JP5196118B2 - Non-aqueous electrolyte secondary battery and manufacturing method thereof - Google Patents

Description

  The present invention relates to a non-aqueous electrolyte secondary battery and a method for manufacturing the same, and more particularly to a lithium ion secondary battery and a method for manufacturing the same.

  In recent years, the use of lithium ion secondary batteries having a high energy density as portable power sources for notebook computers, mobile phones, and digital cameras is increasing. Also, lithium ion secondary batteries are being studied as a power source for electric vehicles that are expected to be put into practical use as environmentally friendly vehicles.

  Conventional lithium-ion secondary batteries have used a carbon material as an active material for the negative electrode. However, due to recent demands for capacity enhancement, they are alloyed with lithium such as silicon that can be expected to have high charge / discharge capacity. It is considered to use metals and their oxides as negative electrode active materials. However, when such an alloying metal is used as an active material, high capacity can be expected, but lithium in the positive electrode material is introduced into the negative electrode material for the first charge, and all lithium cannot be taken out by discharge. Thus, a certain amount of irreversible lithium remains in the negative electrode. As a result, there is a problem that the discharge capacity of the battery is reduced and the battery capacity is reduced. Many measures to solve this problem have been proposed and implemented so far, and many are introduced in patent literature.

  That is, in Patent Document 1 (JP-A-5-226003), a method of replenishing with an irreversible capacity of an organic lithium compound, and in Patent Document 2 (JP-A-10-223259), metallic lithium is disposed on the upper part of the battery case. Japanese Patent No. 3403858 proposes a method of compensating for irreversible capacity lithium by arranging lithium in the cross-sectional direction of the positive electrode. Moreover, in patent document 4 (Unexamined-Japanese-Patent No. 2003-234125), a metal lithium foil is affixed on a battery case, and after injection | pouring of nonaqueous electrolyte, the electric potential of a negative electrode is initial in the range of 2.5V <E <3.2V. Thus, there has been proposed a method for improving the cycle characteristics by suppressing the deposition of impurity metal ions and preventing a minute short circuit by performing the above charging. These are useful methods for reducing the battery capacity, but they are difficult to implement industrially due to limited handling locations such as complicated processes and complicated work in an environment where lithium does not react. It was.

JP-A-5-226003 JP-A-10-223259 Japanese Patent No. 3403858 JP 2003-234125 A

  The present invention has been made in view of the above circumstances, and can easily compensate for irreversible capacity lithium remaining in the negative electrode, improve battery performance, and is excellent in handleability during production. An object of the present invention is to provide a secondary battery and a manufacturing method thereof.

  As a result of intensive studies to achieve the above object, the present inventor has found a simple method and a method that can be easily handled at a dew point of about minus 40 ° C., and has reached the present invention. In other words, by using a lithium-containing film prepared using a metal lithium powder obtained by processing metal lithium in a powder form on the negative electrode, it becomes possible to compensate for irreversible lithium remaining in the negative electrode, and battery capacity Found a way to improve.

Accordingly, the present invention provides the following nonaqueous electrolyte secondary battery and a method for manufacturing the same.
(1) a negative electrode using a negative electrode active material containing silicon capable of inserting and extracting lithium ions;
A positive electrode using a positive electrode active material containing an oxide, sulfide or organic polymer compound capable of inserting and extracting lithium ions;
A lithium-containing film made of a mixture containing a metallic lithium powder or a metallic lithium powder surface-coated with an organic rubber, an organic resin or a metal carbonate, a binder, and a conductive material;
In a non-aqueous electrolyte secondary battery using a non-aqueous electrolyte containing a lithium salt,
A nonaqueous electrolyte secondary battery, wherein the negative electrode has a film containing lithium at least on the positive electrode side.
(2) In the lithium-containing film, the binder is polyvinylidene fluoride, styrene / butadiene copolymer, polytetrafluoroethylene resin, tributadiene rubber, ethylene vinyl alcohol copolymer resin, polyamide resin, polyimide resin, and polyamide. An imide resin is selected, and the amount thereof is 0.1 to 70 parts by mass with respect to 100 parts by mass of metallic lithium, and the amount of the conductive material is 0.1 to 70 parts by mass with respect to 100 parts by mass of metallic lithium. (1) The nonaqueous electrolyte secondary battery as described.
(3) The negative electrode includes a current collector sheet, a negative electrode active material layer is formed on one surface of the negative electrode current collector sheet, and a film containing lithium is formed on the negative electrode active material layer (1 Or the nonaqueous electrolyte secondary battery according to (2).
(4) The negative electrode includes a current collector sheet, and a negative electrode active material layer is formed on both sides of the negative electrode current collector sheet, and a film containing lithium is formed on each of the negative electrode active material layers. The nonaqueous electrolyte secondary battery according to (1) or (2).
(5) The method for producing a non-aqueous electrolyte secondary battery according to (1), wherein metal lithium powder or metal lithium powder surface-coated with organic rubber, organic resin or metal carbonate, a binder, and a conductive material A slurry containing a dehydrated solvent is directly applied to at least the positive electrode side surface of the negative electrode, and dried to form a film containing lithium on at least the positive electrode surface of the negative electrode. A method for producing a water electrolyte secondary battery.
(6) The negative electrode includes a current collector sheet, and a negative electrode active material layer is formed on one surface of the current collector sheet, and the slurry is directly applied on the negative electrode active material layer, and then dried to form lithium. (5) The manufacturing method of the nonaqueous electrolyte secondary battery as described in (5) including the process of forming the film | membrane containing this.
(7) The negative electrode includes a current collector sheet, and the negative electrode active material layers are formed on both sides of the current collector sheet, and the slurry is directly applied on both the negative electrode active material layers and dried. comprising the step of film a film containing lithium Te (5) the method of producing a non-aqueous electrolyte secondary battery according.
(8) A method for producing a non-aqueous electrolyte secondary battery according to (1), wherein metal lithium powder or metal lithium powder surface-coated with organic rubber, organic resin or metal carbonate, a binder, a conductive material, and A method for producing a nonaqueous electrolyte secondary battery, comprising: forming a film containing lithium in advance from a slurry containing a dehydrated solvent; and bonding the film to at least a positive electrode side surface of a negative electrode.
(9) The negative electrode includes a current collector sheet, and includes a step of forming a negative electrode active material layer on one surface of the current collector sheet and bonding the lithium-containing film on the negative electrode active material layer. 8 ) A method for producing a non-aqueous electrolyte secondary battery as described above.
(10) A step in which the negative electrode includes a current collector sheet, and a negative electrode active material layer is formed on both surfaces of the current collector sheet, and a film containing lithium is bonded to each of the negative electrode active material layers. The manufacturing method of the nonaqueous electrolyte secondary battery as described in ( 8 ).
(11) The production method according to any one of (5) to (10), wherein the dehydrated solvent is N-methylpyrrolidone, toluene, xylene, or methyl ethyl ketone.

  According to the production method of the present invention, the irreversible capacity lithium remaining in the negative electrode can be supplemented by a simple method, the battery capacity is improved, and the non-aqueous electrolyte secondary that can be easily handled at a dew point of about −40 ° C. Battery can be provided.

  The non-aqueous electrolyte secondary battery of the present invention includes a negative electrode using a negative electrode active material containing silicon capable of occluding and releasing lithium ions, an oxide capable of occluding and releasing lithium ions, and sulfide. A positive electrode using a positive electrode active material containing a product or an organic polymer compound, and a non-aqueous electrolyte containing a lithium salt.

Here, examples of the positive electrode active material include oxides, sulfides, and organic polymer compounds capable of occluding and releasing lithium ions, and any one or more of these are used. Specifically, for example, TiS ₂ , MoS ₂ , NbS ₂ , ZrS ₂ , VS ₂ , V ₂ O ₅ , MoO ₃ , Mg (V ₃ O ₈ ) ₂ and other metal sulfides and oxides not containing lithium, or lithium composite oxide is exemplified containing lithium and a composite metal such as NbSe ₂ can also be mentioned. Among these, in order to increase the energy density, a lithium composite oxide mainly composed of Li (Met) _x O ₂ is preferable. Specifically, Met is preferably at least one of cobalt, nickel, iron, and manganese, and x is usually a value in the range of 0.05 ≦ x ≦ 1.10. Specific examples of such a lithium composite oxide include LiCoO ₂ , LiNiO ₂ , LiFeO ₂ , Li _x Ni _y Co _1-y O ₂ having a layer structure (where 0.05 ≦ x ≦ 1.10, 0 ≦ y ≦ 1), spinel-structured LiMn ₂ O ₄ and orthorhombic LiMnO ₂ . Furthermore, substituted spinel manganese compounds LiMet _x Mn _1-x O ₄ (where 0 ≦ x ≦ 1) are also used as high voltage types, where Met is titanium, chromium, iron, cobalt, copper, zinc, etc. Is mentioned.

  The lithium composite oxide is obtained by, for example, grinding lithium carbonate, nitrate, chloride or hydroxide and transition metal carbonate, nitrate, oxide or hydroxide according to a desired composition. It is prepared by mixing and baking at a temperature in the range of 600 to 1,000 ° C. in an oxygen atmosphere.

  Furthermore, an organic polymer compound can also be used as the positive electrode active material. Illustrative examples include high molecular compounds such as conductive polymers such as polyacetylene, polypyrrole, polyparaphenylene, polyaniline, polythiophene, polyacene, and polysulfide compounds.

  Examples of the negative electrode active material include an active material containing silicon capable of inserting and extracting lithium ions. Specifically, chemical-grade silicon from which metal impurities are removed by washing with high-purity silicon powder or hydrochloric acid with a metal impurity concentration of 1 ppm or less and then treating with hydrofluoric acid or a mixture of hydrofluoric acid and nitric acid. Powders and metallurgically refined metal silicon processed into powder, their alloys, lower oxides and partial oxides of silicon, silicon nitrides and partial nitrides, and further for conducting a conductive treatment Including those mixed with a carbon material, alloyed by mechanical alloying, etc., coated with a conductive material such as metal by sputtering or plating, and carbon deposited with an organic gas.

  In this case, the negative electrode active material is a particle having a structure in which silicon microcrystals having a size of 1 to 500 nm are dispersed in a silicon-based compound, particularly silicon dioxide, as described in JP-A-2004-47404. Those having a surface coated with carbon are preferred.

There is no restriction | limiting in particular about the preparation methods of a positive electrode and a negative electrode. In general, an active material, a binder, a conductive agent or the like is added to a solvent to form a slurry, which is applied to a current collector sheet, dried and pressed.
Examples of the binder generally include polyvinylidene fluoride, polytetrafluoroethylene, styrene / butadiene rubber, isoprene rubber, various polyimide resins, and the like.
Examples of the conductive agent generally include carbon-based materials such as graphite and carbon black, and metal materials such as copper and nickel.
Examples of the current collector include aluminum or an alloy thereof for the positive electrode, and a metal such as copper, stainless steel, nickel, or an alloy thereof for the negative electrode.

  The separator used between the positive electrode and the negative electrode is not particularly limited as long as it is stable with respect to the electrolytic solution and has excellent liquid retention, but is generally a porous sheet of polyolefin such as polyethylene or polypropylene, or a nonwoven fabric. Is mentioned.

The nonaqueous electrolytic solution of the present invention contains an electrolyte salt and a nonaqueous solvent. Examples of the electrolyte salt include light metal salts. Light metal salts include alkali metal salts such as lithium salts, sodium salts, or potassium salts, alkaline earth metal salts such as magnesium salts or calcium salts, or aluminum salts. Selected. For example, in the case of a lithium salt, LiBF ₄ , LiClO ₄ , LiPF ₆ , LiAsF ₆ , CF ₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, C ₄ F ₉ SO ₃ Li, CF ₃ CO ₂ Li, ( CF ₃ CO ₂ ) ₂ NLi, C ₆ F ₅ SO ₃ Li, C ₈ F ₁₇ SO ₃ Li, (C ₂ F ₅ SO ₂ ) ₂ NLi, (C ₄ F ₉ SO ₂ ) (CF ₃ SO ₂ ) NLi , (FSO ₂ C ₆ F ₄ ) (CF ₃ SO ₂ ) NLi, ((CF ₃ ) ₂ CHOSO ₂ ) ₂ NLi, (CF ₃ SO ₂ ) ₃ CLi, (3,5- (CF ₃ ) ₂ C ₆ F ₃ ) ₄ BLi, LiCF ₃ , LiAlCl _4, or C ₄ BO ₈ Li may be used, and any one or two of these may be used in combination.

  The concentration of the electrolyte salt in the nonaqueous electrolytic solution is preferably 0.5 to 2.0 mol / L from the viewpoint of electrical conductivity. The conductivity of the electrolyte at 25 ° C. is preferably 0.01 S / m or more, and is adjusted by the type of electrolyte salt or its concentration.

The solvent for non-aqueous electrolyte used in the present invention is not particularly limited as long as it can be used for non-aqueous electrolyte. Generally, aprotic high dielectric constant solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, dipropyl carbonate, diethyl ether, tetrahydrofuran, 1,2, -Aprotic low viscosity such as acetate ester or propionate ester such as dimethoxyethane, 1,2-diethoxyethane, 1,3-dioxolane, sulfolane, methylsulfolane, acetonitrile, propionitrile, anisole, methyl acetate A solvent is mentioned. It is desirable to use these aprotic high dielectric constant solvents and aprotic low viscosity solvents in combination at an appropriate mixing ratio. Furthermore, ionic liquids using imidazolium, ammonium, and pyridinium type cations can be used. The counter anion is not particularly limited, and examples thereof include BF ₄ ⁻ , PF ₆ ⁻ , (CF ₃ SO ₂ ) ₂ N ^{− and the} like. The ionic liquid can be used by mixing with the aforementioned non-aqueous electrolyte solvent.

  In the case of a solid electrolyte or gel electrolyte, it is possible to contain silicone gel, silicone polyether gel, acrylic gel, acrylonitrile gel, poly (vinylidene fluoride) and the like as a polymer material. These may be polymerized in advance or may be polymerized after injection. These can be used alone or as a mixture.

  Furthermore, you may add various additives in the non-aqueous electrolyte of this invention as needed. For example, vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, 4-vinylethylene carbonate and the like for the purpose of improving cycle life, biphenyl, alkylbiphenyl, cyclohexylbenzene, t-butylbenzene, diphenyl ether for the purpose of preventing overcharge, Examples include benzofuran, various carbonate compounds for the purpose of deoxidation and dehydration, various carboxylic acid anhydrides, various nitrogen-containing compounds, and sulfur-containing compounds.

  The shape of the battery is arbitrary and is not particularly limited. In general, a coin type in which an electrode punched into a coin shape and a separator are stacked, a cylinder type in which an electrode sheet and a separator are spiraled, and the like can be given.

  In the present invention, in such a nonaqueous electrolyte secondary battery, a film containing lithium is formed on at least the positive electrode side of the negative electrode by coating or bonding.

  In other words, the negative electrode active material containing silicon described above has a higher charge / discharge capacity than graphite conventionally used, but the lithium introduced into the negative electrode material by the first charge is not taken out by discharge and is constant. There is an irreversible capacity lithium that remains in the negative electrode, especially silicon oxide, which is a lower oxide of silicon, which shows excellent cycle characteristics, but the irreversible capacity lithium is large and has a problem in practical use. However, this problem can be solved by forming the lithium-containing film.

  In this case, the film containing lithium is preferably a film of a mixture containing metal lithium powder or surface-coated metal lithium powder, a binder, and a conductive material.

As the metallic lithium powder according to the present invention, it is preferable to use a stabilized lithium powder. By stabilizing the lithium powder, the modification of the lithium powder does not proceed even in a dry room having a dew point of about −40 ° C. Here, the stabilization of the lithium powder is a material having good environmental stability on the surface of the lithium powder, for example, organic rubber such as NBR (nitrile butadiene rubber) and SBR (styrene butadiene rubber), EVA (ethylene vinyl alcohol copolymer resin). ) And other inorganic compounds such as metal carbonates such as Li ₂ CO ₃ , and commercially available products include SLMP manufactured by FMC and lithium powder manufactured by Aldrich.

  Examples of the binder include polyvinylidene fluoride, styrene / butadiene copolymer, polytetrafluoroethylene resin, tributadiene rubber, ethylene vinyl alcohol copolymer resin, polyamide resin, polyimide resin, polyamideimide resin, and the like. Is preferably 0.1 to 70 parts by mass, particularly preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the lithium metal.

  Examples of the conductive material include metal powders such as acetylene black, graphite, carbon fiber, copper, stainless steel, nickel, metal fibers, or powders or fibers of two or more of these alloys. It is preferable to set it as 0.1-70 mass parts with respect to 100 mass parts, especially 0.2-10 mass parts.

  The mixture composed of the lithium metal powder, the binder, and the conductive material is made into a slurry by adding a dehydrated solvent such as N-methylpyrrolidone, toluene, xylene, methyl ethyl ketone, and the like, for example, a nitrogen glove box having a dew point of −40 ° C. In the negative electrode and dried to form a lithium-coated negative electrode, or the slurry is formed into a film, the lithium-containing film is bonded to the negative electrode, and dried to form a lithium bonded negative electrode can do.

  In this case, the lithium-containing film is formed on at least the positive electrode side of the negative electrode, but it is preferable to form the lithium-containing film on the surface of the negative electrode current collector sheet coated with the negative electrode active material by coating or bonding. . That is, a negative electrode active material layer is formed on one surface of the current collector sheet, and a lithium-containing film is formed thereon, or a negative electrode active material layer is formed on both surfaces of the current collector sheet. A lithium-containing film is preferably formed on each layer. The lithium-containing film is arranged so as to face the positive electrode. In this case, for example, the negative electrode active material layer and the lithium-containing film are formed on one surface of the current collector sheet, in a coin-type battery, A mode in which a negative electrode active material layer and a lithium-containing film are formed on both surfaces is effective for a cylinder type battery.

  In the non-aqueous electrolyte secondary battery of the present invention, the lithium film functions so that lithium formed on the current collector sheet is diffused into the negative electrode active material layer by the first charge. Since this lithium film is used to supplement the irreversible capacity of the negative electrode, it is desirable that the amount of addition be less than or equal to the amount sufficient to supplement the irreversible capacity of the negative electrode. The optimum addition amount of lithium varies depending on the amount and material of the negative electrode active material, and the irreversible capacity decreases depending on the addition amount, but if it is too much, lithium is deposited on the negative electrode, and conversely the battery capacity decreases. To do. Therefore, it is preferable to determine the optimum addition amount of lithium after separately obtaining the initial efficiency of the negative electrode, and is determined according to the thickness (use amount) of the negative electrode in battery design.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In the following examples,% indicates mass%.

[Example 1]
[Preparation of negative electrode active material (conductive silicon composite)]
A conductive silicon composite as a negative electrode active material was prepared based on the description in JP-A-2004-47404. The production method is described below.
A mixed powder prepared by mixing silicon dioxide powder (BET specific surface area = 200 m ² / g) and metal silicon powder for chemical grade (BET specific surface area = 4 m ² / g) at an equimolar ratio was 1,350 ° C., 0.1 Torr. Then, the generated SiO _x gas was deposited on a water-cooled SUS substrate. Next, this precipitate was collected and then pulverized with a ball mill in hexane for 5 hours to obtain a silicon oxide powder (SiO _x : x = 1.02) having d ₅₀ = 8 μm. The powder obtained here was subjected to X-ray diffraction using Cu-Kα rays, and it was confirmed that the obtained powder was amorphous silicon oxide (SiO _x ) powder.

The obtained silicon oxide powder was subjected to thermal CVD simultaneously with disproportionation of silicon oxide using a rotary kiln type reactor under the conditions of 1,150 ° C. and average residence time of about 2 hours under methane-argon mixed gas flow. It was. After the operation was completed, the temperature was lowered and black powder was recovered. The amount of deposited carbon of the obtained black powder is 22.0%. From the X-ray diffraction pattern, the obtained black powder is different from silicon oxide powder in Si (111) near 2θ = 28.4 °. There is an assigned diffraction line, and the size of the crystal is obtained by the Scherrer method from the half width of this diffraction line. The size of the silicon crystal dispersed in the silicon dioxide is 11 nm. A conductive silicon composite powder in which (Si) crystals are dispersed in silicon dioxide (SiO ₂ ) was produced.

[Production of negative electrode]
The negative electrode was produced according to the following procedure.
10% of polyimide is added to 5 g of conductive silicon composite powder, N-methylpyrrolidone is further added to form a slurry, and this slurry is applied to one surface of a copper foil having a thickness of 20 μm (coating amount of conductive silicon composite powder: 1.5 mg / cm ² ), after vacuum drying at 80 ° C. for 1 hour, the electrode was press-molded by a roller press and vacuum dried at 350 ° C. for 1 hour to obtain a negative electrode.

[Preparation of paste containing lithium]
The lithium-containing paste was produced according to the following procedure.
0.5 g of acetylene black was added to 1 g of lithium powder 50 to 150 μm (Cat. No. 5905884) manufactured by Aldrich, and polyvinylidene fluoride was further added to 3% of the composition. N-methylpyrrolidone dehydrated with molecular sieves was added to this to form a slurry, which was applied to the other surface of the negative electrode copper foil prepared in a nitrogen glove bag with a dew point of −40 ° C., and vacuum-dried at 100 ° C. for 1 hour. Thus, a lithium-containing film-forming negative electrode was punched out to 2 cm ² .

[Production of battery]
As a positive electrode material, a single layer sheet (Pionix Co., Ltd., trade name: Pioxel C-100) using LiCoO ₂ as an active material and an aluminum foil as a current collector was punched into 2 cm ² to obtain a positive electrode.

  1 mol of lithium hexafluorophosphate as a non-aqueous electrolyte in a 1/1 (volume ratio) mixture of ethylene carbonate and diethyl carbonate in a glove box (dew point -80 ° C or lower) with the obtained positive electrode and lithium-containing negative electrode Using a non-aqueous electrolyte solution dissolved at a concentration of / L, using a polyethylene microporous film having a thickness of 30 μm as a separator, a 2032 type coin battery is stacked in the order of a positive electrode, a separator, and a lithium-containing film-forming negative electrode. A lithium electrolyte secondary battery for evaluation was prepared by adding a water electrolyte solution. In this case, the negative electrode was disposed so that the lithium-containing film was present on the positive electrode side.

The produced lithium ion secondary battery was allowed to stand at room temperature overnight, and then charged with a secondary battery charge / discharge test apparatus (manufactured by Nagano Co., Ltd.) until the voltage of the test cell reached 4.2V. Charging was performed at a constant current of 5 mA / cm ² . Discharging was performed at a constant current of 0.5 mA / cm ² , and when the cell voltage fell below 2.5 V, the discharging was terminated and the discharge capacity was determined. The above charge / discharge test was repeated 50 times, and the cycle retention after 50 cycles was determined. The results are shown in Table 1.

[Example 2]
Using 5 g of the negative electrode active material (conductive silicon composite powder) prepared in Example 1, 10% polyvinylidene fluoride was added thereto, and N-methylpyrrolidone was further added to form a slurry. This slurry was made into copper having a thickness of 20 μm. It apply | coated to one side of foil, and after vacuum-drying at 120 degreeC for 1 hour, the negative electrode was pressure-molded with the roller press.

0.5 g of acetylene black was added to 1 g of lithium powder 50 to 150 μm (Cat. No. 5905884) manufactured by Aldrich. Further, a xylene solution of SBR Tuftec M1943 manufactured by Asahi Kasei Co., Ltd. was added to this composition so as to be 2% with respect to the composition, and further xylene dehydrated with molecular sieves was added to obtain a slurry. This slurry was applied to the other surface of the copper foil of the negative electrode in a nitrogen glove box (dew point −40 ° C.), vacuum-dried at 100 ° C. for 1 hour, and punched into 2 cm ² as a lithium-containing film.
The positive electrode was manufactured by Pionics Co., Ltd., trade name: Pioxel C-100, and punched out to 2 cm ² to obtain a positive electrode.

The obtained positive electrode and lithium-containing film-formed negative electrode were put in an argon glove box (dew point -80 ° C. or lower), and lithium hexafluorophosphate was mixed in 1/1 (volume ratio) of ethylene carbonate and diethyl carbonate as a non-aqueous electrolyte. A non-aqueous electrolyte solution dissolved at a concentration of 1 mol / L is used, a polyethylene microporous film having a thickness of 30 μm is used as a separator, a positive electrode, a separator, and a lithium-containing film-forming negative electrode are sequentially formed in a 2032 type coin battery. A non-aqueous electrolyte solution was put on top of each other to produce a lithium ion secondary battery for evaluation. In this case, the negative electrode was arranged so that the lithium-containing film was present on the positive electrode side.
The manufactured lithium ion secondary battery was subjected to cycle characteristics in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
Using the negative electrode active material (conductive silicon composite powder) prepared in Example 1, 10% polyvinylidene fluoride was added thereto, and further N-methylpyrrolidone was added to form a slurry. This slurry was a copper foil having a thickness of 20 μm. After being dried on one surface and vacuum-dried at 120 ° C. for 1 hour, the negative electrode was pressure-formed by a roller press and punched out to 2 cm ² to obtain a negative electrode.
The positive electrode was manufactured by Pionics Co., Ltd., trade name: Pioxel C-100, and punched out to 2 cm ² to obtain a positive electrode.

The obtained positive electrode and negative electrode were put in an argon glove box (dew point -80 ° C. or lower), and lithium hexafluorophosphate was added as a non-aqueous electrolyte to a 1/1 (volume ratio) mixture of ethylene carbonate and diethyl carbonate at 1 mol / Using a non-aqueous electrolyte solution dissolved at a concentration of L, using a polyethylene microporous film with a thickness of 30 μm as a separator, stack the positive electrode, separator, and negative electrode on a 2032 type coin battery in this order, and put the non-aqueous electrolyte solution Thus, a lithium ion secondary battery for evaluation was produced.
The manufactured lithium ion secondary battery was subjected to cycle characteristics in the same manner as in Example 1. The results are shown in Table 1.

Claims (11)

A negative electrode using a negative electrode active material containing silicon capable of inserting and extracting lithium ions;
A positive electrode using a positive electrode active material containing an oxide, sulfide or organic polymer compound capable of inserting and extracting lithium ions;
A lithium-containing film made of a mixture containing a metallic lithium powder or a metallic lithium powder surface-coated with an organic rubber, an organic resin or a metal carbonate, a binder, and a conductive material;
In a non-aqueous electrolyte secondary battery using a non-aqueous electrolyte containing a lithium salt,
A nonaqueous electrolyte secondary battery, wherein the negative electrode has a film containing lithium at least on the positive electrode side. In the lithium-containing film, the binder is made of polyvinylidene fluoride, styrene / butadiene copolymer, polytetrafluoroethylene resin, tributadiene rubber, ethylene vinyl alcohol copolymer resin, polyamide resin, polyimide resin, and polyamideimide resin. The amount thereof is 0.1 to 70 parts by mass with respect to 100 parts by mass of metallic lithium, and the amount of the conductive material is 0.1 to 70 parts by mass with respect to 100 parts by mass of metallic lithium. The nonaqueous electrolyte secondary battery as described.   The negative electrode includes a current collector sheet, a negative electrode active material layer is formed on one surface of the negative electrode current collector sheet, and a film containing lithium is formed on the negative electrode active material layer. The nonaqueous electrolyte secondary battery as described.   The negative electrode includes a current collector sheet, and a negative electrode active material layer is formed on each side of the negative electrode current collector sheet, and a film containing lithium is formed on each of the negative electrode active material layers. The nonaqueous electrolyte secondary battery according to 1 or 2. The method for producing a non-aqueous electrolyte secondary battery according to claim 1, wherein metal lithium powder or metal lithium powder surface-coated with organic rubber, organic resin or metal carbonate, a binder, a conductive material, and dehydrated. A slurry containing a solvent is applied directly to at least the positive electrode side surface of the negative electrode, and this is dried to form a lithium-containing film on at least the positive electrode side surface of the negative electrode. A method for manufacturing a secondary battery. The negative electrode includes a current collector sheet, and a negative electrode active material layer is formed on one surface of the current collector sheet, and the slurry is directly applied on the negative electrode active material layer , and dried to contain lithium. The manufacturing method of the nonaqueous electrolyte secondary battery of Claim 5 including the process of forming a film | membrane. The negative electrode includes a current collector sheet, and a negative electrode active material layer is formed on both sides of the current collector sheet, and the slurry is directly applied on both the negative electrode active material layers , which are dried to obtain lithium. The method for producing a nonaqueous electrolyte secondary battery according to claim 5 , comprising a step of forming a film containing the film. The method for producing a non-aqueous electrolyte secondary battery according to claim 1, wherein the metal lithium powder or the metal lithium powder surface-coated with an organic rubber, an organic resin or a metal carbonate, a binder, a conductive material, and a dehydrated solvent A method for producing a non-aqueous electrolyte secondary battery, comprising a step of forming a film containing lithium in advance from a slurry containing and adhering the film to at least the positive electrode side surface of the negative electrode. Negative electrode comprises a current collector sheet, to form a negative electrode active material layer on one surface of the current collector sheet, comprising the step of bonding a negative electrode active material containing the lithium on layer film, according to claim 8 Of manufacturing a non-aqueous electrolyte secondary battery. The negative electrode includes a current collector sheet, and includes a step of forming a negative electrode active material layer on each side of the current collector sheet and bonding the lithium-containing film on each of the negative electrode active material layers. A method for producing a nonaqueous electrolyte secondary battery according to claim 8 . The method according to any one of claims 5 to 10, wherein the dehydrated solvent is N-methylpyrrolidone, toluene, xylene, or methyl ethyl ketone.