JP5985137B2 - Manufacturing method of non-aqueous secondary battery - Google Patents

Description

  The present invention relates to a non-aqueous secondary battery having a high capacity and good charge / discharge cycle characteristics.

  Since non-aqueous secondary batteries have high voltage and high capacity, there are great expectations for their development. In addition to Li (lithium) and Li alloys, natural or artificial graphite-based carbon materials that can insert and desorb Li ions are applied to the negative electrode material (negative electrode active material) of nonaqueous secondary batteries. .

  However, recently, there has been a demand for further increase in capacity of batteries for portable devices that are miniaturized and multifunctional, and in response to this, more like Si (silicon), Sn (tin), etc. A material capable of containing Li is attracting attention as a negative electrode material (hereinafter also referred to as “high capacity negative electrode material”).

As one of such high-capacity negative electrode materials for non-aqueous secondary batteries, for example, SiO _x having a structure in which ultrafine particles of Si are dispersed in SiO ₂ has attracted attention (eg, Patent Documents 1 to 3). When this material is used as a negative electrode active material, since Si that reacts with Li is an ultrafine particle, charging / discharging is performed smoothly, while the SiO _x particles having the above structure itself have a small surface area, and therefore contain a negative electrode active material. The properties of the coating material for forming the layer and the adhesion of the negative electrode active material-containing layer to the current collector are also good.

JP 2004-47404 A Japanese Patent Laid-Open No. 2005-259697 JP 2007-242590 A

  By the way, in the non-aqueous secondary battery in which the capacity is increased by using the above-described high-capacity negative electrode material, in particular, a spirally wound electrode body in which a positive electrode and a negative electrode are wound in a spiral shape via a separator is square. In the case of a battery loaded inside a (square tube) outer can or laminate film outer package, there is a risk that the capacity will decrease with repeated charging and discharging, or the thickness may increase greatly due to battery swelling. This has been clarified by the study of the present inventors.

  The present invention has been made in view of the above circumstances, and provides a non-aqueous secondary battery having high capacity, good charge / discharge cycle characteristics, and suppressed battery swelling.

The non-aqueous secondary battery of the present invention is a non-aqueous secondary battery including a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the positive electrode includes a positive electrode current collector, and at least one surface of the positive electrode current collector includes: A positive electrode active material-containing layer containing a Li-containing transition metal oxide is formed, the negative electrode includes a negative electrode current collector, and at least one surface of the negative electrode current collector includes an element capable of being alloyed with Li. A negative electrode active material-containing layer containing a negative electrode active material and at least one binder selected from the group consisting of polyimide, polyamideimide and polyamide is formed, and the 0.2% proof stress of the negative electrode current collector is 250 N / Mm ² or more, or the tensile strength of the negative electrode current collector is 300 N / mm ² or more, and the surface roughness Rz of the negative electrode current collector is 0.6 to 10 μm. And

  A negative electrode active material containing an element that can be alloyed with Li has a high capacity. By using this, the capacity of a non-aqueous secondary battery can be increased. However, when a high-capacity negative electrode material such as that described above is used as the negative electrode active material, the volume of the negative electrode changes greatly due to charging, resulting in a change in volume of the negative electrode and excessive stress due to the expansion of the negative electrode active material. Therefore, the negative electrode may be deformed such as bending. Therefore, due to deformation such as volume change or bending of the negative electrode, there is a problem that the capacity is greatly reduced with the increase in the number of charge / discharge repetitions, or the thickness is greatly increased due to battery swelling. .

  Therefore, in the present invention, polyimide, polyamideimide or polyamide is used for the binder of the negative electrode active material-containing layer, and the negative electrode current collector has a 0.2% proof stress or tensile strength equal to or higher than a specific value, and By using a material having a surface roughness within a certain range, while suppressing deformation of the negative electrode volume due to expansion of the negative electrode active material during charging and bending, and increasing the capacity of the non-aqueous secondary battery, Charging / discharging cycle characteristics are improved, and further, battery swelling during charging is reduced.

  According to the present invention, it is possible to provide a non-aqueous secondary battery with high capacity and good charge / discharge cycle characteristics. Moreover, in the non-aqueous secondary battery of the present invention, for example, even in the case of a square shape (square tube shape) or a flat shape with a small thickness with respect to the width, battery swelling during charging can be reduced.

  The negative electrode according to the nonaqueous secondary battery of the present invention is selected from the group consisting of a negative electrode active material containing an element that can be alloyed with Li, polyimide, polyamideimide, and polyamide on at least one side of the negative electrode current collector. It has a negative electrode active material containing layer containing at least one binder.

Examples of the negative electrode active material containing an element that can be alloyed with Li include a simple substance that can be alloyed with Li and a material containing an element that can be alloyed with Li. As an element that can be alloyed with Li, Si or Sn is preferable. Specifically, as a negative electrode active material containing an element that can be alloyed with Li, Si or Sn (a simple substance of these elements); an alloy containing Sn (Cu ₆ Sn ₅ , Sn ₇ Ni ₃ , Mg ₂ Sn) Etc.); Si or Sn oxides; and the like. These may be used alone or in combination of two or more.

For example, among the above alloys, NiAs type intermetallic compounds belonging to the space group P6 ₃ / mmc such as Cu ₆ Sn ₅ are particularly excellent in reversibility, large capacity, and excellent charge / discharge cycle characteristics. This is preferable because the secondary battery can be easily constructed. The alloy is not necessarily limited to a specific composition, and an alloy having a relatively wide solid solution range may have a composition slightly deviating from the central composition. In addition, a part of the constituent elements may be substituted with other elements. For example, Cu _6-x M _x Sn ₅ (x <6) or Cu ₆ Sn _5-y M _y ( As in y <5), the main constituent element of the alloy can be replaced with another element M to form a multi-element compound.

In addition, a material containing an oxide of Si, that is, a material containing Si (silicon) and O (oxygen) as constituent elements and having an atomic ratio x of O to Si of 0.5 ≦ x ≦ 1.5 (hereinafter, (“SiO _x ”) is also preferable in that the capacity of the non-aqueous secondary battery can be increased.

The SiO _x may contain Si microcrystal or amorphous phase. In this case, the atomic ratio of Si and O is a ratio including Si microcrystal or amorphous phase Si. That is, the SiO _x, oxides of Si, for example, in a matrix of amorphous SiO _2, Si (e.g., microcrystalline Si) is include the dispersed structure, the SiO ₂ in the amorphous In addition, it is sufficient that the atomic ratio x satisfies 0.5 ≦ x ≦ 1.5 by adding Si dispersed therein. For example, in the case of a material in which Si is dispersed in an amorphous SiO ₂ matrix and the molar ratio of SiO ₂ to Si is 1: 1, x = 1. It is written with. In the case of a material having such a structure, for example, in X-ray diffraction analysis, a peak due to the presence of Si (microcrystalline Si) may not be observed, but when observed with a transmission electron microscope, a fine Si phase is observed. Existence can be confirmed.

The SiO _x is preferably a composite that is combined with a conductive material such as a carbon material. For example, the surface of the SiO _x is preferably covered with a conductive material (such as a carbon material). Since SiO _x has poor conductivity, when it is used as a negative electrode active material, from the viewpoint of securing good battery characteristics, a conductive material (conductive aid) is used, and SiO _x and conductive material in the negative electrode are used. Therefore, it is necessary to form a good conductive network by mixing and dispersing with each other. In the case of a composite in which SiO _x is combined with a conductive material, for example, a conductive network in the negative electrode is formed better than when a material obtained by simply mixing SiO _x and a conductive material is used. The

As a composite of SiO _x and a conductive material, as described above, the surface of SiO _x is covered with a conductive material (preferably a carbon material), and SiO _x and a conductive material (preferably a carbon material). And the like.

Further, by using the composite in which the surface of SiO _x is coated with a conductive material (preferably a carbon material) in combination with a conductive material (such as a carbon material), an even better conductive network can be obtained in the negative electrode. Therefore, it is possible to realize a non-aqueous secondary battery having higher capacity and excellent battery characteristics (for example, charge / discharge cycle characteristics). The complex of the SiO _x and a conductive material coated with a conductive material, for example, like granules the mixture was further granulated with SiO _x and a conductive material coated with a conductive material .

As the SiO _x whose surface is coated with a conductive material, a complex with SiO _x and a conductive material resistivity value is less than (e.g. granulate), preferably between SiO _x and the carbon material Those in which the surface of the granulated body is further coated with a carbon material can be preferably used. When the SiO _x and the conductive material are dispersed in the granulated body, a better conductive network can be formed. Therefore, in a non-aqueous secondary battery having a negative electrode containing this as a negative electrode material, a heavy load Battery characteristics such as discharge characteristics can be further improved.

Preferred examples of the conductive material that can be used for forming a composite with SiO _x include carbon materials such as graphite, low crystalline carbon, carbon nanotube, and vapor grown carbon fiber.

  The conductive material may also act as a negative electrode active material such as graphite.

Details of the conductive material include: a fibrous or coiled carbon material; a fibrous or coiled metal; carbon black (including acetylene black and ketjen black), artificial graphite, graphitizable carbon, and non-graphite. At least one material selected from the group consisting of carbonized carbon is preferred. A fibrous or coiled carbon material or a fibrous or coiled metal is preferable in that it easily forms a conductive network and has a large surface area. Carbon black (including acetylene black and ketjen black), artificial graphite, graphitizable carbon, and non-graphitizable carbon have high electrical conductivity and high liquid retention. _{Even if the x} particles expand and contract, it is preferable in that it has a property of easily maintaining contact with the particles.

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

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

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

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

When a composite of SiO _x and a conductive material is used for the negative electrode according to the present invention, the ratio of SiO _x to the conductive material is SiO 2 from the viewpoint of satisfactorily exerting the effect of the composite with the conductive material. _x : It is preferable that an electroconductive material is 5 mass parts or more with respect to 100 mass parts, and it is more preferable that it is 10 mass parts or more. Further, in the composite, if the ratio of the conductive material to be combined with SiO _x is too large, the amount of SiO _x in the negative electrode active material-containing layer may be decreased, and the effect of increasing the capacity may be reduced. Therefore, the conductive material is preferably 50 parts by mass or less and more preferably 40 parts by mass or less with respect to 100 parts by mass of SiO _x .

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

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

Further, a SiO _x, in the case of manufacturing a granulated body with small conductive material resistivity value than SiO _x is adding the conductive material into the dispersions SiO _x are dispersed in a dispersion medium, Using this dispersion, composite particles (granulated bodies) may be formed by the same technique as that for combining SiO _x itself. Further, by granulation process according to the similar mechanical method, it is possible to produce a granular material of SiO _x and a conductive material.

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

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

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

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

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

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

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

  In the non-aqueous secondary battery of the present invention, in order to increase the capacity by using the negative electrode active material described above, in order to suppress deformation such as volume change or bending of the negative electrode due to expansion of the negative electrode active material accompanying charging. The following configuration (1) or (2) is employed.

In the configuration (1), the 0.2% proof stress of the negative electrode current collector is 250 N / mm ² or more, preferably 300 N / mm ² or more. The 0.2% proof stress of the negative electrode current collector referred to in this specification is a measurement sample obtained by cutting a negative electrode current collector into a size of 160 mm × 25 mm using “Small Desktop Testing Machine EZ-L” manufactured by Shimadzu Corporation. Then, a tensile test was conducted under the conditions of a tensile speed of 2 mm / min and a temperature of 20 ° C. to obtain a stress-strain curve, and from this stress-strain curve, specified in “8. (d)” of Japanese Industrial Standard (JIS) Z2241. This means “Fε” which is obtained by the “offset method” in which the permanent elongation is 0.2%.

In the configuration (2), the tensile strength of the negative electrode current collector is 300 N / mm ² or more, preferably 350 N / mm ² or more. The tensile strength of the negative electrode current collector referred to in the present specification is obtained by using a “small desktop testing machine EZ-L” manufactured by Shimadzu Corporation, and cutting the negative electrode current collector into a size of 160 mm × 25 mm as a measurement sample. It is a value obtained by measurement under conditions of 2 mm / min and a temperature of 20 ° C.

  As the material of the negative electrode current collector, Cu, Ni, Ti and alloys thereof can be used. To increase the 0.2% proof stress and tensile strength of the negative electrode current collector as described above, the negative electrode current collector is used. It is preferable to use a current collector (current collector foil) made of a Cu alloy containing at least one element selected from the group consisting of Zr, Cr, Sn, Zn, Ni, Si, and P as the electric body. . If it is Cu alloy containing the above elements, a collector with a large 0.2% yield strength and tensile strength can be comprised as mentioned above.

  More preferable examples of the composition of the Cu alloy include Cu—Cr, Cu—Ni, Cu—Cr—Zn, and Cu—Ni—Si. The amount of alloy components other than Cu in the Cu alloy is preferably 0.01 to 5% by mass (in this case, the balance is, for example, Cu and inevitable impurities).

  In the case of a Cu—Cr—Zn alloy, the content of each alloy component is preferably, for example, Cr: 0.05 to 0.5 mass%, Zr: 0.01 to 0.3 mass%. In the Cu—Cr—Zn alloy, for example, Mg, Zn, Sn, P, and the like may be contained within the range of the preferable content of the alloy components as necessary.

  Further, examples of the Cu—Ni—Si alloy include a Corson alloy. In this case, the content of each alloy component is, for example, Ni: 1.0 to 4.0 mass%, Si: 0.1 to 1 It is preferably 0.0% by mass. If necessary, the Cu—Ni—Si alloy may contain, for example, Mg, Zn, Sn, P, or the like within the range of the preferred content of the alloy components.

  The thickness of the negative electrode current collector is preferably 6 μm or more, and more preferably 8 μm or more, from the viewpoint of increasing the elastic range of the negative electrode current collector and increasing the strength. However, if the negative electrode current collector is too thick, the volume proportion of the negative electrode current collector that does not directly participate in the power generation reaction increases in the battery, and the amount of active material of the positive and negative electrodes decreases, and the negative electrode active material is used. This may reduce the effect of increasing the capacity. Therefore, the thickness of the negative electrode current collector is preferably 16 μm or less, and more preferably 14 μm or less.

Regarding the 0.2% proof stress and tensile strength of the negative electrode current collector, it is difficult to make the thickness of, for example, 16 μm or less with a Cu alloy foil having a very large 0.2% proof stress and tensile strength. When the current collector having such a thickness is used, the effect of increasing the capacity by using the negative electrode active material may be reduced. Therefore, the 0.2% yield strength of the negative electrode current collector is preferably 750 N / mm ² or less, more preferably 700 N / mm ² or less. The tensile strength of the negative electrode current collector is preferably 800 N / mm ² or less, more preferably 750 N / mm ² or less.

  As the negative electrode current collector, for example, a Cu alloy foil having the above-described composition and having the above-described thickness may be selected and used having such 0.2% proof stress or tensile strength. Good. A rolled foil obtained by a rolling method can be preferably used as a negative electrode current collector because a foil having a high tensile strength is easily obtained.

  In addition, in order to sufficiently exhibit the effect of suppressing deformation such as volume change or bending of the negative electrode due to expansion / contraction of the negative electrode active material by the high-strength current collector, the surface of the negative electrode current collector is finely granular. It is necessary to perform a roughening treatment to form a metal layer, and to ensure sufficient adhesive strength between the current collector and the active material. In the roughening treatment, the fine granularity constituting the metal layer is such that the surface roughness of the negative electrode current collector is 0.6 to 10 μm in terms of the ten-point average roughness Rz defined by Japanese Industrial Standard JIS B0601-1994. What is necessary is just to adjust the particle size of a thing.

  Although there is a rolled foil in which Rz is in the range of 0.6 to 10 μm without performing the roughening treatment, sufficient adhesive strength may not be obtained if the value of Rz is in the above range, It is desired to form a fine granular metal layer on the surface by roughening treatment. That is, the anchoring effect obtained by forming the metal layer having the surface roughness can increase the adhesive strength between the negative electrode current collector and the negative electrode active material. In addition, the gap between the current collector and the active material caused by the formation of irregularities on the surface of the negative electrode current collector serves as a stress relaxation field due to expansion and contraction of the active material due to charge and discharge. Strain can be prevented from occurring in the body.

  When Rz is smaller than 0.6 μm, the effect of improving the adhesive strength between the current collector and the active material and the stress relaxation effect during expansion / contraction of the active material are insufficient, and when Rz is larger than 10 μm, the unevenness As a result, a short circuit is likely to occur, and the gap between the current collector and the active material is increased, and the possibility that the adhesive strength is reduced is increased.

  The roughening treatment of the negative electrode current collector surface can be performed by forming a fine granular metal layer on the current collector surface by electrolytic plating, electroless plating, sputtering, vapor deposition, or the like. The formed metal layer may be different from the material constituting the current collector, but is preferably the main constituent element of the current collector or an alloy thereof. For example, in the case of Cu alloy foil, the surface metal layer is It is preferable to comprise Cu or a Cu alloy. In particular, when a metal layer is formed on the surface of a Cu alloy foil using a plating method, the plating layer may not be formed uniformly depending on the type of additive element in the Cu alloy. By including Ni ions (such as nickel sulfate) and P ions (such as phosphoric acid) in (such as a copper sulfate solution), the uniformity of the plating layer can be enhanced.

  Further, it may be a two-stage plating process in which fine particles are further formed on the granular material after the fine granular metal layer is formed.

  The thickness of the metal layer varies depending on the target surface roughness, but is preferably about 0.6 to 10 μm.

  The negative electrode according to the present invention has a structure in which a negative electrode active material-containing layer containing the negative electrode active material is formed on one side or both sides of the negative electrode current collector as described above. In addition to the negative electrode active material, the negative electrode active material-containing layer includes a binder and a conductive material used as necessary (the conductive material used when forming a composite with the negative electrode active material) A suitable solvent (dispersion medium) is added to the negative electrode mixture containing, and a paste-like or slurry-like composition (paint) obtained by sufficiently kneading is applied to the current collector, The solvent (dispersion medium) can be removed by drying or the like to form a film with a predetermined thickness and density.

  In the nonaqueous secondary battery of the present invention, the negative electrode current collector having the above-mentioned value of 0.2% proof stress or tensile strength is used, and at least one of polyimide, polyamideimide, and polyamide is used as the binder of the negative electrode active material-containing layer. By using one type, deformation of the negative electrode due to expansion of the negative electrode active material during charging, deformation such as bending is suppressed as a whole, and deterioration of charge / discharge cycle characteristics and battery swelling are suppressed.

  Polyimide, polyamide-imide, and polyamide bind various components in the negative electrode active material-containing layer (negative electrode active materials, negative electrode active materials and conductive materials described later, and composites containing the negative electrode active material). Therefore, even if the negative electrode active material expands and contracts due to repeated charge and discharge of the battery, these contacts are maintained and the negative electrode active material is contained. It is also possible to keep the conductive network in the layer well.

  Examples of the polyimide include various known polyimides, and any of thermoplastic polyimide and thermosetting polyimide can be used. In the case of a thermosetting polyimide, either a condensation type polyimide or an addition type polyimide may be used. More specifically, for example, “Semicofine (trade name)” manufactured by Toray Industries, “PIX series (trade name)” manufactured by Hitachi Chemical DuPont Microsystems, “HCI series (trade name)” manufactured by Hitachi Chemical, Ube Commercial products such as “U-Varnish (trade name)” manufactured by Kosan Co., Ltd. can be used. For reasons such as good electron mobility, those having an aromatic ring in the molecular chain, that is, aromatic polyimide are more preferred. Only one type of polyimide may be used, or two or more types may be used in combination.

  Examples of the polyamideimide include various known polyamideimides. More specifically, for example, commercially available products such as “HPC series (trade name)” manufactured by Hitachi Chemical Co., Ltd. and “Viromax (trade name)” manufactured by Toyobo Co., Ltd. can be used. Also in polyamideimide, for the same reason as polyimide, those having an aromatic ring in the molecular chain, that is, aromatic polyamideimide is more preferable. Polyamideimide may use only 1 type and may use 2 or more types together.

  As polyamide, various polyamides, such as nylon 66, nylon 6, aromatic polyamide (nylon MXD6 etc.), can be used, for example. Also in the polyamide, those having an aromatic ring in the molecular chain, that is, an aromatic polyamide is more preferable for the same reason as polyimide. Only one type of polyamide may be used, or two or more types of polyamide may be used in combination.

  When using the binder, if heat treatment is required after compression molding the negative electrode active material-containing layer in order to ensure binder adhesion, heat treatment at a lower temperature to prevent softening of the negative electrode current collector It is preferable to use a material that can secure adhesiveness. The heat treatment temperature is preferably 200 ° C. or lower, more preferably 180 ° C. or lower. On the other hand, the heat treatment temperature is set higher than the drying temperature of the negative electrode active material-containing layer, for example, to ensure adhesion. Preferably, the temperature is set to 120 ° C. or higher, more preferably 120 ° C. or higher, and most preferably 140 ° C. or higher.

  Two or more of polyimide, polyamideimide and polyamide may be used in combination for the binder of the negative electrode active material-containing layer.

  Furthermore, binders other than polyimide, polyamideimide, and polyamide can also be used for the negative electrode active material-containing layer. Examples of such a binder include polysaccharides such as starch, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose, diacetyl cellulose, and their modified products; polyvinyl chloride, polyvinyl pyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride. Thermoplastic resins such as polyethylene and polypropylene and their modified products; rubber-like elasticity such as ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber, butadiene rubber, polybutadiene, fluoro rubber, polyethylene oxide, etc. These polymers can be used alone or in combination of two or more thereof. These binders other than polyimide, polyamideimide and polyamide can be used in combination with any of polyimide, polyamideimide and polyamide when the negative electrode according to the present invention does not have a coating layer. In addition, binders other than these polyimide, polyamideimide and polyamide can be used without using any of polyimide, polyamideimide and polyamide when the negative electrode according to the present invention has a coating layer. It is preferable to use in combination with any one of polyimide, polyamideimide and polyamide.

  A conductive material may be further added to the negative electrode active material-containing layer as a conductive additive to form a mixture of the negative electrode active material and the conductive material.

  Such a conductive material is not particularly limited as long as it is an electron conductive material that does not cause a chemical change in the non-aqueous secondary battery. Usually, natural graphite (such as scaly graphite, scaly graphite, earthy graphite), artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder (copper powder, nickel powder, aluminum powder, silver powder, etc.), One or more materials such as metal fibers and polyphenylene derivatives (described in JP-A-59-20971) can be used. Further, the conductive material may act as a negative electrode active material.

  Moreover, you may form a negative electrode active material content layer by methods other than the above. For example, when an elemental element that can be alloyed with Li or an alloy containing an element that can be alloyed with Li is used as the negative electrode active material, physical vapor deposition (PVD), chemical vapor deposition (CVD) It is also possible to form a thin film of a negative electrode active material on the surface of the negative electrode current collector by a thin film formation method such as a method or a liquid phase growth method, and to make this a negative electrode active material-containing layer. Examples of the PVD method include a vacuum deposition method, a sputtering method, an ion plating method, a molecular beam epitaxy (MBE) method, and a laser ablation method. As the CVD method, thermal CVD method, MOCVD (metal organic chemical vapor deposition) method, RF (Radio Frequency) plasma CVD method, ECR (electron cyclotron resonance) plasma CVD method, photo CVD method, laser CVD method, atomic layer epitaxy ( ALE) method. Examples of the liquid phase growth method include a plating method (electrolytic plating method, electroless plating method), an anodic oxidation method, a coating method, and a sol-gel method.

In addition, when Cu ₆ Sn ₅ is used as an alloy (intermetallic compound) containing an element that can be alloyed with Li, for example, several Cu films and Sn films are alternately stacked by the various thin film forming methods described above. Then, Cu ₆ Sn ₅ may be formed by performing a heat treatment to diffuse Cu and Sn to each other.

  In the negative electrode active material-containing layer, from the viewpoint of increasing the capacity of the battery, the content of the negative electrode active material is preferably 60% by mass or more, and more preferably 70% by mass or more. The negative electrode active material-containing layer may be formed of only the negative electrode active material. For example, as described above, a thin film formed of a single element that can be alloyed with Li or an alloy containing an element that can be alloyed with Li is used as the negative electrode active material. It can also be set as a containing layer. Therefore, the content of the negative electrode active material in the negative electrode active material-containing layer may be 100% by mass, but in the case of constituting the negative electrode active material-containing layer in combination with a binder, from the viewpoint of securing the effect by using the binder, The content of the negative electrode active material is preferably 99% by mass or less, and more preferably 98% by mass or less.

  Further, the content of the binder in the negative electrode active material-containing layer is preferably 1% by mass or more, and more preferably 2% by mass or more, from the viewpoint of more effectively exerting the action due to the use of the binder. However, if the amount of the binder in the negative electrode active material-containing layer is too large, for example, the amount of the negative electrode active material may decrease and the capacity may decrease, so the binder content in the negative electrode active material-containing layer is 30 It is preferable that it is mass% or less, and it is more preferable that it is 20 mass% or less.

  As the binder for the negative electrode active material-containing layer, at least one of polyimide, polyamideimide and polyamide is used, and when a binder other than these is used in combination, the polyimide, polyamideimide and The content of polyamide (when only one of these is used, the amount thereof. When two or more of these are used in combination, the total amount thereof) is preferably 1% by mass or more, More preferably, the content is adjusted so as to satisfy the above-mentioned preferable binder amount while setting the content to 2% by mass or more. By making the content of polyimide, polyamideimide and polyamide in the negative electrode active material-containing layer as described above, the effects of these use can be more effectively exhibited.

  In the negative electrode active material-containing layer, a conductive material (conducting aid, carbon in the case where the surface of the oxide is coated with carbon, and a composite of the oxide coated with carbon on the surface and the conductive material) In the case of using a conductive material and a conductive material in particles in which the surface of the granulated body of the oxide and the conductive material is coated with carbon.), The conductivity is increased from the viewpoint of increasing the capacity of the battery. The total amount of materials is preferably 50% by mass or less, and more preferably 40% by mass or less. Further, from the viewpoint of more effectively exerting the effect of using the conductive material in the negative electrode active material-containing layer, the total amount of the conductive material in the negative electrode active material-containing layer is preferably 5% by mass or more, More preferably, it is 10 mass% or more.

  The thickness of the negative electrode active material-containing layer (thickness per side of the current collector; the same shall apply hereinafter) varies depending on the composition and forming method of the negative electrode active material-containing layer, but from the viewpoint of suppressing the hardness of the negative electrode to some extent, In the case of a configured negative electrode active material-containing layer (for example, in the case of a negative electrode active material-containing layer formed using the above-described negative electrode active material-containing layer forming composition, the same applies hereinafter), it is 50 μm or less. Is preferably 30 μm or less, and in the case of the negative electrode active material-containing layer constituted by the negative electrode active material thin film, it is preferably 20 μm or less, and more preferably 10 μm or less. preferable. However, if the negative electrode active material-containing layer is too thin, the effect of increasing the capacity of the battery may be reduced. Therefore, the thickness of the negative electrode active material-containing layer may include a negative electrode active material composed of a negative electrode mixture. In the case of a layer, it is preferably 5 μm or more, more preferably 10 μm or more, and in the case of a negative electrode active material-containing layer constituted by a thin film of the negative electrode active material, it is 1 μm or more. The thickness is preferably 3 μm or more.

  Moreover, the porous layer (coat layer) containing the insulating material which does not react with Li can be provided in the surface (surface on the opposite side to a negative electrode collector) of a negative electrode active material content layer. By using the negative electrode current collector having a large 0.2% proof stress or tensile strength as described above and further forming the coat layer, it is possible to further suppress deformation such as volume change and bending of the negative electrode. In addition, it is possible to satisfactorily achieve a reduction in the charge / discharge cycle characteristics of the nonaqueous secondary battery and a reduction in battery swelling.

  The coat layer according to the negative electrode is a layer (porous layer) that contains an insulating material that does not react with Li and has pores to the extent that a nonaqueous electrolyte (electrolytic solution) can pass through.

The insulating material that does not react with Li for constituting the coat layer is preferably, for example, electrochemically stable and electrically insulating fine particles, and there are no particular restrictions on such fine particles, Inorganic fine particles are more preferable. Specifically, inorganic oxide fine particles such as iron oxide, silica (SiO ₂ ), alumina (Al ₂ O ₃ ), TiO ₂ , BaTiO ₃ ; inorganic nitride fine particles such as aluminum nitride and silicon nitride; calcium fluoride, Examples include slightly soluble ionic crystal particles such as barium fluoride and barium sulfate; and covalently bonded crystal particles such as silicon and diamond. Here, the inorganic oxide fine particles may be fine particles such as boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, mica, or a mineral resource-derived material or an artificial product thereof. In addition, the inorganic fine particles electrically insulate the surface of a conductive material exemplified by metals, SnO ₂ , conductive oxides such as tin-indium oxide (ITO); carbonaceous materials such as carbon black and graphite; Particles that have electrical insulation properties by coating with a material having a property (for example, the above-described inorganic oxide) may be used.

  Organic fine particles can also be used for the insulating material that does not react with Li. Specific examples of organic fine particles include polyimides, melamine resins, phenol resins, crosslinked polymethyl methacrylate (crosslinked PMMA), crosslinked polystyrene (crosslinked PS), polydivinylbenzene (PDVB), and high crosslinking amounts such as benzoguanamine-formaldehyde condensates. Molecular fine particles; heat-resistant polymer fine particles such as thermoplastic polyimide; and the like. The organic resin (polymer) constituting these organic fine particles is a mixture, modified body, derivative, copolymer (random copolymer, alternating copolymer, block copolymer, graft copolymer) of the materials exemplified above. ) Or a crosslinked product (in the case of the heat-resistant polymer).

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

  As the fine particles, it is preferable to use particles having a ratio of particles having a particle size of 0.2 μm or less and particles having a particle size of 2 μm or more of 10% by volume or less, a narrow particle size distribution and a uniform particle size. . Thereby, even if it is thin, it can be set as the coating layer with the high effect which prevents the volume change and curvature of a negative electrode.

  The particle diameter of the fine particles is based on volume measured by dispersing the fine particles in a medium that does not swell or dissolve (for example, water) using a laser scattering particle size distribution analyzer (for example, “LA-920” manufactured by HORIBA). It can be determined by measuring the particle size distribution. That is, if the value (d10) of 10% in the volume-based integrated fraction is 0.2 μm or more, it indicates that the proportion of particles having a particle size of 0.2 μm or less is 10% by volume or less. If the value of 90% (d90) in the integrated fraction is 2 μm or less, it indicates that the proportion of particles having a particle size of 2 μm or more is 10% by volume or less, so that the fine particles have such a particle size distribution May be used.

  The coat layer may contain an electron conductive material. Although the electron conductive material is not an essential component of the coat layer, as described later, when Li is introduced into the negative electrode active material in advance, the electron conductive material is included in the coat layer.

  Examples of the electron conductive material that can be used for the coating layer include carbon materials such as carbon particles and carbon fibers; metal materials such as metal particles and metal fibers; and metal oxides. Among these, carbon particles and metal particles having low reactivity with Li are preferable.

  As the carbon material, for example, a known carbon material that is used as a conductive additive in an electrode constituting a battery can be used. Specifically, carbon such as carbon black (thermal black, furnace black, channel black, lamp black, ketjen black, acetylene black, etc.), graphite (natural graphite such as flake graphite, earth graphite, and artificial graphite) Examples include particles and carbon fibers.

  Among the carbon materials described above, the combined use of carbon black and graphite is particularly preferable from the viewpoint of dispersibility with a binder described later. Further, as the carbon black, ketjen black and acetylene black are particularly preferable.

  The particle size of the carbon particles is, for example, preferably 0.01 μm or more, more preferably 0.02 μm or more, preferably 10 μm or less, more preferably 5 μm or less.

  Among the electron conductive materials constituting the coat layer, the metal particles and the metal fibers are preferably composed of a metal element that has low reactivity with Li and is difficult to form an alloy. Specific metal elements constituting the metal particles and metal fibers include, for example, Ti, Fe, Ni, Cu, Mo, Ta, and W.

  In the case of metal particles, the shape is not particularly limited, and may be any shape such as a lump shape, a needle shape, a column shape, or a plate shape. Further, the metal particles and the metal fibers are preferably those whose surfaces are not oxidized so much, and those that are excessively oxidized are preferably subjected to heat treatment in a reducing atmosphere in advance and then subjected to coating layer formation. .

  The particle size of the metal particles is, for example, preferably 0.02 μm or more, more preferably 0.1 μm or more, preferably 10 μm or less, more preferably 5 μm or less.

  In forming the coating layer, it is preferable to use a binder for the purpose of binding the insulating material which does not react with the Li. As the binder, for example, various materials exemplified as the binder for the negative electrode active material-containing layer can be used. Similarly to the binder of the negative electrode active material-containing layer, the binder of the coat layer is also made of polyimide, polyamideimide, and polyamide. Use of at least one of them is preferable because the adhesion between the negative electrode active material-containing layer and the coating layer is improved.

  When a binder is used for forming the coat layer, the content of the binder in the coat layer is preferably 2% by mass or more, more preferably 4% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass. % Or less.

  When the coating layer contains an electron conductive material, when the total of the insulating material that does not react with Li and the material having electron conductivity is 100% by mass, the material having electron conductivity. The ratio of, for example, is preferably 2.5% by mass or more, more preferably 5% by mass or more, and 96% by mass or less, more preferably 95% by mass or less. In other words, the insulating property that does not react with Li The ratio of the material is, for example, preferably 4% by mass or more, more preferably 5% by mass or more, and 97.5% by mass or less, more preferably 95% by mass or less.

  The thickness of the coat layer is, for example, preferably 1 μm or more, more preferably 2 μm or more, particularly preferably 3 μm or more, preferably 10 μm or less, more preferably 8 μm or less, and particularly preferably 6 μm or less. If the coating layer has such a thickness, deformation such as volume change and bending of the negative electrode can be suppressed more efficiently, and the battery capacity can be increased, charge / discharge cycle characteristics can be prevented from lowering, and battery swelling can be further reduced. Can be achieved well. For example, if the thickness of the coating layer becomes too thin relative to the surface roughness of the negative electrode active material-containing layer, it becomes difficult to cover the entire surface of the negative electrode active material-containing layer without pinholes, and the coating layer is formed. There is a possibility that the effect is reduced. On the other hand, if the coat layer is too thick, it leads to a reduction in the capacity of the battery.

  As described above, by using fine particles having a uniform particle size as an insulating material that does not react with Li, formation of a coating layer with good properties that does not include pinholes while reducing the thickness as described above Becomes easy.

  Moreover, since the affinity between the negative electrode and the non-aqueous electrolyte is improved by providing the coat layer, there is an effect that the non-aqueous electrolyte can be easily introduced into the battery.

  For the coating layer, for example, an appropriate solvent (dispersion medium) is sufficiently added to a mixture containing an insulating material that does not react with Li, a material having electronic conductivity used as necessary, and a binder. Apply the paste-like or slurry-like composition (paint) obtained by kneading to the surface of the negative electrode active material-containing layer formed on the surface of the negative electrode current collector, and remove the solvent (dispersion medium) by drying or the like. Thus, it can be formed with a predetermined thickness. The coat layer may be formed by methods other than those described above. For example, after the composition for forming the negative electrode active material-containing layer is applied to the surface of the current collector, the composition for forming the coat layer is applied and dried before the coating film is completely dried. The substance-containing layer and the coat layer may be formed at the same time. Furthermore, in addition to the sequential method of sequentially applying the composition for forming a negative electrode active material-containing layer and the composition for forming a coat layer as described above, application of the composition for forming a negative electrode active material-containing layer, The negative electrode active material-containing layer and the coating layer may be formed simultaneously by a simultaneous coating method in which coating with the composition for forming the coating layer is performed simultaneously.

Since the negative electrode active material (eg, SiO _x ) used in the negative electrode according to the present invention has a relatively large irreversible capacity, it is also preferable to introduce Li in advance in the negative electrode according to the present invention. Further increase in capacity is possible.

  As a method for introducing Li into the negative electrode, for example, a Li-containing layer is formed on the surface opposite to the negative electrode active material-containing layer of the negative electrode coat layer (a coat layer that also contains a material having electronic conductivity). A method of introducing Li from the Li-containing layer to the negative electrode active material in the negative electrode active material-containing layer is preferable.

  When Li is introduced into the negative electrode active material, the negative electrode may be bent due to a volume change of the negative electrode active material. However, if a coating layer is formed on the negative electrode, in an environment where the non-aqueous electrolyte (electrolytic solution) of the battery is present (for example, inside the battery), the negative electrode active material in the negative electrode active material-containing layer is added to the Li in the Li-containing layer. Is introduced electrochemically, but in an environment where a non-aqueous electrolyte is not present, the reaction of introducing Li into the negative electrode active material hardly occurs. Thus, when employing the above-described Li introduction method, the coat layer according to the negative electrode also has a function of supplying Li in the Li-containing layer to the negative electrode active material-containing layer via the nonaqueous electrolyte. Thus, the reactivity between the negative electrode active material and Li can be controlled, and bending of the negative electrode accompanying the introduction of Li can be suppressed.

  The Li-containing layer for introducing Li into the negative electrode is preferably formed by a general vapor phase method (vapor phase deposition method) such as resistance heating or sputtering (that is, a vapor deposition film). If the Li-containing layer is directly formed on the surface of the coat layer as a vapor deposition film by a vapor phase method, it is easy to form a uniform layer with a desired thickness over the entire surface of the coat layer. It can introduce | transduce without excess and deficiency with respect to the irreversible capacity | capacitance part of a negative electrode active material.

  When the Li-containing layer is formed by a vapor phase method, the vapor deposition source and the coat layer related to the negative electrode may be opposed to each other in a vacuum chamber, and vapor deposition may be performed until the layer has a predetermined thickness.

  The Li-containing layer may be composed only of Li, for example, Li-Al, Li-Al-Mn, Li-Al-Mg, Li-Al-Sn, Li-Al-In, Li-Al-Cd. Or a Li alloy such as When the Li-containing layer is composed of a Li alloy, the content ratio of Li in the Li-containing layer is preferably, for example, 50 to 90 mol%.

  The thickness of the Li-containing layer is, for example, preferably 2 μm or more, more preferably 4 μm or more, preferably 10 μm or less, and more preferably 8 μm or less. By forming the Li-containing layer with such a thickness, Li can be introduced more or less with respect to the irreversible capacity of the negative electrode active material. That is, if the Li-containing layer is too thin, the amount of Li relative to the amount of the negative electrode active material present in the negative electrode active material-containing layer is reduced, and the capacity improvement effect due to introducing Li into the negative electrode in advance may be reduced. On the other hand, if the Li-containing layer is too thick, the amount of Li may be excessive, and the amount of vapor deposition increases, resulting in a decrease in productivity.

  As the positive electrode according to the present invention, a paste or slurry obtained by adding an appropriate solvent (dispersion medium) to a mixture (positive electrode mixture) containing a positive electrode active material, a conductive additive, and a binder and kneading the mixture sufficiently. The positive electrode mixture-containing composition can be applied to a positive electrode current collector to form a positive electrode active material-containing layer having a predetermined thickness and density. The positive electrode according to the present invention is not limited to the one obtained by the above production method, and may be one produced by another production method.

Examples of the positive electrode active material include Li _y CoO ₂ (where 0 ≦ y ≦ 1.1), Li _z NiO ₂ (where 0 ≦ z ≦ 1.1), and Li _e MnO _2. (provided that _{0 ≦ e ≦ 1.1.),} Li a Co b M 1 1-b O 2 ( where the ^{M 1} is, Mg, Mn, Fe, Ni , Cu, Zn, Al, Ti, It is at least one metal element selected from the group consisting of Ge and Cr, and 0 ≦ a ≦ 1.1 and 0 <b <1.0.), Li _c Ni _1-d M ² _d O ₂ (However, M ² is at least one metal element selected from the group consisting of Mg, Mn, Fe, Co, Cu, Zn, Al, Ti, Ge, and Cr, and 0 ≦ c ≦ 1.1. a _{0 <d <1.0.),} Li f Mn g Ni h Co 1-g-h O 2 ( provided that And Li-containing transition metal oxides having a layered structure such as 0 ≦ f ≦ 1.1, 0 <g <1.0, and 0 <h <1.0. May be used, or two or more may be used in combination.

  As the binder relating to the positive electrode, the above-described binders exemplified as those for the negative electrode can be used. Moreover, also about the conductive support agent which concerns on a positive electrode, each said conductive support agent illustrated as a thing for negative electrodes can be used.

  In the positive electrode active material-containing layer according to the positive electrode, the content of the positive electrode active material is, for example, 80 to 99% by mass, and the content of the binder is, for example, 0.5 to 20% by mass. It is preferable that content of an agent is 0.5-20 mass%, for example.

  Examples of the non-aqueous electrolyte used in the battery according to the present invention include an electrolytic solution prepared by dissolving the following inorganic ion salt in the following solvent.

  Examples of the solvent include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate, diethyl carbonate (DEC), methyl ethyl carbonate (MEC), γ-butyrolactone, and 1,2-dimethoxyethane. , Tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane, dioxolane derivatives, sulfolane, 3 Non-prototypes such as methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, diethyl ether, 1,3-propane sultone Sex organic solvents may be used alone or in combination.

As the inorganic ion salt, Li salt, for _{example, LiClO 4, LiBF 4, LiPF} 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiB 10 Cl 10, lower aliphatic carboxylic acids Li, LiAlCl ₄ , LiCl, LiBr, LiI, chloroborane Li, Li tetraphenylborate, or the like can be used alone or in combination.

Among the electrolytic solutions in which the inorganic ion salt is dissolved in the solvent, a solvent containing at least one selected from the group consisting of 1,2-dimethoxyethane, diethyl carbonate, and methyl ethyl carbonate, and ethylene carbonate or propylene carbonate In addition, an electrolytic solution in which at least one inorganic ion salt selected from the group consisting of LiClO ₄ , LiBF ₄ , LiPF ₆ , and LiCF ₃ SO ₃ is dissolved is preferable. An appropriate concentration of the inorganic ion salt in the electrolytic solution is, for example, 0.2 to 3.0 mol / dm ³ .

  The non-aqueous secondary battery of the present invention can be obtained by assembling a battery using the negative electrode, the positive electrode and the non-aqueous electrolyte.

  The non-aqueous secondary battery of the present invention only has to include the above-described negative electrode, the above-described positive electrode, and the above-described non-aqueous electrolyte. Various components and structures employed in non-aqueous secondary batteries can be applied.

  For example, as the separator, a separator having sufficient strength and capable of holding a large amount of electrolytic solution is preferable. From such a viewpoint, polyethylene, polypropylene, or ethylene having a thickness of 10 to 50 μm and an aperture ratio of 30 to 70% is used. A microporous film or a nonwoven fabric containing a propylene copolymer is preferred.

  Moreover, in the non-aqueous secondary battery of this invention, there is no restriction | limiting in particular also about the shape. For example, any of a coin shape, a button shape, a sheet shape, a laminated shape, a cylindrical shape, a flat shape, a square shape, a large size used for an electric vehicle, etc. may be used. As described above, when the negative electrode active material is used, in the case of a battery constituted by using a rectangular (square tube) outer can, a flat outer can, a laminate film outer casing, etc. having a small thickness with respect to the width. In particular, the problem of battery swelling is likely to occur. However, in the battery of the present invention, since the occurrence of such battery swelling can be satisfactorily suppressed, a rectangular battery or a flat battery having an exterior body (exterior can) as described above is obtained. In some cases, the effect is particularly prominent.

  In addition, when introducing a positive electrode, a negative electrode, and a separator into a non-aqueous secondary battery, depending on the form of the battery, a laminated electrode body in which a plurality of positive electrodes and a plurality of negative electrodes are stacked via a separator, or a positive electrode and a negative electrode Can be used as a wound electrode body obtained by laminating a film through a separator and then winding it in a spiral shape. As described above, when the negative electrode active material is used, particularly when a wound electrode body is used, problems due to deformation such as volume change and curvature of the negative electrode are likely to occur. Because it can suppress deformation such as volume change and curvature of the winding well, it can be used for wound electrode bodies (especially for winding batteries used in flat batteries using rectangular batteries, flat outer cans, laminated film outer bodies, etc. The effect is particularly prominent when the battery has a wound electrode body whose cross section perpendicular to the flat surface is flat.

  The non-aqueous secondary battery of the present invention has a high capacity and various battery characteristics such as charge / discharge cycle characteristics. Therefore, taking advantage of these characteristics, a power source for a small and multifunctional portable device can be used. First, it can be preferably used for various applications to which conventionally known non-aqueous secondary batteries are applied.

  Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention. In the following examples, the average particle diameters of various composite particles, α-alumina, and graphite are measured by a laser diffraction particle size distribution measurement method using “MICROTRAC HRA (Model: 9320-X100)” manufactured by Microtrack. The volume average value. The 0.2% proof stress and tensile strength of the negative electrode current collector are values measured by the methods described above.

Example 1
Preparation of negative electrode active material SiO (average particle size 5.0 μm) was heated to about 1000 ° C. in a boiling bed reactor, and a mixed gas of methane and nitrogen gas at 25 ° C. was brought into contact therewith, and 1000 ° C. for 60 minutes. A CVD process was performed. Thus, carbon (hereinafter also referred to as “CVD carbon”) generated by thermally decomposing the mixed gas was deposited on SiO to form a coating layer, thereby obtaining a negative electrode material (negative electrode active material).

  When the composition of the negative electrode material was calculated from the mass change before and after the formation of the coating layer, it was SiO: CVD carbon = 90: 10 (mass ratio).

Production of negative electrode current collector Rolled copper alloy foil containing 0.02% Zr and having a thickness of 10 μm (“HCL-02Z” manufactured by Hitachi Cable, 0.2% proof stress 270 N / mm ² , tensile strength 350 N / mm ² ) A negative electrode current collector was prepared as follows. The surface of the alloy foil is degreased by electrolytic degreasing beforehand, and after washing with water, further pickling in a sulfuric acid solution, washing with water, and then plating in a plating bath containing copper sulfate and sulfuric acid. A metal layer made of fine copper particles having a thickness of about 2 μm was formed on each of these to form a negative electrode current collector. The surface roughness Rz of this negative electrode current collector was 2 μm.

Production of Negative Electrode A negative electrode was produced using the negative electrode material. 80% by mass of the negative electrode material (content in the total solid content; the same shall apply hereinafter), 10% by mass of graphite, 2% by mass of ketjen black (average particle size 0.05 μm) as a conductive additive, and polyamide as a binder A negative electrode mixture-containing slurry was prepared by mixing 8% by mass of imide (“HPC-9000-21” manufactured by Hitachi Chemical Co., Ltd.) and dehydrated N-methylpyrrolidone (NMP). Α-alumina (average particle size 1 μm, d10: 0.64 μm, d90: 1.55 μm, the proportion of particles having a particle size of 0.2 μm or less, and the proportion of particles having a particle size of 2 μm or more 10 volume% or less) 95 mass% (content in the total solid content. The same applies hereinafter), polyvinylidene fluoride (PVDF) 5 mass%, and dehydrated NMP were mixed to prepare a slurry for forming a coating layer. .

  Using a blade coater, apply the negative electrode mixture-containing slurry as a lower layer and the coat layer forming slurry as an upper layer on both sides of the negative electrode current collector, dry at 100 ° C., and then compress with a roller press. Thus, a negative electrode active material-containing layer having a thickness of 35 μm and a coating layer having a thickness of 5 μm were formed on both surfaces of the current collector. The laminate in which the negative electrode active material-containing layer and the coating layer were formed on the current collector surface was dried in vacuum at 100 ° C. for 15 hours.

  The laminated body after drying was further heat-treated at 160 ° C. for 15 hours using a far infrared heater. In the laminated body after the heat treatment, the adhesion between the negative electrode active material-containing layer and the current collector and the adhesion between the negative electrode active material-containing layer and the coat layer are strong, and the negative electrode active material-containing layer can be formed by cutting or bending. There was no peeling from the current collector, and the coating layer did not peel from the negative electrode active material-containing layer.

  The laminate was cut into a width of 37 mm to obtain a strip-shaped negative electrode.

Production of positive electrode A positive electrode was produced as follows. First, 96% by mass of LiCoO ₂ as a positive electrode material (positive electrode active material) (content in the total solid content; the same shall apply hereinafter) and 2% by mass of ketjen black (average particle size 0.05 μm) as a conductive auxiliary agent Then, a positive electrode mixture-containing slurry obtained by mixing 2% by mass of PVDF as a binder and dehydrated NMP was applied to both sides of a current collector made of an aluminum foil having a thickness of 15 μm, dried and pressed, and a current collector A positive electrode active material-containing layer having a thickness of 85 μm per one surface was formed on both surfaces of the laminate to obtain a laminate. The laminate was cut into a width of 36 mm to obtain a strip-shaped positive electrode.

Production of non-aqueous secondary battery A negative electrode, a separator made of a microporous polyethylene film, and a positive electrode were wound into a roll, and then welded to a terminal to make aluminum having a thickness of 4 mm, a width of 34 mm, and a height of 43 mm (463443 type) Was inserted into the positive electrode can and welded with a lid. Thereafter, 2.5 g of an electrolytic solution (non-aqueous electrolyte) prepared by dissolving 1 mol of LiPF ₆ in a solvent of EC: DEC = 3: 7 (volume ratio) was poured into the container from the liquid inlet of the lid and sealed. Thus, a square non-aqueous secondary battery was obtained.

(Example 2)
SiO (average particle size 1 μm), fibrous carbon (average length 2 μm, average diameter 0.08 μm), and polyvinylpyrrolidone 10 g are mixed in 1 L of ethanol, and these are further mixed in a wet jet mill. Thus, a slurry was obtained. The total mass of SiO and fibrous carbon (CF) used for the preparation of this slurry was 100 g, and the mass ratio was SiO: CF = 89: 11. Next, composite particles of SiO and CF were produced using the slurry by a spray drying method (atmospheric temperature 200 ° C.). The average particle size of the composite particles was 10 μm. Subsequently, the composite particles are heated to about 1000 ° C. in a boiling bed reactor, a mixed gas of 25 ° C. composed of benzene and nitrogen gas is brought into contact with the heated composite particles, and a CVD treatment is performed at 1000 ° C. for 60 minutes. went. In this way, carbon generated by thermal decomposition of the mixed gas was deposited on the composite particles to form a coating layer, and a negative electrode material (negative electrode active material) was obtained.

  When the composition of the negative electrode material was calculated from the mass change before and after the coating layer was formed, it was SiO: CF: CVD carbon = 80: 10: 10 (mass ratio).

  Next, 90% by mass of the negative electrode material (content in the total solid content; the same shall apply hereinafter), 2% by mass of Ketjen black (average particle size 0.05 μm) as a conductive additive, and polyamideimide (Hitachi as a binder) 8% by mass of “HPC-9000-21” manufactured by Kasei Co., Ltd. and dehydrated NMP were mixed to prepare a negative electrode mixture-containing slurry. A negative electrode was prepared in the same manner as in Example 1 except that this negative electrode mixture-containing slurry was used to form the negative electrode active material-containing layer. Except that this negative electrode was used, a rectangular non-aqueous solution was obtained in the same manner as in Example 1. A secondary battery was produced.

(Example 3)
SiO (average particle size 1 μm), graphite (average particle size 2 μm), and polyvinylpyrrolidone 10 g were mixed in 1 L of ethanol, and these were further mixed in a wet jet mill to obtain a slurry. The mass ratio of SiO and graphite used for the preparation of this slurry was SiO: graphite = 91: 9. Next, composite particles of SiO and graphite were produced using the slurry by a spray drying method (atmosphere temperature 200 ° C.). The average particle size of the composite particles was 15 μm. Subsequently, the composite particles are heated to about 1000 ° C. in a boiling bed reactor, a mixed gas of 25 ° C. composed of benzene and nitrogen gas is brought into contact with the heated composite particles, and a CVD treatment is performed at 1000 ° C. for 60 minutes. went. In this way, carbon generated by thermal decomposition of the mixed gas was deposited on the composite particles to form a coating layer, and composite particles covered with the carbon coating layer were obtained.

  Subsequently, 100 g of the composite particles covered with the carbon coating layer and 40 g of phenol resin are dispersed in 1 L of ethanol, and the dispersion is sprayed and dried (atmosphere temperature 200 ° C.) to be covered with the carbon coating layer. The surface of the composite particles was coated with a phenol resin. Thereafter, the coated composite particles were fired at 1000 ° C. to form a material layer containing non-graphitizable carbon covering the carbon coating layer, and a negative electrode material (negative electrode active material) was obtained.

  The composition of the negative electrode material was calculated from the mass change before and after the formation of the carbon coating layer and before and after the formation of the material layer containing non-graphitizable carbon. SiO: graphite: CVD carbon: non-graphitizable carbon = 75: 7: 10: 8 (Mass ratio).

  Next, 90% by mass of the negative electrode material (content in the total solid content; the same shall apply hereinafter), 2% by mass of Ketjen black (average particle size 0.05 μm) as a conductive additive, and polyamideimide (Hitachi as a binder) 8% by mass of “HPC-9000-21” manufactured by Kasei Co., Ltd. and dehydrated NMP were mixed to prepare a negative electrode mixture-containing slurry. A negative electrode was prepared in the same manner as in Example 1 except that this negative electrode mixture-containing slurry was used to form the negative electrode active material-containing layer. Except that this negative electrode was used, a rectangular non-aqueous solution was obtained in the same manner as in Example 1. A secondary battery was produced.

Example 4
SiO (average particle size 1 μm), graphite (average particle size 3 μm), and polyethylene resin particles as a binder are put into a 4 L stainless steel container, and further stainless steel balls are put in a vibration mill and mixed for 3 hours. , Pulverization and granulation. As a result, composite particles (composite particles of SiO and graphite) having an average particle diameter of 20 μm could be produced. Subsequently, the composite particles are heated to about 950 ° C. in a boiling bed reactor, a mixed gas of 25 ° C. composed of toluene and nitrogen gas is brought into contact with the heated composite particles, and CVD treatment is performed at 950 ° C. for 60 minutes. went. In this way, carbon produced by thermal decomposition of the mixed gas was deposited on the composite particles to form a coating layer, and a negative electrode material (negative electrode active material) was obtained.

  When the composition of the negative electrode material was calculated from the mass change before and after the carbon coating layer was formed, it was SiO: graphite: CVD carbon = 80: 10: 10 (mass ratio).

  Next, 90% by mass of the negative electrode material (content in the total solid content; the same shall apply hereinafter), 2% by mass of Ketjen black (average particle size 0.05 μm) as a conductive additive, and polyamideimide (Hitachi as a binder) 8% by mass of “HPC-9000-21” manufactured by Kasei Co., Ltd. and dehydrated NMP were mixed to prepare a negative electrode mixture-containing slurry. A negative electrode was prepared in the same manner as in Example 1 except that this negative electrode mixture-containing slurry was used to form the negative electrode active material-containing layer. Except that this negative electrode was used, a rectangular non-aqueous solution was obtained in the same manner as in Example 1. A secondary battery was produced.

(Example 5)
A negative electrode was produced in the same manner as in Example 1 except that the binder in the negative electrode mixture was changed to polyimide, and a rectangular non-aqueous secondary battery was produced in the same manner as in Example 1 except that this negative electrode was used. .

(Example 6)
95% by mass of the same α-alumina as used in Example 1 (content in the total solid content; the same shall apply hereinafter), 5% by mass of polyamideimide (“HPC-9000-21” manufactured by Hitachi Chemical Co., Ltd.), A slurry for forming a coating layer was prepared by mixing with dehydrated NMP. A negative electrode was produced in the same manner as in Example 1 except that the above-mentioned slurry for forming a coat layer was used for forming the coat layer on the surface of the negative electrode active material-containing layer. A rectangular non-aqueous secondary battery was produced in the same manner.

(Example 7)
A negative electrode was produced in the same manner as in Example 1 except that the coat layer was not formed. A square non-aqueous secondary battery was produced in the same manner as in Example 1 except that this negative electrode was used.

(Comparative Example 1)
Using electrolytic copper foil (0.2% proof stress 210 N / mm ² , tensile strength 250 N / mm ² ) with a thickness of 10 μm, in the same manner as in Example 1, copper fine particles having a thickness of about 2 μm on each side A negative electrode current collector having a metal layer formed thereon was produced. The surface roughness Rz of this negative electrode current collector was 2 μm. A negative electrode was produced in the same manner as in Example 1 except that the negative electrode current collector was used. A square nonaqueous secondary battery was produced in the same manner as in Example 1 except that this negative electrode was used.

(Comparative Example 2)
A negative electrode was produced in the same manner as in Example 1 except that the binder in the negative electrode mixture was changed to PVDF, and a square nonaqueous secondary battery was produced in the same manner as in Example 1 except that this negative electrode was used. .

(Comparative Example 3)
A negative electrode was produced in the same manner as in Comparative Example 1 except that no coating layer was formed, and a rectangular non-aqueous secondary battery was produced in the same manner as in Example 1 except that this negative electrode was used.

(Comparative Example 4)
A negative electrode was prepared in the same manner as in Example 7 except that the metal layer was not formed on the surface of the rolled copper alloy foil and used as it was as a negative electrode current collector. Except that this negative electrode was used, Example 7 and A rectangular non-aqueous secondary battery was produced in the same manner.

  For the batteries of Examples 1 to 7 and Comparative Examples 1 to 4, the battery thickness change measurement during charging, the discharge capacity measurement, and the charge / discharge cycle characteristics (capacity maintenance rate at the 200th charge / discharge cycle) were evaluated. went.

  The charge / discharge of the battery in the measurement of the discharge capacity and evaluation of the charge / discharge cycle characteristics was performed under the following conditions. Charging was performed at a constant current with a current of 400 mA. After the charging voltage reached 4.2 V, the charging was performed at a constant voltage until the current became 1/10. The discharge was performed at a constant current with a current of 400 mA, and the discharge end voltage was 2.5V. The series of operations of charging and discharging was defined as one cycle. And the discharge capacity of the battery was evaluated by the discharge capacity (C1) at the second charge / discharge cycle. Further, the capacity maintenance rate at the 200th cycle was calculated from the C1 and the discharge capacity (C2) at the 200th cycle by the following formula.

Capacity maintenance rate (%) = (C2 / C1) × 100
Further, charging is performed under the same charging conditions as in the battery characteristic evaluation described above, and the thickness of each battery is measured after the end of charging in the first cycle. The amount was determined.

  Table 1 shows the measurement results regarding the discharge capacity measurement, the discharge capacity retention ratio at the 200th cycle, and the amount of change in battery thickness during charging, together with the 0.2% proof stress and tensile strength of the negative electrode current collector.

  As shown in Table 1, the prismatic non-aqueous secondary batteries of Examples 1 to 7 have a high capacity, and the amount of change in battery thickness is less than that of the prismatic non-aqueous secondary batteries of Comparative Examples 1 to 4. Furthermore, in the batteries of Examples 1 to 7 (particularly, the batteries of Examples 1 to 6), it can be confirmed that the discharge capacity retention rate after repeated charge and discharge is high and the charge and discharge cycle characteristics are excellent.

  Each of the above results shows that in the batteries of Examples 1 to 7, a high strength copper foil having a large 0.2% proof stress or tensile strength was used for the negative electrode current collector, and the surface of the negative electrode current collector was roughened. In addition, by using a specific binder in the negative electrode active material-containing layer, it was possible to suppress deformations such as volume change and bending of the negative electrode due to expansion / contraction of the active material during charge / discharge it is conceivable that.

  According to the present invention, it is possible to provide a non-aqueous secondary battery with high capacity, good charge / discharge cycle characteristics, and suppressed battery swelling.

Claims (13)

A positive electrode current collector, a positive electrode having a positive electrode active material-containing layer containing a Li-containing transition metal oxide formed on at least one surface of the positive electrode current collector, a negative electrode current collector , and at least one of the negative electrode current collectors A method for producing a non-aqueous secondary battery comprising a negative electrode having a negative electrode active material-containing layer formed on one side and a non-aqueous electrolyte,
0.2% proof stress of the negative electrode current collector is 250 N / mm ² or more, or the tensile strength of the negative electrode current collector is 300 N / mm ² or more,
On the surface of the negative electrode assembly, the 10-point average roughness Rz of the surface is 0.6 to 10 μm.
A roughening treatment step of providing a fine granular metal layer to be,
At least one of the roughened surfaces of the negative electrode current collector has Si and O as constituent elements, and the atomic ratio x of O to Si is 0.5 ≦ x ≦ 1.5. Forming a negative electrode active material-containing layer containing a negative electrode active material containing a material and at least one binder selected from the group consisting of polyimide, polyamideimide and polyamide;
Heat-treating the negative electrode active material-containing layer at 200 ° C. or lower;
The manufacturing method of the non-aqueous secondary battery characterized by including.   2. The non-aqueous electrolyte according to claim 1, wherein the negative electrode current collector is made of a Cu alloy containing at least one element selected from the group consisting of Zr, Cr, Sn, Zn, Ni, Si, and P. 3. A method for manufacturing a secondary battery.   The method for producing a non-aqueous secondary battery according to claim 1, wherein the negative electrode current collector is a rolled foil. The method for producing a non-aqueous secondary battery according to claim 1, wherein the roughening treatment step is performed by any one of electrolytic plating, electroless plating, sputtering, and vapor deposition. The metal layer of the fine particulate, the nonaqueous secondary battery manufacturing method according to claims 1 to 4, wherein the configuring the main constituent metal or an alloy negative electrode current collector. Wherein the anode active material-containing layer, the negative active material with, method for producing a nonaqueous secondary battery according to any one of claims 1 to 5 you containing a carbon material as a conductive material. The negative electrode active material, comprising Si and O as constituent elements, a material in which an atomic ratio x of O to Si is 0.5 ≦ x ≦ 1.5, and the carbon contained in the negative electrode active material-containing layer method for producing a nonaqueous secondary battery according to claim 6 which constitutes a complex with at least a portion of the material. The method for producing a nonaqueous secondary battery according to claim 6 or 7, wherein the surface of the negative electrode active material is covered with at least a part of the carbon material.   The method for producing a non-aqueous secondary battery according to claim 6, wherein the amount of the conductive material in the negative electrode active material-containing layer is 5 to 50% by mass. Wherein the surface opposite to the negative electrode active material-containing layer and the negative electrode current collector, according to claim 1 including the step of forming a porous layer containing a material of the insulating which does not react with Li Manufacturing method for non-aqueous secondary battery.   The method for manufacturing a non-aqueous secondary battery according to claim 10, wherein the insulating material that does not react with Li is alumina or boehmite. Wherein the porous layer, a polyimide, a manufacturing method of a non-aqueous secondary battery according to claim 10 or 11 you containing at least one binder selected from the group consisting of polyamide-imide and polyamide.   The method for producing a non-aqueous secondary battery according to claim 10, wherein the porous layer has a thickness of 2 to 10 μm.