JP4741526B2 - Nonaqueous electrolyte secondary battery - Google Patents

Nonaqueous electrolyte secondary battery Download PDF

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JP4741526B2
JP4741526B2 JP2007019525A JP2007019525A JP4741526B2 JP 4741526 B2 JP4741526 B2 JP 4741526B2 JP 2007019525 A JP2007019525 A JP 2007019525A JP 2007019525 A JP2007019525 A JP 2007019525A JP 4741526 B2 JP4741526 B2 JP 4741526B2
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positive electrode
negative electrode
non
secondary battery
aqueous electrolyte
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JP2008071731A (en
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智之 中村
有治 内田
剛彦 諏訪
貴弘 遠藤
広隆 酒井
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ソニー株式会社
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Priority claimed from US11/836,038 external-priority patent/US7955731B2/en
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Description

  The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a non-aqueous electrolyte secondary battery that has excellent cycle characteristics and can suppress or prevent swelling during high-temperature storage.

In recent years, many portable electronic devices such as camera-integrated VTRs (videotape recorders), mobile phones, and portable computers have appeared, and their size and weight have been reduced. Accordingly, the development of batteries, particularly secondary batteries, has been actively promoted as portable power sources for electronic devices. Among these, lithium ion secondary batteries are attracting attention as being capable of realizing a high energy density.
In recent years, batteries have been further reduced in size, weight, and thickness by using a laminate film or the like as an exterior member instead of a metal can such as aluminum or iron.

On the other hand, in a secondary battery using a metal can as an exterior body, it has been proposed to improve cycle characteristics and the like by controlling the amount of electrolyte and the amount of voids per battery capacity (Patent Literature). 1-3.)
In all of these, in a so-called liquid battery using an electrolyte as an electrolyte, the amount of the electrolyte is regulated in relation to the gap, such as prevention of liquid leakage and prevention of an increase in internal pressure.
Japanese Patent No. 2646657 Japanese Patent No. 2757398 JP 2000-285959 A

However, when the amount of the electrolytic solution described in Patent Documents 1 to 3 described above is applied to a secondary battery using a laminate film as an exterior member, there is a problem in that it swells greatly during high-temperature storage.
Such swelling during high-temperature storage can be suppressed by reducing the amount of electrolyte in the battery, but the amount of electrolyte is reduced too much and the electrolyte does not completely fill the periphery of the active material. As a result, the battery reaction does not proceed in a portion of the electrode that is not in contact with the electrolytic solution, and a sufficient battery capacity may not be obtained.
Furthermore, since the electrolyte solution between the positive and negative electrodes is consumed as charge and discharge are repeated, the discharge capacity of the battery gradually decreases before the positive and negative electrode active materials deteriorate, and cycle characteristics due to insufficient electrolyte solution. There are also problems such as lowering of the internal temperature and occurrence of internal short circuits.

In the non-aqueous electrolyte secondary battery in which the non-aqueous electrolyte is supported on the polymer support, the present invention exists between the electrode body and the exterior body without being supported by the electrolyte with respect to the amount of the electrolyte in the exterior body. It has been found that the ratio of the amount of electrolyte is greatly related to the characteristics and swelling of the battery.
The present invention has been made on the basis of such knowledge, and its object is to provide a nonaqueous electrolyte secondary battery that has excellent cycle characteristics and can suppress or prevent swelling during high-temperature storage. It is in.

  As a result of intensive studies to achieve the above object, the present inventors have arranged a predetermined polymer support at a predetermined position, and an electrode body and an exterior body with respect to the amount of non-aqueous electrolyte present in the exterior body The present inventors have found that the above object can be achieved by setting the ratio of the amount of the non-aqueous electrolyte existing between and a predetermined value or less, and have completed the present invention.

That is, the non-aqueous electrolyte secondary battery of the present invention includes a positive electrode formed by forming a positive electrode active material layer containing a positive electrode active material on a current collector and a negative electrode active material layer containing a negative electrode active material on the current collector. An electrode body formed by winding or laminating a negative electrode comprising a positive electrode or a negative electrode current collector with the separator as the outermost periphery , a non-aqueous electrolyte, and an exterior body composed of an exterior member of a laminate film containing these A polymer support layer that forms a gel-like non-aqueous electrolyte layer holding the non-aqueous electrolyte between at least one of the positive electrode and the negative electrode and the separator, and the polymer support A layer adheres to or adheres to at least one of the positive electrode and the negative electrode and the separator, and the electrode body and the exterior body with respect to the amount M A present inside the exterior body with respect to the non-aqueous electrolyte. The ratio of the amount M O present between (M O / M A ) is 0.04 or less.

Further, in the above KiHisui electrolyte, the cyclic carbonate derivative having halogen atoms is contained, since the cycle characteristics are improved, and more preferable.

  According to the present invention, a predetermined polymer support is disposed at a predetermined position, and the ratio of the amount of the non-aqueous electrolyte existing between the electrode body and the exterior body with respect to the amount of the non-aqueous electrolyte existing inside the exterior body. Therefore, it is possible to provide a non-aqueous electrolyte secondary battery that has excellent cycle characteristics and can suppress or prevent swelling during high-temperature storage.

  Hereinafter, the nonaqueous electrolyte secondary battery of the present invention will be described in detail. In the present specification, “%” for content, concentration, and the like represents a mass percentage unless otherwise specified.

As described above, the non-aqueous electrolyte secondary battery of the present invention has a positive electrode formed by forming a positive electrode active material layer containing a positive electrode active material on a current collector and a negative electrode active material layer containing a negative electrode active material on the current collector. An outer body comprising an electrode body formed by winding or laminating a negative electrode formed through a separator with a positive electrode or a negative electrode current collector as the outermost periphery , a non-aqueous electrolyte, and an outer packaging member of a laminate film containing them A polymer support layer forming a gel-like non-aqueous electrolyte layer holding the non-aqueous electrolyte between at least one of the positive electrode and the negative electrode and the separator, and the polymer support The body layer is in close contact with or bonded to at least one of the positive electrode and the negative electrode and the separator, and the electrode body and the exterior body with respect to the amount M A existing inside the exterior body with respect to the non-aqueous electrolyte. The ratio of the amount M O present between them (M O / M A ) is 0.04 It is the following.

Here, exterior body interior, i.e. the non-aqueous electrolyte volume present in the nonaqueous electrolyte secondary battery M A is measured by the method described in example below, it may be calculated.
First, the battery mass is measured, then the electrode body is taken out, then the electrode body is decomposed into a positive electrode, a negative electrode and a separator, and then the positive electrode, the negative electrode, the separator and the outer package are immersed in a cleaning solution such as dimethyl carbonate for 2 days. , filtered, and vacuum drying for 3 days, further measuring the battery mass after vacuum drying, and thereafter, by subtracting the battery mass after vacuum drying from the initial battery mass, M a is obtained.
On the other hand, the non-aqueous electrolyte amount M O existing between the electrode body and the exterior body, that is, in the non-aqueous electrolyte secondary battery and outside the electrode body may be measured and calculated by the method described below, for example. .
First, the mass of the battery is measured, and the electrode body is taken out. Next, the taken-out electrode body is sandwiched between materials such as cloth to absorb the non-aqueous electrolyte, and all the non-aqueous electrolyte exuded by applying a load of 10 kPa is wiped off. Moreover, the exterior body which took out the electrode body is immersed in cleaning liquids, such as a dimethyl carbonate, and is dried. Furthermore, it measures the total weight of the treated electrode material and wiping exterior body, thereafter, by subtracting the total weight of the electrode body after treatment wiping the exterior member from the first cell mass, M O is determined.

When this way defined by M O / M A exceeds 0.04, it is impossible to suppress or prevent swelling during high-temperature storage.
Further, M O / M A is preferably smaller the value, it is considered that M O / M A is optimal to be 0, even 0.03 or less, to obtain a further remarkable swelling suppression effect it can.

Hereinafter, the nonaqueous electrolyte secondary battery of the present invention will be described in more detail based on the drawings.
FIG. 1 is an exploded perspective view showing an example of a laminated secondary battery according to the first embodiment of the nonaqueous electrolyte secondary battery of the present invention.
As shown in the figure, this secondary battery is configured by enclosing a wound battery element 20 to which a positive electrode terminal 11 and a negative electrode terminal 12 are attached in an exterior body 30 composed of film-shaped exterior members 30A and 30B. Has been.
The positive electrode terminal 11 and the negative electrode terminal 12 are led out from the inside of the exterior body 30 to the outside, for example, in the same direction. The positive electrode terminal 11 and the negative electrode terminal 12 are each made of a metal material such as aluminum (Al), copper (Cu), nickel (Ni), or stainless steel.
In addition, the wound battery element 20 includes a wound electrode body and a non-aqueous electrolyte described later in detail.

The exterior members 30A and 30B are made of, for example, a rectangular laminate film in which a nylon film, an aluminum foil, and a polyethylene film are bonded together in this order. The exterior members 30A and 30B are disposed, for example, so that the polyethylene film side and the wound battery element 20 face each other, and the outer edge portions are joined to each other by fusion or an adhesive.
An adhesion film 31 for preventing intrusion of outside air is inserted between the exterior members 30 </ b> A and 30 </ b> B and the positive electrode terminal 11 and the negative electrode terminal 12. The adhesion film 31 is made of a material having adhesion to the positive electrode terminal 11 and the negative electrode terminal 12. For example, when the positive electrode terminal 11 and the negative electrode terminal 12 are made of the metal materials described above, polyethylene, polypropylene, modified It is preferably composed of a polyolefin resin such as polyethylene or modified polypropylene.

The exterior members 30A and 30B may be configured by other structures, for example, a laminate film having no metal material, a polymer film such as polypropylene, or a metal film, instead of the above-described laminate film.
Here, the general structure of an exterior member can be represented by the laminated structure of an exterior layer / metal foil / sealant layer (however, the exterior layer and the sealant layer may be composed of a plurality of layers), and the above. In this example, the nylon film corresponds to the exterior layer, the aluminum foil corresponds to the metal foil, and the polyethylene film corresponds to the sealant layer.
In addition, as metal foil, it is sufficient if it functions as a moisture-permeable barrier film, and not only aluminum foil but also stainless steel foil, nickel foil and plated iron foil can be used, but it is thin and lightweight. Thus, an aluminum foil excellent in workability can be suitably used.

  As the exterior member, usable configurations are listed in the form of (exterior layer / metal foil / sealant layer): Ny (nylon) / Al (aluminum) / CPP (unstretched polypropylene), PET (polyethylene terephthalate) / Al / CPP, PET / Al / PET / CPP, PET / Ny / Al / CPP, PET / Ny / Al / Ny / CPP, PET / Ny / Al / Ny / PE (polyethylene), Ny / PE / Al / LLDPE (direct) Chain low density polyethylene), PET / PE / Al / PET / LDPE (low density polyethylene), and PET / Ny / Al / LDPE / CPP.

  FIG. 2 is a schematic cross-sectional view taken along the line II-II of the wound battery element shown in FIG. In the figure, a wound battery element 20 is positioned so that a positive electrode 21 and a negative electrode 22 face each other with a polymer support layer (details will be described later) 23 holding a non-aqueous electrolyte and a separator 24 interposed therebetween. The outermost peripheral part is protected by a protective tape 25.

Here, FIG. 3 shows a second embodiment of the non-aqueous electrolyte secondary battery of the present invention. That is, FIG. 3 is an exploded perspective view showing another example of the laminated secondary battery according to the second embodiment of the nonaqueous electrolyte secondary battery of the present invention. In addition, the same code | symbol is attached | subjected to the member substantially the same as the winding type secondary battery mentioned above, and the description is abbreviate | omitted.
As shown in the figure, this secondary battery has the same configuration as that of the wound secondary battery shown in FIG. 1 except that a laminated battery element 20 ′ is provided instead of the wound battery element 20 described above.

In the laminated battery element 20 ′, a sheet-like positive electrode and a negative electrode are positioned to face each other with a polymer support layer and a separator holding a non-aqueous electrolyte, for example, a negative electrode sheet, a polymer support It has a laminated structure in which a layer, a separator, a polymer support layer, and a positive electrode sheet are laminated in this order.
In the embodiment shown in FIG. 3, the laminated battery element 20 ′ is obtained by alternately laminating sheet-like negative electrodes (negative electrode sheets) and sheet-like positive electrodes (positive electrode sheets) via separators. Further, a polymer support layer is disposed between the positive electrode sheet and the separator and between the negative electrode sheet and the separator. In other words, the stacked battery element 20 ′ includes a stacked electrode body and a non-aqueous electrolyte.
Except for this point, the winding type secondary battery has substantially the same configuration as the winding type secondary battery shown in FIG. 1. Therefore, the winding type secondary battery is taken as an example again, and the nonaqueous electrolyte secondary battery of the present invention is used. Continue to explain the next battery.

As shown in FIG. 2, the positive electrode 21 has a structure in which a positive electrode active material layer 21B is coated on both surfaces or one surface of a positive electrode current collector 21A having a pair of opposed surfaces, for example. The positive electrode current collector 21 </ b> A has a portion exposed without being covered with the positive electrode active material layer 21 </ b> B at one end portion in the longitudinal direction, and the positive electrode terminal 11 is attached to the exposed portion.
The positive electrode current collector 21A is made of a metal foil such as an aluminum foil, a nickel foil, or a stainless steel foil.

The positive electrode active material layer 21B includes one or more positive electrode materials capable of inserting and extracting lithium as a positive electrode active material, and includes a conductive material and a binder as necessary. You may go out.
Examples of the positive electrode material capable of inserting and extracting lithium include disulfides such as sulfur (S), iron disulfide (FeS 2 ), titanium disulfide (TiS 2 ), and molybdenum disulfide (MoS 2 ). , Chalcogenides (particularly layered compounds and spinel compounds) containing no lithium, such as niobium diselenide (NbSe 2 ), vanadium oxide (V 2 O 5 ), titanium dioxide (TiO 2 ) and manganese dioxide (MnO 2 ), Examples thereof include lithium-containing compounds containing lithium, and conductive polymer compounds such as polyaniline, polythiophene, polyacetylene, and polypyrrole.

  Among these, lithium-containing compounds are preferable because some compounds can obtain a high voltage and a high energy density. Examples of such a lithium-containing compound include a composite oxide containing lithium and a transition metal element, and a phosphate compound containing lithium and a transition metal element. From the viewpoint of obtaining a higher voltage, cobalt is particularly preferred. (Co), nickel (Ni), manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), chromium (Cr), vanadium (V), titanium (Ti) or any mixture thereof. The inclusion is preferred.

Such lithium-containing compounds are typically represented by the following general formula (1) or (2)
Li x M I O 2 (1)
Li y M II PO 4 (2)
(In the formula, M I and M II represent one or more transition metal elements, and the values of x and y vary depending on the charge / discharge state of the battery, but usually 0.05 ≦ x ≦ 1.10, 0.05 ≦ y ≦ 1.10), and the compound of the formula (1) generally has a layered structure, and the compound of the formula (2) generally has an olivine structure.

Specific examples of the composite oxide containing lithium and a transition metal element include lithium cobalt composite oxide (Li x CoO 2 ), lithium nickel composite oxide (Li x NiO 2 ), lithium nickel cobalt composite oxide ( Examples include Li x Ni 1-z Co z O 2 (0 <z <1)) and lithium manganese composite oxide (LiMn 2 O 4 ) having a spinel structure.
Furthermore, specific examples of the phosphate compound containing lithium and a transition metal element include, for example, a lithium iron phosphate compound (LiFePO 4 ) or a lithium iron manganese phosphate compound (LiFe 1-v Mn v PO 4 ( v <1)).
In these composite oxides, for the purpose of stabilizing the structure, a transition metal is partially substituted with Al, Mg or other transition metal elements or included in the crystal grain boundary, and a part of oxygen is fluorine. The thing substituted by etc. can also be mentioned. Further, at least a part of the surface of the positive electrode active material may be coated with another positive electrode active material. Moreover, you may use a positive electrode active material in mixture of multiple types.

On the other hand, similarly to the positive electrode 21, the negative electrode 22 has a structure in which a negative electrode active material layer 22B is provided on both surfaces or one surface of a negative electrode current collector 22A having a pair of opposed surfaces, for example. The negative electrode current collector 22A has an exposed portion without being provided with the negative electrode active material layer 22B at one end in the longitudinal direction, and the negative electrode terminal 12 is attached to the exposed portion.
The anode current collector 22A is made of a metal foil such as a copper foil, a nickel foil, or a stainless steel foil.

The negative electrode active material layer 22B includes one or more of a negative electrode material capable of inserting and extracting lithium and metal lithium as a negative electrode active material, and a conductive material and a binder as necessary. An agent may be included.
Examples of the negative electrode material capable of inserting and extracting lithium include a carbon material, a metal oxide, and a polymer compound. Examples of carbon materials include non-graphitizable carbon materials, artificial graphite materials, and graphite-based materials. More specifically, pyrolytic carbons, cokes, graphites, glassy carbons, organic polymer compound firing Body, carbon fiber, activated carbon and carbon black.
Among these, coke includes pitch coke, needle coke and petroleum coke, and the organic polymer compound fired body is carbonized by firing a polymer material such as phenol resin or furan resin at an appropriate temperature. Say things. In addition, examples of the metal oxide include iron oxide, ruthenium oxide, and molybdenum oxide, and examples of the polymer compound include polyacetylene and polypyrrole.

In addition, examples of the negative electrode material capable of inserting and extracting lithium include materials containing at least one of a metal element and a metalloid element capable of forming an alloy with lithium as a constituent element. 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 invention, alloys include those containing one or more metal elements and one or more metalloid elements in addition to those 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 these.

Examples of such metal elements or metalloid elements include tin (Sn), lead (Pb), magnesium (Mg), aluminum, indium (In), silicon (Si), zinc (Zn), antimony (Sb), Bismuth (Bi), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), hafnium (Hf), zirconium (Zr) and yttrium (Y) can be mentioned.
Among them, a group 14 metal element or metalloid element in the long-period type periodic table is preferable, and silicon or tin is particularly preferable. This is because silicon and tin have a large ability to occlude and release lithium, and a high energy density can be obtained.

As an alloy of tin, for example, as a second constituent element other than tin, silicon, magnesium, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium (Ti), germanium, bismuth, antimony and chromium ( And those containing at least one member of the group consisting of Cr).
As an alloy of silicon, for example, as a second constituent element other than silicon, tin, magnesium, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, and chromium can be used. The thing containing at least 1 sort (s) of them is mentioned.

  Examples of the tin compound or the silicon compound include those containing oxygen (O) or carbon (C), and may contain the second constituent element described above in addition to tin or silicon.

  The negative electrode material as described above may be an element that forms a complex oxide with lithium, such as titanium. Of course, metallic lithium may be precipitated and dissolved, and magnesium and aluminum other than lithium may be precipitated and dissolved.

Next, the polymer support layer 23 has ionic conductivity and can hold a non-aqueous electrolyte. In the embodiment shown in FIG. 2, the polymer support layer 23 adheres or adheres to the separator 24, but does not adhere to the separator and the electrode as in the separator 24 and the positive electrode 21 and the separator 24 and the negative electrode 22. It may be adhered, or may not be adhered or adhered to the separator, and may be adhered or adhered only to either one or both of the positive electrode 21 and the negative electrode 22.
Here, “adhesion” means that the polymer support layer 23 and the separator 24, the positive electrode 21, and the negative electrode 22 are in contact with each other to the extent that they do not move relative to each other unless a predetermined force is applied. .

  The polymer support layer 23 and the separator 24, or the polymer support layer 23 and the positive electrode or the negative electrode are in close contact or bonded to each other, so that the polymer support layer 23 holds the non-aqueous electrolyte and has a gel-like shape. In a state where the nonaqueous electrolyte layer is formed, the positive electrode 21 or the negative electrode 22 and the separator 24 are bonded via the nonaqueous electrolyte layer. The degree of adhesion is preferably such that, for example, the peel strength between the exposed portion of the positive electrode 21 and the negative electrode 22 where the active material layer is not provided and the current collector is exposed and the separator is 5 mN / mm or more. . The peel strength is measured between 6 seconds and 25 seconds after the current collector is placed on a support stand, pulled in a 180 ° direction at a speed of 10 cm / min, and the current collector is peeled off from the separator. , The average force required to peel.

With such close contact or adhesion, in the embodiment shown in FIG. 2, it is possible to further reduce the excess nonaqueous electrolyte that does not substantially participate in the battery reaction, and the nonaqueous electrolyte is efficiently supplied around the electrode active material. Is done.
Therefore, the non-aqueous electrolyte secondary battery of the embodiment shown in FIG. 2 exhibits excellent cycle characteristics even when the amount of non-aqueous electrolyte is smaller than that of the conventional one, and the amount of non-aqueous electrolyte used is small. Therefore, the leakage resistance is also excellent.

The polymer support constituting the polymer support layer is not particularly limited as long as it retains the non-aqueous electrolyte and exhibits ionic conductivity, but the acrylonitrile copolymer is 50% or more. 80% or more of acrylonitrile polymer, aromatic polyamide, acrylonitrile / butadiene copolymer, acrylic polymer comprising acrylate or methacrylate homopolymer or copolymer, acrylamide polymer, vinylidene fluoride, etc. Examples thereof include a polymer, polysulfone, and polyallylsulfone. In particular, a polymer having a copolymerization amount of 50% or more of acrylonitrile has a CN group in its side chain, so that a polymer gel electrolyte having a high dielectric constant and high ion conductivity can be produced.
In order to improve the support of non-aqueous electrolytes for these polymers and the ionic conductivity of polymer gel electrolytes from these polymers, acrylonitrile and vinyl carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, acrylamide, Methacrylsulfonic acid, hydroxyalkylene glycol (meth) acrylate, alkoxyalkylene glycol (meth) acrylate, vinyl chloride, vinylidene chloride, vinyl acetate, various (meth) acrylates, etc. are preferably used at a ratio of 50% or less, particularly 20% or less. A polymerized product can also be used.
In addition, since the aromatic polyamide is a high heat-resistant polymer, it is a preferable high-molecular polymer when a polymer gel electrolyte that requires high heat resistance such as an automobile battery is required. Further, a polymer having a crosslinked structure obtained by copolymerizing butadiene or the like can also be used.
In particular, a polymer containing vinylidene fluoride as a constituent component, that is, a homopolymer, a copolymer, and a multi-component copolymer are preferable. Specifically, polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene copolymer A combination (PVdF-HFP) and a polyvinylidene fluoride-hexafluoropropylene-chlorotrifluoroethylene copolymer (PVdF-HEP-CTFE) can be mentioned.
Moreover, as a polymer support which comprises a polymer support layer, what shows melting | fusing point or gel melting | fusing point lower than the separator mentioned later can be used suitably. That is, the ends of the polymer support exhibiting a melting point or gel melting point lower than that of the separator are protruded from the positive and negative electrodes by, for example, 0.3 mm or more to heat-bond the polymer support layers to each other by heating during battery production. As a result, a secondary effect that the fall safety can be improved is obtained. Furthermore, the secondary effect that the drop safety can be improved can be obtained by making the width of the separator with the polymer support layer larger than the internal dimension of the exterior body.

  Further, as the separator 24, for example, a porous film made of a polyolefin-based synthetic resin such as polypropylene or polyethylene, or a porous film made of an inorganic material such as a ceramic nonwoven fabric has a high ion permeability and a predetermined mechanical property. It is comprised from the insulating thin film which has intensity | strength, and it is good also as a structure which laminated | stacked these 2 or more types of porous films. In particular, those containing a polyolefin-based porous membrane are suitable because they have excellent separability between the positive electrode 21 and the negative electrode 22 and can further reduce internal short-circuiting and open circuit voltage reduction.

Moreover, the non-aqueous electrolyte should just contain electrolyte salt and a non-aqueous solvent.
Here, as the electrolyte salt, any electrolyte salt may be used as long as it dissolves or disperses in a nonaqueous solvent described later, and lithium hexafluorophosphate (LiPF 6 ) can be suitably used. Needless to say, it is not limited.
That is, lithium tetrafluoroborate (LiBF 4), lithium hexafluoroarsenate (LiAsF 6), lithium hexafluoro antimonate (LiSbF 6), lithium perchlorate (LiClO 4), four lithium aluminum chloride acid ( Inorganic lithium salts such as LiAlCl 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis (trifluoromethanesulfone) imide (LiN (CF 3 SO 2 ) 2 ), lithium bis (pentafluoromethanesulfone) imide (LiN (C 2 F 5 SO 2 ) 2 ) and lithium salts of perfluoroalkanesulfonic acid derivatives such as lithium tris (trifluoromethanesulfone) methide (LiC (CF 3 SO 2 ) 3 ) can also be used. These can be used alone or in combination of two or more. It is also possible to use it.

  In addition, the content of such an electrolyte salt is preferably in the range of 0.1 mol to 3.0 mol, and more preferably in the range of 0.5 mol to 2.0 mol with respect to 1 liter (L) of the solvent. This is because higher ion conductivity can be obtained within this range.

Examples of the non-aqueous solvent include various high dielectric constant solvents and low viscosity solvents.
As the high dielectric constant solvent, ethylene carbonate can be preferably used, but is not limited thereto, and propylene carbonate, butylene carbonate, vinylene carbonate, 4-fluoro-1,3-dioxolan-2-one ( Fluoroethylene carbonate), 4-chloro-1,3-dioxolan-2-one (chloroethylene carbonate), and cyclic carbonates such as trifluoromethylethylene carbonate can be used.

  Further, as a high dielectric constant solvent, instead of or in combination with a cyclic carbonate, a lactone such as γ-butyrolactone and γ-valerolactone, a lactam such as N-methylpyrrolidone, and a cyclic carbamate such as N-methyloxazolidinone A sulfone compound such as tetramethylene sulfone can also be used.

  On the other hand, diethyl carbonate can be preferably used as the low-viscosity solvent, but besides this, chain carbonates such as dimethyl carbonate, ethyl methyl carbonate and methyl propyl carbonate, methyl acetate, ethyl acetate, methyl propionate Chain carboxylic acid esters such as ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethylacetate and ethyl trimethylacetate, chain amides such as N, N-dimethylacetamide, methyl N, N-diethylcarbamate and N, Chain carbamates such as ethyl N-diethylcarbamate and ethers such as 1,2-dimethoxyethane, tetrahydrofuran, tetrahydropyran and 1,3-dioxolane can be used.

In addition, as a non-aqueous electrolyte used for the non-aqueous electrolyte secondary battery of the present invention, the above-mentioned high dielectric constant solvent and low-viscosity solvent may be used alone or in combination of two or more. However, those containing 20 to 50% cyclic carbonate and 50 to 80% low-viscosity solvent are preferable, and those having a boiling point of 130 ° C. or less as the low-viscosity solvent are particularly desirable.
By using such a non-aqueous electrolyte, the polymer support can be satisfactorily swollen with a small amount of non-aqueous electrolyte, and it is possible to further suppress battery swelling and prevent leakage and achieve high conductivity. Can be planned.
If the ratio between the cyclic carbonate and the low-viscosity solvent deviates from the above range, the conductivity of the electrolytic solution is lowered, and the cycle characteristics may be lowered. Specifically, when the amount of the low-viscosity solvent is too large, the dielectric constant is lowered, and conversely, when the amount of the low-viscosity solvent is too small, the viscosity is lowered. In either case, sufficient conductivity is obtained. Therefore, there is a possibility that good battery characteristics cannot be obtained.
In the present invention, the ratio of the proportion of the non-aqueous electrolyte volume present between the electrode body and the outer body (M O / M A) is small, even by using a low boiling low viscosity solvent 50% or more, blistering Can be reduced.
Examples of the chain carbonate having a boiling point of 130 ° C. or lower include dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate.
Moreover, when the non-aqueous electrolyte contains a cyclic carbonate derivative having a halogen atom as the above-mentioned cyclic carbonate, it is more preferable because cycle characteristics are improved. Examples of the cyclic carbonate derivative include 4-fluoro-1,3-dioxolan-2-one and 4-chloro-1,3-dioxolan-2-one, and these can be used alone or in combination. . As content, 0.5 to 2% is preferable. This is because when the content is small, the effect of improving the cycle characteristics is small, and when the content is too large, the swelling during high-temperature storage increases.

Next, an example of a method for manufacturing the secondary battery described above will be described.
The wound secondary battery can be manufactured as follows.
First, the positive electrode 21 is produced. For example, when a particulate positive electrode active material is used, a positive electrode mixture is prepared by mixing a positive electrode active material and, if necessary, a conductive material and a binder, and a dispersion medium such as N-methyl-2-pyrrolidone. To produce a positive electrode mixture slurry.
Next, the positive electrode mixture slurry is applied to the positive electrode current collector 21A, dried, and compression molded to form the positive electrode active material layer 21B.

  Moreover, the negative electrode 22 is produced. For example, when a particulate negative electrode active material is used, a negative electrode mixture is prepared by mixing a negative electrode active material and, if necessary, a conductive material and a binder, and a dispersion medium such as N-methyl-2-pyrrolidone. To prepare a negative electrode mixture slurry. Thereafter, the negative electrode mixture slurry is applied to the negative electrode current collector 22A, dried, and compression molded to form the negative electrode active material layer 22B.

Then, the polymer support layer 23 is formed on the separator 24. As a method of forming the polymer support layer 23 on the separator 24, a method of applying a solution containing the polymer support to the surface of the separator 24 and removing the solvent, and a separately formed polymer support layer are used. A technique of closely fixing to the surface of the separator 24 is exemplified.
As a method of applying a solution containing a polymer support to the surface of the separator 24, a method of immersing the separator in a solution containing a polymer support, a method of supplying and applying by a T-die extrusion method, a spray method, a roll coater, a knife A technique of applying the solution to the surface of the substrate with a coater or the like can be mentioned.
Examples of the solvent removal treatment method for removing the solvent include a method for drying and removing, a method for extracting and removing the solvent by immersing it in a poor solvent for the polymer support, and a method for drying and removing the poor solvent, or a combination thereof. Can be used.
As a method of bringing the separately formed polymer support layer into close contact with the surface of the separator 24, it is possible to adhere using an adhesive, but in this case, the type of electrolyte used (acid, alkali, organic solvent, etc.) Accordingly, it is necessary to select an adhesive appropriately according to the condition and to prevent clogging.
Moreover, as a method of closely attaching the polymer support layer formed on the separator, heat fusion at a temperature equal to or higher than the gel transition point can be mentioned. In particular, heat fusion while applying pressure such as hot roll compression is preferable.

  Next, the positive electrode terminal 11 is attached to the positive electrode 21 and the negative electrode terminal 12 is attached to the negative electrode 22, and then the separator 24 with the polymer support layer 23, the positive electrode 21, the same separator 24, and the negative electrode 22 are sequentially laminated and wound. Rotate and adhere the protective tape 25 to the outermost periphery to form a wound electrode body. Further, the wound electrode body is sandwiched between the exterior members 30A and 30B, and the outer peripheral edge except one side is heat-sealed to form a bag shape.

Thereafter, a nonaqueous electrolytic solution containing an electrolyte salt such as lithium hexafluorophosphate and a nonaqueous solvent such as ethylene carbonate is prepared and injected into the spirally wound electrode body from the opening of the exterior body 30. The ratio of the amount M O present between the electrode body and the outer body relative to abundance M A of the exterior body portion of the non-aqueous electrolyte solution (M O / M A) is the amount of electrolyte in the battery, the polymer type and amount of support, is influenced by the manufacturing method of the battery, the M O / M a to 0.04 or less reduces the amount of electrolytic solution, using a large polymeric retention ability of the electrolyte, Adjustments may be made such as increasing the amount of the polymer support or opening the battery after manufacturing to remove excess electrolyte. And the opening part of the exterior body 30 is heat-sealed and sealed.
Thereby, the non-aqueous electrolyte is held on the polymer support layer 23, and the wound battery element 20 having the wound electrode body and the non-aqueous electrolyte as constituent elements is housed in the outer package 30. FIG. The wound secondary battery shown in FIG.
In this way, after the polymer support layer is formed and stored, the electrolyte is swollen to form an electrolyte. In this method, the precursor and solvent that are the raw materials for forming the polymer support are removed in advance, and the electrolyte is almost completely removed from the electrolyte. It is possible not to leave it, and the polymer support forming step can be well controlled. Therefore, the separator, the positive electrode, the negative electrode, and the polymer support layer can be adhered to each other.

  In the secondary battery described above, when charged, lithium ions are released from the positive electrode active material layer 21 </ b> B and occluded in the negative electrode active material layer 22 </ b> B through the non-aqueous electrolyte held in the polymer support layer 23. Is done. When discharging is performed, lithium ions are released from the negative electrode active material layer 22B, and are inserted in the positive electrode active material layer 21B through the polymer support layer 23 and the nonaqueous electrolytic solution.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.
Specifically, the operations described in the following examples were performed to produce a wound secondary battery as shown in FIGS. 1 and 2, and its performance was evaluated.

Example 1
<Preparation of positive electrode>
First, lithium carbonate (LiCO 3) were mixed at a ratio of cobalt carbonate (CoCO 3) 1 mol with respect to 0.5 mol, by firing for 5 hours at 900 ° C. in air, the lithium-cobalt composite oxide as the positive electrode active material ( LiCoO 2 ) was obtained.
Next, 85 parts by mass of the obtained lithium cobalt composite oxide, 5 parts by mass of graphite as a conductive agent, and 10 parts by mass of polyvinylidene fluoride as a binder are uniformly mixed to prepare a positive electrode mixture, Further, the mixture was dispersed in N-methyl-2-pyrrolidone as a dispersion medium to obtain a positive electrode mixture slurry.
Next, the obtained positive electrode mixture slurry was uniformly applied to both surfaces of a positive electrode current collector made of an aluminum foil having a thickness of 20 μm, dried, and compression-molded with a roll press to form a positive electrode active material layer, A positive electrode was produced. Thereafter, a positive electrode terminal was attached to the positive electrode.

<Production of negative electrode>
Next, the pulverized graphite powder is prepared as a negative electrode active material, and 90 parts by mass of the graphite powder and 10 parts by mass of polyvinylidene fluoride as a binder are homogeneously mixed to prepare a negative electrode mixture and further dispersed. The mixture was dispersed in N-methyl-2-pyrrolidone as a medium to obtain a negative electrode mixture slurry.
Next, the obtained negative electrode mixture slurry was uniformly applied to both surfaces of a negative electrode current collector made of a copper foil having a thickness of 15 μm, dried, and compression-molded with a roll press to form a negative electrode active material layer, A positive electrode was produced. Thereafter, a negative electrode terminal was attached to the negative electrode.

<Disposition of polymer support>
Next, a polymer solution in which a polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP) copolymer was added at a ratio of 15 parts by mass with respect to 100 parts by mass of N-methyl-2-pyrrolidone was used to form micropores having a thickness of 20 μm. A separator made of a polyethylene film is coated on both sides of a separator made of a conductive polyethylene film with a coating device, and then the polyethylene film is immersed in deionized water and then dried to form a polymer support layer having a thickness of 5 μm per side made of a polyethylene film. Arranged.

<Production of battery>
The positive electrode and the negative electrode prepared as described above are in close contact with each other through the separator prepared as described above, and then wound in the longitudinal direction, and then a protective tape is applied to the outermost periphery, whereby a wound electrode The body was made.
Next, the obtained wound electrode body was sandwiched between exterior members, and three sides were heat-sealed to form a bag. As the exterior member, a moisture-proof aluminum laminate film in which a nylon film having a thickness of 20 μm, an aluminum foil having a thickness of 40 μm, and a polypropylene film having a thickness of 30 μm are laminated in order from the outermost layer was used.
Thereafter, 1.6 mL of a non-aqueous electrolyte was injected into this, and the remaining one side was heat-sealed under reduced pressure and sealed. At that time, as the non-aqueous electrolyte, lithium hexafluorophosphate was dissolved at a rate of 1.2 mol / L in a solvent mixed at a rate of ethylene carbonate: diethyl carbonate = 4: 6 (mass ratio). Was used.
Then, it was sandwiched between iron plates and heated at 70 ° C. for 3 minutes to adhere the separator to the positive electrode and the negative electrode through the polymer support layer.
Thereby, the nonaqueous electrolyte secondary battery (width: 34 mm, depth: 50 mm, thickness: 50 mm) of this example as shown in FIGS. 1 and 2 was obtained.

About the obtained nonaqueous electrolyte secondary battery, its battery mass was measured, then the electrode body was taken out, then the electrode body was decomposed into a positive electrode, a negative electrode and a separator, and then the positive electrode, the negative electrode, the separator and the outer package were dimethyl carbonate solution was immersed for 2 days in, filtered, and vacuum dried for 3 days, further measuring the battery mass after vacuum drying, and thereafter, by subtracting the mass after vacuum drying from the initial weight, M a Asked. Also, the battery mass is measured, the electrode body is taken out, and then the taken-out electrode body is sandwiched between materials such as cloth to absorb the non-aqueous electrolyte, and all the non-aqueous electrolyte exuded by applying a load of 10 kPa is wiped off. In addition, the exterior body from which the electrode body has been taken out is dipped in a dimethyl carbonate solution, dried, and further, the total mass of the exterior body and the wiped electrode body is measured. by subtracting the total weight of the electrode body after treatment wiping it was determined M O. As a result, were M O / M A = 0.030.

(Comparative Examples 1-3)
A non-aqueous electrolyte secondary battery of each example was obtained by repeating the same operation as in Example 1 except that the polymer support layer was not formed and the injection amount was changed as shown in Table 1. As a result of obtaining M A and M O in the same manner as in Example 1, M O / M A was as shown in Table 1.

(Examples 2-7 and Comparative Examples 4-6)
Except having changed the thickness of PVdF-HFP and the amount of liquid injection as shown in Table 1, the same operation as Example 1 was repeated, and the nonaqueous electrolyte secondary battery of each example was obtained. As a result of obtaining M A and M O in the same manner as in Example 1, M O / M A was as shown in Table 1.

(Examples 8-12 and Comparative Examples 7 and 8)
The same operation as in Example 1 was repeated except that polyvinylidene fluoride (PVdF) was used as the polymer support, and the PVdF thickness and the injection amount were changed as shown in Table 1. The next battery was obtained. As a result of obtaining M A and M O in the same manner as in Example 1, M O / M A was as shown in Table 1.

(Example 13)
After sealing, the same operation as Example 1 was repeated except that it was sandwiched between iron plates for 3 minutes and not heated at 70 ° C., to obtain a nonaqueous electrolyte secondary battery of this example. As a result of obtaining M A and M O in the same manner as in Example 1, M O / M A was as shown in Table 1.

(Example 14)
The same operation as in Example 13 was repeated except that polyvinylidene fluoride (PVdF) was used as the polymer support to obtain a nonaqueous electrolyte secondary battery of this example. As a result of obtaining M A and M O in the same manner as in Example 1, M O / M A was as shown in Table 1.

(Comparative Example 9)
Except that the injection amount of the nonaqueous electrolyte was 1.5 mL, the same operation as in Example 1 was repeated to obtain a nonaqueous electrolyte secondary battery, the nonaqueous electrolyte secondary battery was opened, and the same 0.10 mL of the nonaqueous electrolyte was injected, the total injection volume was 1.6 mL, and the solution was sealed again under reduced pressure to obtain the nonaqueous electrolyte secondary battery of this example. As a result of obtaining M A and M O in the same manner as in Example 1, M O / M A was as shown in Table 1. Table 1 shows the specifications of each example.

[Performance evaluation]
(First discharge capacity)
For the non-aqueous electrolyte secondary battery in each of the above examples, a constant current / constant voltage charge of 200 mA was performed at 23 ° C. for 7 hours to an upper limit of 4.2 V, and then a constant current discharge of 200 mA was performed to a final voltage of 2.5 V. The capacity was measured. The obtained results are also shown in Table 1.

(Discharge capacity maintenance rate)
For the nonaqueous electrolyte secondary batteries of the above examples, following the measurement of the initial discharge capacity, a constant current and constant voltage charge of 500 mA was performed at 23 ° C. for 2 hours to an upper limit of 4.2 V, and then the constant current discharge of 500 mA was terminated. A charge / discharge cycle of up to a voltage of 2.5 V was performed for 300 cycles, and a discharge capacity retention rate at the 300th cycle was measured and calculated when the discharge capacity at the first cycle in a 500 mA discharge was taken as 100%. The obtained results are also shown in Table 1.

(Blowing amount)
About the nonaqueous electrolyte secondary battery of each said example, it preserve | saved at 90 degreeC for 6 hours, and the swelling amount in that case was measured. The obtained results are also shown in Table 1.

As shown in Table 1, when a polymer support layer to which PVdF-HFP or PVdF is applied as the polymer support is formed, it can be seen that the initial discharge capacity and the discharge capacity retention rate can be kept high. Further, by setting the M O / M A 0.04 or less, it can be seen that it is possible to swelling amount when stored for 6 hours at 90 ° C. to 1mm or less. On the other hand, if M O / M A is greater than 0.04, it can be seen that the swollen amount when stored for 6 hours at 90 ° C. increases. In particular, as in Comparative Example 5, even the total pouring weight 1.6 mL, when M O / M A is large, the swelling amount when stored for 6 hours at 90 ° C. increases I understand. Therefore, the amount of swelling depends on the M O / M A, by this to 0.04 or less, it was confirmed that can suppress or prevent swelling during high-temperature storage. The value of M O / M A is pouring amount seen as high tends large, it tends to be less the greater the amount of the polymer support is seen. In the polymeric support using this, swelling of the electrolyte is more of PVdF-HFP is higher than PVdF, cheaper to use swellable high polymer support, the M O / M A There is also a tendency for the value to decrease.
On the other hand, when not forming a polymer support layer, as compared with the case of forming the polymeric support layers, the value of M O / M A tends to increase observed. However, the range in which M O / M A is 0.04 or less, the amount blistering when stored for 6 hours at 90 ° C. is a 1mm or less, it can be seen that becomes smaller the discharge capacity retention ratio in this range .
Therefore, it has been confirmed that a polymer support layer needs to be disposed in order to achieve both suppression of the amount of swelling during high-temperature storage and excellent cycle characteristics. Further, by comparing Examples 1 to 12 with Examples 13 and 14, the disposed polymer support is heated, and is further heat-sealed with a separator or an electrode, thereby further improving cycle characteristics. It was confirmed that

(Examples 15 to 21)
As a non-aqueous electrolyte, instead of the solvent mixed at a ratio of ethylene carbonate: diethyl carbonate = 4: 6 (mass ratio), the solvent mixed at a ratio of ethylene carbonate: diethyl carbonate = 4: 6 (mass ratio) was 4 -Add one or both of fluoro-1,3-dioxolan-2-one (FEC) and 4-chloro-1,3-dioxolan-2-one (CEC) to the concentrations shown in Table 2. Except for using the obtained solvent, the same operation as in Example 1 was repeated to obtain the nonaqueous electrolyte secondary battery of each example. Table 2 shows the specifications of each example.

[Performance evaluation]
About the nonaqueous electrolyte secondary battery of each said example, evaluation was performed similarly to evaluation of the said initial stage discharge capacity, discharge capacity maintenance factor, and the amount of swelling. The obtained results are shown in Table 2 together with the results of Example 1.

  As can be seen from Table 2, Examples 15 to 21 include any one or both of 4-fluoro-1,3-dioxolan-2-one and 4-chloro-1,3-dioxolan-2-one in the electrolytic solution. , The discharge capacity retention rate was excellent, and a tendency to improve cycle characteristics was observed. That is, it can be said that it is more preferable that the electrolyte contains one or both of 4-fluoro-1,3-dioxolan-2-one and 4-chloro-1,3-dioxolan-2-one.

As mentioned above, although this invention was demonstrated with some embodiment and an Example, this invention is not limited to these, A various deformation | transformation is possible within the range of the summary of this invention.
For example, in the above-described embodiment, the case where the wound battery element 20 in which the positive electrode 21 and the negative electrode 22 are stacked and wound is described. However, a flat battery element in which a pair of positive and negative electrodes are stacked, or a plurality of battery elements 20 The present invention can also be applied to a case where a laminated battery element in which a positive electrode and a negative electrode are laminated is provided.
Further, in the above embodiment, the case where a film-like exterior member is used has been described. However, the same applies to, for example, a battery whose exterior body is a rectangular can, which is common as an important technical problem to suppress swelling during high-temperature storage. The present invention can be applied to.
Furthermore, it is applicable not only to a secondary battery but also to a primary battery.

  Furthermore, as described above, the present invention relates to a battery using lithium as an electrode reactant, but the technical idea of the present invention is that other alkali metals such as sodium (Na) or potassium (K), magnesium ( The present invention can also be applied to the case of using an alkaline earth metal such as Mg) or calcium (Ca), or another light metal such as aluminum.

1 is an exploded perspective view showing an example of a laminated secondary battery according to a first embodiment of a non-aqueous electrolyte secondary battery of the present invention. It is typical sectional drawing along the II-II line of the wound battery element shown in FIG. It is 2nd Embodiment of the nonaqueous electrolyte secondary battery of this invention, Comprising: It is a disassembled perspective view which shows the other example of a laminate type secondary battery.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 ... Positive electrode terminal, 12 ... Negative electrode terminal, 20 ... Winding battery element, 20 '... Laminated battery element, 21 ... Positive electrode, 21A ... Positive electrode collector, 21B ... Positive electrode active material layer, 22 ... Negative electrode, 22A ... Negative electrode collector Electrical body, 22B ... negative electrode active material layer, 23 ... polymer support layer, 24 ... separator, 25 ... protective tape, 30 ... exterior body, 30A, 30B ... exterior member, 31 ... adhesion film

Claims (5)

  1. A positive electrode formed by forming a positive electrode active material layer containing a positive electrode active material on a current collector and a negative electrode formed by forming a negative electrode active material layer containing a negative electrode active material on a current collector are collected via a separator. An electrode body formed by winding or laminating the body as the outermost periphery , a non-aqueous electrolyte, and an exterior body composed of an exterior member of a laminate film that accommodates these,
    Between at least one of the positive electrode and the negative electrode and the separator, a polymer support layer that forms a gel-like non-aqueous electrolyte layer holding the non-aqueous electrolyte ,
    The polymer support layer is in close contact with or adhered to at least one of the positive electrode and the negative electrode and the separator;
    For the non-aqueous electrolyte, the ratio (M O / M A ) of the amount M O existing between the electrode body and the outer package to the amount M A existing inside the outer package is 0.04 or less. Non-aqueous electrolyte secondary battery.
  2.   The nonaqueous electrolyte secondary battery according to claim 1, wherein the polymer support layer contains polyvinylidene fluoride-hexafluoropropylene.
  3.   The nonaqueous electrolyte secondary battery according to claim 1, wherein the nonaqueous electrolyte contains a cyclic carbonate and a chain carbonate.
  4.   The nonaqueous electrolyte secondary battery according to claim 1, wherein the nonaqueous electrolyte contains a cyclic carbonate derivative having a halogen atom.
  5.   5. The non-aqueous electrolyte 2 according to claim 4, which contains at least one of 4-fluoro-1,3-dioxolan-2-one and 4-chloro-1,3-dioxolan-2-one as the cyclic carbonate derivative. Next battery.
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US11/836,038 US7955731B2 (en) 2006-08-14 2007-08-08 Nonaqueous electrolyte secondary cell
KR1020070081420A KR101432672B1 (en) 2006-08-14 2007-08-13 Nonaqueous electrolyte secondary cell
CN201310020097.8A CN103094603B (en) 2006-08-14 2007-08-14 Nonaqueous electrolyte secondary cell
CN200710140457.2A CN101127409B (en) 2006-08-14 2007-08-14 Non aqueous electrolyte secondary battery
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