JP4035760B2 - Nonaqueous electrolyte secondary battery - Google Patents

Nonaqueous electrolyte secondary battery Download PDF

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Publication number
JP4035760B2
JP4035760B2 JP2001369220A JP2001369220A JP4035760B2 JP 4035760 B2 JP4035760 B2 JP 4035760B2 JP 2001369220 A JP2001369220 A JP 2001369220A JP 2001369220 A JP2001369220 A JP 2001369220A JP 4035760 B2 JP4035760 B2 JP 4035760B2
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Prior art keywords
battery
carbon
negative electrode
aqueous electrolyte
coated
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JP2001369220A
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Japanese (ja)
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JP2003168426A (en
Inventor
稔 手嶋
徹 田渕
寿之 青木
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株式会社ジーエス・ユアサコーポレーション
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a non-aqueous electrolyte secondary battery having a large discharge capacity.
[0002]
[Prior art]
In recent years, with the rapid miniaturization and diversification of consumer mobile phones, portable electronic devices and personal digital assistants, etc., the batteries that are power supplies are small, lightweight, high energy density, and repeated for a long time. There is a strong demand for the development of secondary batteries that can be charged and discharged.
[0003]
Above all, non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries have been put into practical use as active batteries as secondary batteries that meet these requirements compared to lead batteries and nickel cadmium batteries that use aqueous electrolytes. Research is being conducted.
[0004]
Such a non-aqueous electrolyte secondary battery includes, for example, a positive electrode plate in which a positive electrode active material that absorbs and releases lithium ions is held in a current collector, and a negative electrode active material that stores and releases lithium ions in a current collector. The negative electrode plate is made of an electrolyte containing a lithium salt such as LiBF 4 or LiPF 6 dissolved in an aprotic organic solvent, and is interposed between the positive electrode plate and the negative electrode plate to prevent a short circuit between both electrodes. It is made up of separators.
[0005]
The electrolyte of a non-aqueous electrolyte secondary battery generally includes a mixed solvent of a high dielectric constant solvent such as ethylene carbonate or propylene carbonate and a low viscosity solvent such as dimethyl carbonate or diethyl carbonate, LiBF 4 or LiPF 6 or the like. A solution in which the supporting salt is dissolved is used.
[0006]
Examples of the positive electrode active material of the non-aqueous electrolyte secondary battery include titanium disulfide, vanadium pentoxide, trioxide, and various compounds represented by the general formula Li x MO 2 (where M is one or more transition metals). It is being considered.
[0007]
Among them, lithium cobalt composite oxide, lithium nickel composite oxide, lithium manganese composite oxide, and the like are used as positive electrode active materials because they are charged and discharged at an extremely noble potential of 4 V (vs. Li / Li + ) or higher. Thus, a nonaqueous electrolyte secondary battery having a high discharge voltage can be realized.
[0008]
Materials that can occlude and release lithium ions, including lithium-containing alloys, have been studied as negative electrode active materials for nonaqueous electrolyte secondary batteries. There is an advantage that a water electrolyte secondary battery can be obtained and safety is high, and it is now in practical use.
[0009]
Recently, metal, metalloid, and metalloid metals having a large amount of occlusion of lithium, such as Japanese Patent Laid-Open No. 10-3920 and Japanese Patent Laid-Open No. 2000-215887, are made of carbon materials. A nonaqueous electrolyte secondary battery using a coated negative electrode active material has also been proposed.
[0010]
[Problems to be solved by the invention]
When a carbon-based material is used for the negative electrode active material, there is a limit to the theoretical capacity of lithium that can be occluded / released, which has been an obstacle to obtaining a non-aqueous electrolyte secondary battery with higher capacity and higher energy density. Therefore, a nonaqueous electrolyte secondary battery using silicon, an alloy thereof, or an oxide as a negative electrode active material replacing a carbon material has been studied.
[0011]
When these negative electrode active materials are used, the theoretical capacity of the active material itself is high. However, when used for batteries, the influence of expansion and contraction of the active material accompanying charge / discharge is large, and current collection is likely to deteriorate. However, since the electronic conductivity of the active material itself is low, the initial charge / discharge efficiency is low, and the battery has a problem that a high energy density cannot be obtained. Recently, Japanese Patent Laid-Open No. 2000-215887 and Japanese Patent Laid-Open No. 2000-285919 have also proposed means for increasing the current collecting property by coating a carbon material on the surface of silicon. Not in.
[0012]
The present invention has been made to solve the above-mentioned problems in non-aqueous electrolyte secondary batteries using silicon as a negative electrode active material, and an object thereof is to provide a non-aqueous electrolyte secondary battery having a large discharge capacity. .
[0013]
[Means for Solving the Problems]
The invention according to claim 1, a positive electrode comprising a lithium ion from a material capable of absorbing and desorbing, a negative electrode comprising a lithium ion from a material absorbing and releasing, in a non-aqueous electrolyte secondary battery composed of a non-aqueous electrolyte, d Fibrous silicon whose surface is coated with a carbon material in the range of 002 = 0.34 to 0.37 nm is used as the negative electrode material.
[0014]
According to the invention of claim 1, spherical silicon or lump silicon coated with a carbon material is used by using fibrous silicon whose surface is coated with a carbon material in the range of d 002 = 0.34 to 0.37 nm as a negative electrode material. As compared with the case where is used for the negative electrode active material, the contact current collecting property can be secured, and a non-aqueous electrolyte secondary battery having a large discharge capacity can be obtained.
[0015]
According to a second aspect of the invention, a positive electrode comprising a lithium ion from a material capable of absorbing and desorbing, a negative electrode comprising a lithium ion from a material absorbing and releasing, in a non-aqueous electrolyte secondary battery composed of a non-aqueous electrolyte, d A mixture of fibrous silicon having a surface coated with a carbon material in the range of 002 = 0.34 to 0.37 nm and a carbon material is used as the negative electrode material.
[0016]
According to the invention of claim 2, by adding a carbon material to the negative electrode, it is possible to obtain a non-aqueous electrolyte secondary battery having higher current collecting performance and a large discharge capacity.
[0017]
According to a third aspect of the present invention, in the non-aqueous electrolyte secondary battery according to the first or second aspect, in the fibrous silicon whose surface is coated with a carbon material, the carbon coating amount with respect to the total weight of silicon and carbon is 3 to 60% by weight. It is characterized by being.
[0018]
According to the invention of claim 3, a non-aqueous electrolyte secondary battery having good adhesion between the negative electrode active material and the current collector can be obtained.
[0019]
The invention of claim 4 is the nonaqueous electrolyte secondary battery according to claim 1, 2, or 3, wherein the fiber diameter of the fibrous silicon whose surface is coated with a carbon material is 0.01 to 50 μm. .
[0020]
According to the invention of claim 4, it is possible to obtain a non-aqueous electrolyte secondary battery exhibiting excellent charge / discharge characteristics with quick diffusion of lithium in the negative electrode active material and small polarization.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a non-aqueous electrolyte secondary battery comprising a positive electrode made of a material that occludes / releases lithium ions, a negative electrode made of a material that occludes / releases lithium ions, and a non-aqueous electrolyte. D 002 = 0 A fibrous silicon whose surface is coated with a carbon material in the range of .34 to 0.37 nm is used as the negative electrode material.
[0022]
As the negative electrode active material, the use of fibrous silicon whose surface is coated with a carbon material in the range of d 002 = 0.34 to 0.37 nm is more effective than the bulk powdery silicon whose surface is coated with a carbon material . The charge / discharge efficiency is improved, and a nonaqueous electrolyte battery having a large discharge capacity is obtained. The reason for this is that the negative electrode active material is in the form of a fiber, so that the current collecting property can be sufficiently secured, and the coated carbon suppresses the degree of expansion and contraction associated with charging / discharging, so that charging due to current collection deterioration can be achieved. It is considered that the decrease in discharge efficiency is suppressed.
[0023]
In addition, the negative electrode active material of the present invention can provide a larger discharge capacity than conventional batteries that use natural graphite as the negative electrode active material. This is because the lithium ion storage capacity of the negative electrode is improved by using a composite of silicon and carbon as compared with the conventional graphite negative electrode.
[0024]
As the fibrous silicon material, a silicon compound such as silicon alone or a carbide or oxide thereof can be used, which contains a different element within a range not exceeding the present invention, or a compound with lithium. It doesn't matter.
[0025]
Further, the crystallinity of the coated carbon is not particularly limited as long as sufficient electron conductivity can be ensured, and among these, a carbon material having a range of d 002 = 0.34 to 0.37 nm is used .
[0026]
As a method of coating the surface of fibrous silicon with a carbon material, a method of chemically depositing carbon, pitch, tar, phenol resin, imide resin, furan resin, polyacrylonitrile, furfuryl alcohol, etc. are held on the silicon surface. And a method of coating the carbon material by applying mechanical energy between the fibrous silicon and the carbon material.
[0027]
The carbon material may completely cover the surface of the fibrous silicon, or may cover a part of the surface of the fibrous silicon so that a part of the silicon is exposed.
[0028]
The present invention also provides a nonaqueous electrolyte secondary battery comprising a positive electrode made of a material that occludes and releases lithium ions, a negative electrode made of a material that occludes and releases lithium ions, and a nonaqueous electrolyte. A mixture of fibrous silicon coated with a carbon material and a carbon material is used as a negative electrode material.
[0029]
By mixing the carbon material with fibrous silicon whose surface as the negative electrode active material is coated with the carbon material, the current collecting property can be further improved. In this case, the carbon material to be mixed is preferably one or a mixture of carbon materials made of natural graphite, artificial graphite, acetylene black, ketjen black, or vapor grown carbon fiber.
[0030]
In the fibrous silicon in which the surface of the present invention is coated with a carbon material, the carbon coating amount with respect to the total weight of silicon and carbon is preferably 3 to 60% by weight. If the coating amount of the carbon material is more than 60% by weight, the charge / discharge efficiency is inferior because of poor adhesion to the current collector, the capacity is reduced, and the coating carbon amount is less than 3% by weight. This is not enough to ensure sufficient current collection.
[0031]
In the fibrous silicon of the present invention whose surface is coated with a carbon material in the range of d 002 = 0.34 to 0.37 nm, the fiber diameter is preferably in the range of 0.01 to 50 μm. When the fiber diameter is larger than 50 μm, it is considered that the diffusion of lithium ions in the active material is slowed down, and the capacity is reduced by increasing the polarization. On the other hand, if the fiber diameter is smaller than 0.01 μm, handling becomes difficult and the process for producing the negative electrode becomes complicated.
[0032]
As the positive electrode active material of the nonaqueous electrolyte secondary battery in the present invention, Li x MO 2 , Li y M 2 O 4 (where M is one or more transition metals, 0 ≦ x ≦ 1, 0 ≦ y ≦ 2) Or a metal chalcogenide having a tunnel structure or a layered structure, a metal oxide and a metal sulfide can be used alone or in admixture of two or more. Specific examples thereof include LiCoO 2 , LiCo x Ni 1-x O 2 , L x iMnO 4 , LiMn 2 O 4 , LiFePO 4 , MnO 2 , TiO 2 , V 2 O 5 , FeS 2 , TiS 2 , Li 1 + x such as NiO 2, LiNi x Mn 2- x O 4 and the like. In particular, it is preferable to use Co, Ni, or Mn as the transition metal M because of the high discharge voltage. Examples of the organic compound include conductive polymers such as polyaniline and sulfur compounds.
[0033]
Nonaqueous electrolyte solvents include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, trifluoropropylene carbonate, γ-butyrolactone, 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, γ-valerolactone, sulfolane, 1,2-methoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyltetrahydrofuran, 3-methyl-1,3-dioxolane, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, dimethyl Carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl isopropyl carbonate, dibutyl carbonate, dimethyl carbonate Le formamide, dimethyl acetamide, can be used singly or as a mixture of two or more of methyl acetate, acetonitrile. In particular, a mixed system of a cyclic carbonate and a chain carbonate is preferable from the viewpoint of stability to oxidation and reduction.
[0034]
The electrolyte is used by dissolving the supporting salt in these nonaqueous solvents. LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiCF 3 CF 2 SO 3 , LiCF 3 CF 2 CF 2 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F) 5 SO 2 ) 2 , LiPF 3 (CF 3 ) 3 , LiCF 3 CO 2 , LiCl, LiBr, LiSCN, or other lithium salts can be used alone or in admixture of two or more. Among them, LiPF 6 is preferably used as the supporting salt.
[0035]
Further, instead of such a liquid electrolyte, an ion conductive polymer electrolyte and an organic electrolyte can be used in combination. Specific examples of the ion conductive polymer electrolyte include polyethers such as polyethylene oxide and polypropylene oxide, polyolefins such as polyethylene and polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, poly Methyl methacrylate, polymethyl acrylate, polyvinyl alcohol, polymethacrylonitrile, polyvinyl acetate, polyvinyl pyrrolidone, polycarbonate, polyethylene terephthalate, polyhexamethylene aipamide, polycaprolactam, polyurethane, polyethyleneimine, polybutadiene, polystyrene, polyisoprene and their Derivatives can be used alone or in combination.
[0036]
Moreover, you may use the polymer containing the various monomers which comprise the said polymer. In addition to the polymer electrolyte, an inorganic solid electrolyte, a mixed material of an organic polymer electrolyte and an inorganic solid electrolyte, an inorganic solid powder bound by an organic binder, or the like can be used.
[0037]
Further, the nonaqueous electrolyte secondary battery of the present invention is composed of a combination of a positive electrode, a negative electrode, and a separator and a nonaqueous electrolyte as its configuration, but as a separator, a woven fabric, a nonwoven fabric, a polyolefin type such as polyethylene or polypropylene, Porous polymer films such as polyimide and porous polyvinylidene fluoride films and ion conductive polymer electrolyte films can be used alone or in combination.
[0038]
Furthermore, the shape of the battery can be various shapes such as a cylindrical shape, a square shape, a coin shape, a button shape, and a laminate shape. As the material of the battery case, stainless steel, nickel-plated iron, aluminum, titanium, or an alloy thereof and a plated material can be used. As the material of the laminate resin film, aluminum, aluminum alloy, titanium foil, or the like can be used. The material of the heat-welded portion of the metal laminate resin film may be any material as long as it is a thermoplastic polymer material such as polyethylene, polypropylene, polyethylene terephthalate. Further, the metal laminate resin layer and the metal foil layer are not limited to one layer, but may be two or more layers.
[0039]
【Example】
Specific examples to which the present invention is applied will be described. However, the present invention is not limited to these examples, and can be appropriately modified and implemented within a range not exceeding the gist thereof.
[0040]
A schematic cross-sectional structure of the rectangular non-aqueous electrolyte secondary battery used here is shown in FIG. In FIG. 1, 1 is a nonaqueous electrolyte battery, 2 is a power generation element, 3 is a positive electrode plate, 4 is a negative electrode plate, 5 is a separator, 6 is a battery case, 7 is a battery lid, 8 is a safety valve, 9 is a positive electrode terminal, 10 Is a positive electrode lead.
[0041]
The nonaqueous electrolyte secondary battery 1 has a thickness of 5.0 mm, and includes a positive electrode plate 3 formed by applying a positive electrode mixture containing a positive electrode active material to an aluminum current collector, and a negative electrode active material in a copper current collector. A wound power generation element 2 in which a negative electrode plate 4 formed by applying a negative electrode mixture is wound through a separator 5 into which a nonaqueous electrolytic solution is injected is housed in a battery case 6 that is nickel-plated on iron. Is. A battery lid 7 provided with a safety valve 8 is attached to the battery case 6 by laser welding, the positive electrode terminal 9 is connected to the positive electrode plate 3 via the positive electrode lead 10, and the negative electrode plate 4 is connected to the inner wall of the battery case 6. Connected by contact.
[0042]
The positive electrode was prepared by mixing 90% by weight of LiCoO 2 as an active material, 5% by weight of acetylene black as a conductive agent, and 5% by weight of polyvinylidene fluoride as a binder to form a positive electrode mixture, and N-methyl-2 -The slurry was prepared by dispersing in pyrrolidone. The slurry was uniformly applied to an aluminum current collector having a thickness of 20 μm, dried, and then compression-molded with a roll press to a thickness of 180 μm.
[0043]
For the negative electrode, a slurry was prepared by mixing 90% by weight of the negative electrode active material and 10% by weight of polyvinylidene fluoride as a binder to form a negative electrode mixture and dispersing it in N-methyl-2-pyrrolidone. This slurry was uniformly applied to a copper current collector having a thickness of 10 μm, dried, and then compression-molded with a roll press to obtain a thickness of 180 μm.
[0044]
As the separator, a microporous polyethylene film having a thickness of 25 μm was used. In addition, as the electrolyte, a battery is manufactured by using an electrolytic solution in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) are mixed at a volume ratio of 1: 1 and LiPF 6 is dissolved at 1.0 mol / l as a lithium salt. did.
[0045]
The produced nonaqueous electrolyte secondary battery was charged at a constant current and a constant voltage up to 3.9 V at a current of 1 C at 25 ° C. for 3 hours to obtain a fully charged state. Subsequently, the battery was discharged at a current of 1 C to 2.75 V, and the discharge capacity and charge / discharge efficiency in the first cycle were measured.
[0046]
[Example 1]
Batteries using the following three types as negative electrode active materials were produced and their characteristics were compared. 1) The surface of a silicon fiber having a fiber diameter of 5 μm is coated with a carbon material having an average interplanar spacing d 002 = 0.34 nm. However, the carbon coating amount relative to the total weight of silicon and carbon was 30% by weight. This was designated as Battery A. 2) The surface of bulk powder silicon having an average particle diameter of 20 μm is coated with a carbon material having an average interplanar spacing d 002 = 0.34 nm. However, the carbon coating amount relative to the total weight of silicon and carbon was 30% by weight. This was designated as Battery B. 3) Scaly natural graphite. This was designated as Battery C. The measurement results are shown in Table 1.
[0047]
[Table 1]
[0048]
From Table 1, the charge / discharge efficiency of battery C was larger than batteries A and B, but the discharge capacity was small. Battery A has a considerably larger discharge capacity and charge / discharge efficiency than battery B. As described above, it was found that a non-aqueous electrolyte secondary battery having a large discharge capacity can be obtained by using fibrous silicon of which the surface is coated with a carbon material as a negative electrode material.
[0049]
[Example 2]
As a negative electrode active material, a surface of a silicon fiber having a fiber diameter of 5 μm is coated with a carbon material having an average interplanar spacing d 002 = 0.34 nm, and the carbon coating amount with respect to the total weight of silicon and carbon is 0 to 70 wt. 7 batteries (battery D to battery J) varied between% and charge / discharge characteristics at the first cycle were measured. The measurement results are shown in Table 2.
[0050]
[Table 2]
[0051]
From Table 2, in the nonaqueous electrolyte secondary battery using fibrous silicon whose surface is coated with a carbon material as a negative electrode active material, the carbon coating amount with respect to the total weight of silicon and carbon is 3 to 60% by weight. In the batteries E to I, the discharge capacity was large and the charge / discharge efficiency was 80% or more, whereas in the batteries D and J in which the carbon coating amount was outside the scope of the present invention, the discharge capacity and charge / discharge It turned out that both efficiency became small.
[0052]
[Example 3]
As the negative electrode active material, a material in which the surface of silicon fiber is coated with a carbon material having an average interplanar spacing d 002 = 0.34 nm is used, and the carbon coating amount with respect to the total weight of silicon and carbon is 30% by weight. Six types of batteries (battery K to battery P) with diameters varied between 0.005 and 70 μm were prepared, and charge / discharge characteristics at the first cycle were measured. The measurement results are shown in Table 3.
[0053]
[Table 3]
[0054]
From Table 3, in the nonaqueous electrolyte secondary battery using fibrous silicon whose surface is coated with a carbon material as the negative electrode active material, the fiber L of the present invention, in which the fiber diameter of the silicon fiber is 0.01 to 50 μm In O, the discharge capacity was large and the charge / discharge efficiency was 80% or more, whereas in the batteries K and P where the fiber diameter of the silicon fiber was outside the scope of the present invention, both the discharge capacity and the charge / discharge efficiency were small. I found out that
[0055]
[Example 4]
The surface of silicon fiber having a fiber diameter of 5 μm is coated with a carbon material having an average interplanar spacing d 002 = 0.34 nm, and X is defined as 30% by weight of carbon with respect to the total weight of silicon and carbon. And the non-aqueous electrolyte secondary battery using the negative electrode active material which mixed X and the carbon material was produced.
[0056]
Non-aqueous electrolyte secondary battery using negative electrode active material using flaky artificial graphite as carbon material and ratio of X to total weight being 90%, 80% and 60% by weight, and acetylene black as carbon material And a non-aqueous electrolyte secondary battery using a negative electrode active material in which the ratio of X to the total weight was 90% by weight was produced, and charge / discharge characteristics at the first cycle were measured. The measurement results are shown in Table 4.
[0057]
[Table 4]
[0058]
From Table 4, it was found that the discharge capacities of the batteries Q to T were almost the same, and the charging / discharging efficiency was slightly improved as the amount of carbon material added increased.
[0059]
【The invention's effect】
A non-aqueous electrolyte secondary battery according to the present invention includes a non-aqueous electrolyte battery composed of a positive electrode made of a material that absorbs and releases lithium ions, a negative electrode made of a material that absorbs and releases lithium ions, and a non-aqueous electrolyte. In the secondary battery, fibrous silicon whose surface is coated with a carbon material in the range of d 002 = 0.34 to 0.37 nm is used as the negative electrode material.
[0060]
When fibrous silicon whose surface is coated with a carbon material in the range of d 002 = 0.34 to 0.37 nm is used as the negative electrode active material, the shape of the negative electrode active material is fibrous, so that the current collecting property is Sufficiently secured, and by suppressing the degree of expansion and contraction of the coated carbon during charging and discharging, the decrease in charging and discharging efficiency due to current collection deterioration is suppressed, so the initial charging and discharging efficiency is improved, and the discharge capacity A large non-aqueous electrolyte battery can be obtained.
[Brief description of the drawings]
FIG. 1 is a diagram showing a schematic cross-sectional structure of a prismatic nonaqueous electrolyte secondary battery in FIG.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Nonaqueous electrolyte secondary battery 2 Power generation element 3 Positive electrode plate 4 Negative electrode plate 5 Separator 6 Battery case 7 Battery cover 8 Safety valve 9 Positive electrode terminal 10 Positive electrode lead

Claims (4)

  1. In a non-aqueous electrolyte secondary battery including a positive electrode made of a material that occludes / releases lithium ions, a negative electrode made of a material that occludes / releases lithium ions, and a non-aqueous electrolyte, d 002 = 0.34-0 A non-aqueous electrolyte secondary battery using, as a negative electrode material, fibrous silicon whose surface is coated with a carbon material in the range of 37 nm .
  2. In a non-aqueous electrolyte secondary battery including a positive electrode made of a material that occludes / releases lithium ions, a negative electrode made of a material that occludes / releases lithium ions, and a non-aqueous electrolyte, d 002 = 0.34-0 A non-aqueous electrolyte secondary battery using, as a negative electrode material, a mixture of fibrous silicon having a surface coated with a carbon material in the range of 37 nm and a carbon material.
  3. 3. The nonaqueous electrolyte secondary battery according to claim 1 or 2, wherein the fibrous silicon whose surface is coated with a carbon material has a carbon coating amount of 3 to 60% by weight relative to the total weight of silicon and carbon.
  4. 4. The nonaqueous electrolyte secondary battery according to claim 1, wherein the fiber diameter of the fibrous silicon whose surface is coated with a carbon material is 0.01 to 50 [mu] m.
JP2001369220A 2001-12-03 2001-12-03 Nonaqueous electrolyte secondary battery Expired - Fee Related JP4035760B2 (en)

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