mass] × 100 [%]) is 6% or more and 36% or less. The nonaqueous electrolyte secondary battery according to any one of [1] to [9].
[11]
The non-aqueous electrolyte secondary according to any one of [1] to [10], wherein the non-aqueous solvent further contains at least one of a cyclic carbonate having a carbon-carbon multiple bond and a halogenated cyclic carbonate. battery.
[12]
The positive electrode includes lithium, a lithium composite oxide having at least one member selected from the group consisting of cobalt, nickel, and manganese, and phosphorus, nickel, cobalt, manganese, iron, aluminum on the surface of the lithium composite oxide. The nonaqueous electrolyte secondary battery according to any one of [1] to [11], which contains, as a positive electrode active material, a positive electrode material having a covering element consisting of at least one member selected from the group consisting of magnesium and zinc.
[13]
The nonaqueous electrolyte secondary battery according to any one of [1] to [12], wherein an electrode body including the positive electrode and the negative electrode is packaged with a laminate film.
[14]
A non-aqueous electrolyte containing a non-aqueous solvent and an electrolyte salt,
The non-aqueous solvent is
Cyclic alkylene carbonate;
A dinitrile compound represented by formula (1),
Content of the said cyclic alkylene carbonate is a non-aqueous electrolyte which is 80 mass% or more with respect to the total mass of the said non-aqueous electrolyte.
Formula (1)
NC- (CH _{2) n} -CN
(In the formula, n is an integer of 1 or more.)
[15]
The nonaqueous electrolyte secondary battery according to [1],
A control unit for controlling the non-aqueous electrolyte secondary battery;
A battery pack having an exterior enclosing the non-aqueous electrolyte secondary battery.
[16]
Having the nonaqueous electrolyte secondary battery according to [1],
An electronic device that receives power from the non-aqueous electrolyte secondary battery.
[17]
The nonaqueous electrolyte secondary battery according to [1],
A conversion device that receives supply of electric power from the non-aqueous electrolyte secondary battery and converts it into driving force of a vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the non-aqueous electrolyte secondary battery.
[18]
Having the nonaqueous electrolyte secondary battery according to [1],
A power storage device that supplies electric power to an electronic device connected to the non-aqueous electrolyte secondary battery.
[19]
The power storage device according to [18], including a power information control device that transmits and receives signals to and from other devices via a network, and performing charge / discharge control of the non-aqueous electrolyte secondary battery based on information received by the power information control device. apparatus.
[20]
The electric power system which receives supply of electric power from the nonaqueous electrolyte secondary battery as described in [1], or supplies electric power to the nonaqueous electrolyte secondary battery from a power generator or a power network.

  30 ... wound electrode body, 31 ... positive electrode lead, 32 ... negative electrode lead, 33 ... positive electrode, 33A ... positive electrode current collector, 33B ... positive electrode active material layer, 34 ... Negative electrode, 34A ... negative electrode current collector, 34B ... negative electrode active material layer, 35 ... separator, 36 ... electrolyte, 37 ... protective tape, 40 ... exterior member, 41 ... -Adhesive film, 100 ... Power storage system, 101 ... Housing, 102a ... Thermal power generation, 102b ... Nuclear power generation, 102c ... Hydroelectric power generation, 102 ... Centralized power system, 103 ... Power storage device 104 ... Home power generation device 105 ... Power consumption device 105a ... Refrigerator 105b ... Air conditioner 105c ... TV receiver 105d ... Bath 106 ... Electric vehicle, 106a ... Electricity Vehicle, 106b ... Hybrid car, 106c ... Electric motorcycle, 107 ... Smart meter, 108 ... Power hub, 109 ... Power network, 110 ... Control device, 111 ... Sensor, 112 ··· Information network 113 ··· Server, 200 ··· Hybrid vehicle, 201 ··· Engine, 202 ··· Generator, 203 · · · Electric power / driving force conversion device, 204a · · · Drive wheels, 204b · ..Drive wheel, 204a, 204b ... drive wheel, 205a, wheel ... 205b, 208 ... battery, 209 ... vehicle control device, 210 ... various sensors, 211 ... charge port, 301 ... Battery pack, 301a ... Secondary battery, 302a ... Charge control switch, 302b ... Diode, 303a ... Discharge control switch, 303b .. Diode, 304 ... Switch unit, 307 ... Current detection resistor, 308 ... Temperature detection element, 310 ... Control unit, 311 ... Voltage detection unit, 313 ... Current measurement unit, 314: Switch control unit, 317 ... Memory, 318 ... Temperature detection unit, 321 ... Positive terminal, 322 ... Negative terminal

Claims (20)

A positive electrode;
A negative electrode,
A non-aqueous electrolyte including a non-aqueous electrolyte containing a non-aqueous solvent and an electrolyte salt,
The open circuit voltage in a fully charged state per pair of positive electrode and negative electrode is set within a range of 4.25V to 4.50V,
The non-aqueous solvent is
Cyclic alkylene carbonate;
A dinitrile compound represented by formula (1),
The non-aqueous electrolyte secondary battery in which the content of the cyclic alkylene carbonate is 80% by mass or more based on the total mass of the non-aqueous electrolyte.
Formula (1)
NC- (CH _{2) n} -CN
(In the formula, n is an integer of 1 or more.)   The nonaqueous electrolyte secondary battery according to claim 1, wherein the nonaqueous electrolyte is a gel electrolyte further including a polymer compound that holds the nonaqueous electrolyte solution.   The non-aqueous electrolyte secondary battery according to claim 2, wherein the gel electrolyte contains ceramic powder.   The non-aqueous electrolyte secondary battery according to claim 1, wherein the cyclic alkylene carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and 1,2-butylene carbonate. The cyclic alkylene carbonate includes ethylene carbonate and another cyclic alkylene carbonate other than the ethylene carbonate,
The nonaqueous electrolyte secondary battery according to claim 1, wherein a ratio of the mass of the ethylene carbonate to the total mass of the cyclic alkylene carbonate is 20% or more and 60% or less. The non-aqueous electrolyte secondary battery according to claim ₃ , wherein the ceramic powder is at least one selected from the group consisting of Al ₂ O ₃ , ZrO, TiO ₂ , and MgO ₂ .   The nonaqueous electrolyte secondary battery according to claim 1, wherein the n, which indicates the number of hydrocarbon groups in the formula (1), is 1 or more and 6 or less.   2. The nonaqueous electrolyte secondary battery according to claim 1, wherein a content of the cyclic carbonate is 80% by mass or more and 95% by mass or less with respect to a total mass of the nonaqueous electrolyte solution.   2. The non-aqueous solution according to claim 1, wherein the content of the dinitrile compound represented by the formula (1) is 0.1% by mass or more and 5.0% by mass or less with respect to the total mass of the non-aqueous electrolyte solution. Electrolyte secondary battery.   The mass percentage of the content of the electrolyte salt relative to the content of the ditolyl compound represented by the above formula (1) ([dinitrile compound mass / electrolyte salt mass] × 100 [%]) is 6% or more and 36% or less. The nonaqueous electrolyte secondary battery according to claim 1.   The nonaqueous electrolyte secondary battery according to claim 1, wherein the nonaqueous solvent further contains at least one of a cyclic carbonate having a carbon-carbon multiple bond and a halogenated cyclic carbonate.   The positive electrode includes lithium, a lithium composite oxide having at least one member selected from the group consisting of cobalt, nickel, and manganese, and phosphorus, nickel, cobalt, manganese, iron, aluminum on the surface of the lithium composite oxide. The nonaqueous electrolyte secondary battery according to claim 1, comprising a positive electrode material having a covering element made of at least one member selected from the group consisting of magnesium and zinc as a positive electrode active material.   The non-aqueous electrolyte secondary battery according to claim 1, wherein an electrode body including the positive electrode and the negative electrode is covered with a laminate film. A non-aqueous electrolyte containing a non-aqueous solvent and an electrolyte salt,
The non-aqueous solvent is
Cyclic alkylene carbonate;
A dinitrile compound represented by formula (1),
Content of the said cyclic alkylene carbonate is a non-aqueous electrolyte which is 80 mass% or more with respect to the total mass of the said non-aqueous electrolyte.
Formula (1)
NC- (CH _{2) n} -CN
(In the formula, n is an integer of 1 or more.) The nonaqueous electrolyte secondary battery according to claim 1;
A control unit for controlling the non-aqueous electrolyte secondary battery;
A battery pack having an exterior enclosing the non-aqueous electrolyte secondary battery. The nonaqueous electrolyte secondary battery according to claim 1,
An electronic device that receives power from the non-aqueous electrolyte secondary battery. The nonaqueous electrolyte secondary battery according to claim 1;
A conversion device that receives supply of electric power from the non-aqueous electrolyte secondary battery and converts it into driving force of a vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the non-aqueous electrolyte secondary battery. The nonaqueous electrolyte secondary battery according to claim 1,
A power storage device that supplies electric power to an electronic device connected to the non-aqueous electrolyte secondary battery. The electrical storage according to claim 18, further comprising: a power information control device that transmits and receives signals to and from other devices via a network, and performing charge / discharge control of the nonaqueous electrolyte secondary battery based on information received by the power information control device. apparatus.   The electric power system which receives supply of electric power from the nonaqueous electrolyte secondary battery of Claim 1, or supplies electric power to the said nonaqueous electrolyte secondary battery from a power generator or a power network.

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