JP5272492B2 - Negative electrode material for non-aqueous electrolyte secondary battery and method for producing the same, and negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative electrode material, or the like, for a non-aqueous electrolyte secondary battery in which the nonaqueous electrolyte secondary battery that has high initial charge/discharge efficiency, and is superior in the cycle performance can be obtained, while maintaining high battery capacity and a low volume expansion rate, after charging. <P>SOLUTION: This is the negative material for the nonaqueous electrolyte secondary battery which contains an active material, composed of covered silicon oxide particles and silicon particles in which the surface of the silicon oxide particles is covered by a graphite coating, and a binder of 1 to 20 wt.%, and in which as for the graphite coating of the covered silicon oxide particles, the intensity ratio of a scattering peak in a raman spectrum analysis is 1.5&lt;I<SB>1330</SB>&lt;I<SB>1580</SB>&lt;3.0, in solid NMR (<SP>29</SP>Si-DDMAS) measurement, a ratio S<SB>-84</SB>/S<SB>-110</SB>of a broad signal area having the -110 ppm vicinity as the center and a signal area of the -84 ppm vicinity is 0.5&lt;S<SB>-84</SB>/S<SB>-110</SB>&lt;1.1, and the proportion of the silicon particles in the active material is 1 to 50 wt.%. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a negative electrode material for a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery, a negative electrode for a non-aqueous electrolyte secondary battery using the negative electrode material, and a non-aqueous electrolyte secondary battery.

In recent years, with the remarkable development of portable electronic devices, communication devices, etc., there is a strong demand for non-aqueous electrolyte secondary batteries with high energy density from the viewpoints of economy and downsizing and weight reduction of devices. Conventionally, as a measure for increasing the capacity of this type of non-aqueous electrolyte secondary battery, for example, negative electrode materials such as oxides such as B, Ti, V, Mn, Co, Fe, Ni, Cr, Nb, and Mo and composites thereof A method using an oxide (see Patent Document 1: Japanese Patent No. 3008228, Patent Document 2: Japanese Patent No. 3242751, etc.) M _100-x Si _x (x ≧ 50 at%, M = Ni, Fe) , Co, Mn) as a negative electrode material (see Patent Document 3: Japanese Patent No. 3,846,661), a method using silicon oxide as a negative electrode material (Patent Document 4: Japanese Patent No. 2,997,741), and Si _{2 as} a negative electrode material. A method using N ₂ O, Ge ₂ N ₂ O and Sn ₂ N ₂ O (Patent Document 5: Japanese Patent No. 3918311) has been proposed.

Silicon shows the theoretical capacity of 4200 mAh / g, which is far higher than the theoretical capacity of 372 mAh / g of the carbon material currently in practical use, and is the most expected material for battery miniaturization and high capacity. Various forms of silicon having different crystal structures are known depending on the production method. For example, a lithium ion secondary battery using single crystal silicon as a support for a negative electrode active material has been proposed (Patent Document 6: Japanese Patent No. 2964732), and includes single crystal silicon, polycrystalline silicon, and amorphous silicon. A lithium ion secondary battery using a lithium alloy of Li _x Si (where x is 0 to 5) has been proposed (Patent Document 7: Japanese Patent No. 3079343), and particularly Li _x using amorphous silicon. Si is preferable, and a pulverized product of crystalline silicon coated with amorphous silicon obtained by plasma decomposition of monosilane is exemplified. However, in this case, as in the example, 30 parts of silicon and 55 parts of graphite as a conductive agent were used, and the battery capacity of silicon could not be fully exhibited.

  Further, for the purpose of imparting conductivity to the negative electrode material, a method of mechanically alloying a metal oxide such as silicon oxide and graphite, followed by carbonization treatment (Patent Document 8: JP 2000-243396 A), Si A method in which the particle surface is coated with a carbon layer by chemical vapor deposition (Patent Document 9: Japanese Patent Laid-Open No. 2000-215887), and a method in which the surface of silicon oxide particles is coated with a carbon layer by chemical vapor deposition (Patent Document 10: Japanese Patent Laid-Open No. 2002-2002). -42806). However, the conductivity can be improved by providing a carbon layer on the particle surface, but the large volume change accompanying charging / discharging, which is a problem to be overcome by the silicon negative electrode, is mitigated, and the current collecting deterioration and cycle are associated with this. The characteristic deterioration could not be prevented.

For this reason, in recent years, methods for suppressing the volume expansion by limiting the battery capacity utilization rate of silicon (Patent Document 9: JP 2000-215887 A, Patent Document 11: JP 2000-173596 A, Patent Document 12: Japanese Patent No. 3291260, Patent Document 13: Japanese Patent Application Laid-Open No. 2005-317309, or a technique of rapidly cooling a silicon melt to which alumina is added as a method of using a grain boundary of a polycrystalline particle as a buffer zone for volume change (Patent Document 14) : JP-A-2003-109590), polycrystalline particles made of α, β-FeSi ₂ mixed phase polycrystal (Patent Document 15: JP-A-2004-185991), high-temperature plastic working of single-crystal silicon ingot (patent) Document 16: Japanese Patent Laid-Open No. 2004-303593) has been proposed.

  A method of reducing volume expansion by devising a laminated structure of a silicon active material has also been proposed. For example, a method of disposing a silicon negative electrode in two layers (Patent Document 17: JP-A-2005-190902), carbon and others Method of suppressing collapse of particles by coating or encapsulating with metal and oxide (Patent Document 18: JP-A-2005-235589, Patent Document 19: JP-A-2006-216374, Patent Document 20: JP-A-2006) No. 236684, Patent Document 21: Japanese Patent Laid-Open No. 2006-339092, Patent Document 22: Japanese Patent No. 3622629, Patent Document 23: Japanese Patent Laid-Open No. 2002-75351, Patent Document 24: Japanese Patent No. 3622631) and the like. It is disclosed. In addition, in a method in which silicon is directly vapor-grown on a current collector, a method of suppressing a decrease in cycle characteristics due to volume expansion by controlling the growth direction has also been proposed (Patent Document 25: Japanese Patent Application Laid-Open No. 2006-338996). Publication).

  However, the method of improving the cycle characteristics of the negative electrode material by, for example, coating the silicon surface with carbon to make it conductive or coating with an amorphous metal layer can only exhibit about half of the original battery capacity of silicon. Therefore, further increase in capacity has been demanded. In addition, with polycrystalline silicon having crystal grain boundaries, it is difficult to control the cooling rate by the proposed method, and it is difficult to reproduce stable physical properties.

  On the other hand, silicon oxide can be expressed as SiOx (where x is slightly larger than the theoretical value 1 because it is an oxide film), but amorphous silicon of about several nanometers to several tens of nanometers is analyzed by X-ray diffraction. It has a finely dispersed structure. For this reason, although the battery capacity is small compared to silicon, the battery capacity is 5-6 times higher than the mass, and further, the volume expansion is small. However, silicon oxide has a large irreversible capacity, and the initial efficiency is very low at about 70%. Therefore, when a battery is actually manufactured, the battery capacity of the positive electrode is excessively required, and the capacity increase by 5 to 6 times per active material. The battery capacity could not be expected to increase to meet

  A practical problem of silicon oxide is that the initial efficiency is remarkably low, and means for solving this include a method of replenishing the irreversible capacity and a method of suppressing the irreversible capacity. For example, it has been reported that a method for compensating for the irreversible capacity by doping Li metal in advance is effective. However, in order to dope Li metal, a method of attaching Li foil to the surface of the negative electrode active material (Patent Document 26: Japanese Patent Laid-Open No. 11-0868847) and a method of depositing Li on the surface of the negative electrode active material (Patent Document 27: JP, 2007-122992, A) and the like are disclosed. However, it is difficult to obtain a Li thin body corresponding to the initial efficiency of the silicon oxide negative electrode by attaching Li foil, and the cost is high, and vapor deposition using Li vapor is not practical due to complicated manufacturing process. there were.

  On the other hand, a method for increasing the initial efficiency by increasing the mass ratio of Si irrespective of Li doping is disclosed. One is a method in which silicon powder is added to silicon oxide powder to reduce the mass ratio of silicon oxide (Patent Document 28: Japanese Patent No. 3982230). On the other hand, silicon vapor is simultaneously generated in the production stage of silicon oxide. This is a method of obtaining a mixed solid of silicon and silicon oxide by precipitation (Patent Document 29: JP 2007-290919 A). However, silicon has both high initial efficiency and battery capacity compared to silicon oxide, but is an active material that exhibits a volume expansion coefficient of 400% during charging, and even when added to a mixture of silicon oxide and carbon material. In addition, the volume expansion coefficient of silicon oxide cannot be maintained, and as a result, it was necessary to add 20% by mass or more of a carbon material to suppress the battery capacity to 1000 mAh / g. On the other hand, the method of obtaining a mixed solid by simultaneously generating vapors of silicon and silicon oxide requires a manufacturing process at a high temperature exceeding 2000 ° C. because the vapor pressure of silicon is low, and has a problem in operation.

  As described above, even if the silicon-based active material is a single metal or its oxide, each has a problem to be solved, which has been a problem in practical use. It is possible to sufficiently suppress the volume change due to insertion and extraction of Li, to reduce pulverization due to particle cracking, and to reduce the decrease in conductivity due to peeling from the current collector. There has been a demand for a negative electrode active material that is advantageous and can be applied to applications in which repetitive cycle characteristics are particularly important, such as for mobile phones.

Japanese Patent No. 3008228 Japanese Patent No. 3242751 Japanese Patent No. 3846661 Japanese Patent No. 2999741 Japanese Patent No. 3918311 Japanese Patent No. 2964732 Japanese Patent No. 3079343 JP 2000-243396 A JP 2000-215887 A JP 2002-42806 A JP 2000-173596 A Japanese Patent No. 3291260 JP 2005-317309 A JP 2003-109590 A JP 2004-185991 A JP 2004-303593 A JP 2005-190902 A JP 2005-235589 A JP 2006-216374 A JP 2006-236684 A JP 2006-339092 A Japanese Patent No. 3622629 JP 2002-75351 A Japanese Patent No. 3622631 JP 2006-338996 A Japanese Patent Laid-Open No. 11-086847 JP 2007-122992 A Japanese Patent No. 3982230 JP 2007-290919 A

  The present invention is a negative electrode material that is effective for a negative electrode of a nonaqueous electrolyte secondary battery having high initial charge / discharge efficiency and excellent cycle characteristics, while maintaining a high battery capacity of silicon oxide and a low volume expansion rate after charging, and It aims at providing the nonaqueous electrolyte secondary battery negative electrode and nonaqueous electrolyte secondary battery which used this negative electrode material.

  The present inventors have studied an active material having a high initial charge / discharge efficiency that exceeds the battery capacity of the carbon material, has a small volume expansion after charge, overcomes the low initial charge / discharge efficiency, which is a drawback of silicon oxide, and the like. . As a result, it has been found that the above problems can be solved by using both specific coated silicon oxide particles having a specific graphite film and 1 to 50% by mass of silicon particles as active materials. That is, when silicon is added to the specific graphite-coated silicon oxide of the present invention, the volume expansion after charging as observed in general silicon exceeding 400% is not observed, and is almost the same as that of silicon oxide. It was found that the volume expansion rate was maintained. For this reason, the battery capacity per volume is increased, the conductivity can be improved by adding or coating a conductive agent, and the conductivity is improved by coating graphite, and the initial charge / discharge efficiency is increased, By blending 1 to 20% by mass of the binder into the negative electrode material, the negative electrode material can be prevented from being destroyed or pulverized even if the expansion and contraction due to charge and discharge are repeated, and the conductivity of the electrode itself does not decrease. It has been found that when a negative electrode material is used as a nonaqueous electrolyte secondary battery, a nonaqueous electrolyte secondary battery with good cycle characteristics can be obtained, and the present invention has been made.

Accordingly, the present invention provides the following inventions.
[1]. Non-water containing active material (A) composed of coated silicon oxide particles (A1) and silicon particles (A2) whose surfaces are coated with a graphite film, and binder (B) 1 to 20% by mass A negative electrode material for an electrolyte secondary battery,
Graphite coating of the coated silicon oxide particles (A1) is, in the Raman spectrum analysis, have a scattering peak at 1330 cm ^-1 and 1580 cm ^-1, their intensity ratio I ₁₃₃₀ / I ₁₅₈₀ is 1.5 <I ₁₃₃₀ / I _In the solid state NMR ( ²⁹ Si-DDMAS) measurement of the coated silicon oxide particles (A1) with ₁₅₈₀ <3.0, the ratio S between the broad signal area centered around −110 ppm and the signal area around −84 ppm ₋₈₄ / S ₋₁₁₀ is 0.5 <S ₋₈₄ / S ₋₁₁₀ <1.1, the ratio of the coated silicon oxide particles (A1) in the active material (A) is 70 to 95% by mass, A negative electrode material for a nonaqueous electrolyte secondary battery, wherein the ratio of silicon particles (A2) is 5 to 30 % by mass.
[2]. The nonaqueous electrolyte according to [1], wherein the silicon oxide particles are formed by depositing silicon oxide gas obtained by heating a mixture of silicon dioxide and metal silicon at 1000 to 1500 ° C. under reduced pressure at 500 to 1100 ° C. Secondary battery negative electrode material.
[3]. The negative electrode material for a nonaqueous electrolyte secondary battery according to [1] or [2], wherein the silicon particles (A2) are coated silicon particles whose surfaces are coated with a graphite film.
[4]. The negative electrode material for a nonaqueous electrolyte secondary battery according to [1], [2] or [3], wherein the binder (B) is a polyimide resin.
[5]. The manufacturing method of the negative electrode material for nonaqueous electrolyte secondary batteries as described in [1] including following process (I) and (II).
(I) The silicon oxide particles are chemically vapor-deposited at 600 to 1100 ° C. under reduced pressure of 50 to 30000 Pa in an organic gas and / or vapor to prepare a coated silicon oxide particle (A1). The process of
(II) A step of mixing the coated silicon oxide particles (A1), the silicon particles (A2), and the binder (B) obtained in step (I) to prepare a negative electrode material for a nonaqueous electrolyte secondary battery.
[6]. In all steps in which the negative electrode material for a nonaqueous electrolyte secondary battery is obtained from step (I), the silicon oxide particles and the coated silicon oxide particles are in an atmosphere of 1100 ° C. or lower [5] Manufacturing method of negative electrode material.
[7]. [1] - a negative electrode containing a negative electrode material for a nonaqueous electrolyte secondary battery according to any one of [4], non, wherein the volume after charging is less than 2 times the previous charging Negative electrode for water electrolyte secondary battery.
[8]. [7] A nonaqueous electrolyte secondary battery comprising the negative electrode for a nonaqueous electrolyte secondary battery, a positive electrode, a separator, and a nonaqueous electrolyte.
[9]. The nonaqueous electrolyte secondary battery according to [8], wherein the nonaqueous electrolyte secondary battery is a lithium ion secondary battery.

  By using the negative electrode material for a non-aqueous electrolyte secondary battery obtained in the present invention, it has high initial charge / discharge efficiency and excellent cycle characteristics while maintaining a high battery capacity and a low volume expansion after charging. A nonaqueous electrolyte secondary battery can be obtained.

A negative electrode material for a non-aqueous electrolyte secondary battery according to the present invention includes an active material (A) composed of coated silicon oxide particles and silicon particles (A2) in which the surface of silicon oxide particles (A1) is coated with a graphite film, and a binder. agent (B) it is one which contains a 1 to 20 mass%, graphite coating of the coated silicon oxide particles, in the Raman spectrum analysis, have a scattering peak at 1330 cm ^-1 and 1580 cm ^-1, their strength The ratio I ₁₃₃₀ / I ₁₅₈₀ is 1.5 <I ₁₃₃₀ / I ₁₅₈₀ <3.0, and a broad signal centered around −110 ppm in the solid state NMR ( ²⁹ Si-DDMAS) measurement of the coated silicon oxide particles. The ratio S ₋₈₄ / S _{−110 of the} area to the signal area in the vicinity of ₋₈₄ ppm is 0.5 <S ₋₈₄ / S ₋₁₁₀ <1.1, and the silicon particles (A2) in the active material (A) Non-feature characterized by a proportion of 1-50 mass A negative electrode material for electrolyte secondary battery.

[Active material (A)]
It consists of the coated silicon oxide particles (A1) and the silicon particles (A2) in which the surface of the silicon oxide particles is coated with a graphite film, each of which can be used alone or in combination of two or more.
(A1) Coated silicon oxide particles Coated silicon oxide particles have a broad signal area of -98 to -145 ppm centered around -110 ppm and -45 to -84 ppm around -84 ppm in solid state NMR ( ²⁹ Si-DDMAS) measurement. The ratio S ₋₈₄ / S ₋₁₁₀ to the signal area of 98 ppm is 0.5 <S ₋₈₄ / S ₋₁₁₀ <1.1, preferably 0.6 to 1.0, and 0.6 to 0. 8 is more preferable. In the above spectrum, amorphous silicon oxide only shows a broad peak centered around −110 ppm, but a peak characteristic of Si diamond crystal is detected near −84 ppm by thermal history. That is, it is preferable that the area centered on the signal attributed to the Si diamond crystal is small. In order to obtain such coated silicon oxide particles, silicon oxide in the above range is used.

  In the present invention, silicon oxide is an amorphous silicon oxide obtained by cooling and precipitating silicon oxide gas generated by heating a mixture of silicon dioxide and metal silicon, and is represented by the general formula SiOx, The range of x is preferably 1.0 ≦ x <1.6, and more preferably 1.0 ≦ x ≦ 1.2. The molar ratio of silicon dioxide to metallic silicon is approximately 1: 1.

  The silicon oxide used in the present invention is, for example, a silicon oxide gas obtained by heating a mixture of silicon dioxide and metal silicon under reduced pressure, preferably at 5 to 200 Pa, and 1000 to 1500 ° C. at 500 to 1100 ° C. It can be obtained by precipitation. In order to make the area ratio within the above range, it is important to keep the deposition chamber at 500 to 1100 ° C., preferably 600 to 950 ° C. If the area ratio is as described above, silicon contained in silicon oxide is nanoparticles of several nm to several tens of nm, and the volume expansion at the time of charge / discharge is very small, so that it can be suitably used in the present invention. it can. On the other hand, when disproportionation occurs due to the thermal history and the area ratio exceeds 1.1, silicon particles tend to increase and the volume expansion tends to increase. Silicon is used.

The silicon oxide is further pulverized into silicon oxide particles. The particle diameter is determined by the laser diffraction / scattering particle size distribution measurement method, and when the cumulative curve is obtained by setting the total volume of the particle to 100%, the particle diameter at the point where the cumulative curve becomes 10%, 50%, and 90%. The 10% diameter, 50% diameter, and 90% diameter (μm) are evaluated. In the present invention, a cumulative median diameter D ₅₀ (median diameter) of 50% diameter was used. The silicon oxide particles of the present invention preferably have a median diameter D ₅₀ of 0.1 to ₅₀ μm, more preferably 1 to 20 μm. Median diameter D ₅₀ is too the specific surface area is large small, sometimes negative electrode film density is too small, which may cause a short circuit through the negative electrode film when the median diameter D ₅₀ is too large.

  In order to make the silicon oxide particles have a predetermined particle size, a well-known pulverizer and classifier are used. The pulverizer, for example, moves the grinding media such as balls and beads, and uses the impact force, friction force, and compression force due to the kinetic energy to pulverize the material to be crushed, the media agitation mill, and the compression force by the roller. A roller mill that uses pulverization, a jet mill that makes crushed objects collide with the lining material or collide with each other at high speed, and pulverizes by the impact force of the impact, and a rotor with a fixed hammer, blade, pin, etc. A hammer mill, a pin mill, a disk mill, a colloid mill using a shearing force, a high-pressure wet opposed collision disperser “Ultimizer”, or the like is used. For pulverization, both wet and dry processes are used. In order to adjust the particle size distribution after pulverization, dry classification, wet classification or sieving classification is used. In the dry classification, the process of dispersion, separation (separation of fine particles and coarse particles), collection (separation of solid and gas), and discharge are performed sequentially or simultaneously, mainly using air flow. Prior to classification (adjustment of moisture, dispersibility, humidity, etc.) or airflow to be used so as not to reduce the classification efficiency due to the shape, turbulence of the airflow, velocity distribution, static electricity, etc. It is used by adjusting the moisture and oxygen concentration. Further, in a dry type in which a classifier is integrated, pulverization and classification are performed at a time, and a desired particle size distribution can be obtained.

The coated silicon oxide particles are obtained by coating the surface of the silicon oxide particles with a graphite film. In the present invention, the type and ratio of graphite coating the surface of the silicon oxide particles are within a specific range, and the graphite of the coated silicon oxide particles. coating, in the Raman spectrum analysis, have a scattering peak at 1330 cm ^-1 and 1580 cm ^-1, important that their intensity ratio I ₁₃₃₀ / I ₁₅₈₀ is a _{1.5 <I 1330 / I 1580 <} 3.0 It is. Generally, graphite materials are divided into three allotropes, namely diamond, graphite (graphite), and amorphous carbon (amorphous carbon). Each of these graphite materials has characteristic physical properties. That is, diamond has high strength, high density, and high insulation, and graphite has excellent electrical conductivity. In the present invention, the above characteristics are optimized by optimizing the ratio of the graphite material having the diamond structure and the graphite material having the graphite structure as the graphite material covering the surface of the silicon oxide particles. Electrode destruction due to expansion and contraction of the accompanying electrode material can be prevented and a negative electrode material having a conductive network can be obtained.

Here, the ratio between the graphite material having a diamond structure and the graphite material having a graphite structure can be obtained from a Raman spectrum obtained by microscopic Raman analysis (ie, Raman spectroscopic analysis). That is, diamond has a sharp scattering peak with a Raman shift of 1330 cm ⁻¹ and graphite with a Raman shift of 1580 cm ⁻¹ , and the ratio of the graphite material having the diamond structure and the graphite material having the graphite structure is simply determined by the intensity ratio. be able to.

The findings of the present inventors, an intensity ratio I ₁₃₃₀ / I ₁₅₈₀ of the scattering peak of scattering peak and the Raman shift of Raman shift 1330 cm ^-1 is 1580 cm ^-1 is _{1.5 <I 1330 / I 1580 <} 3.0, Preferably, when silicon oxide having a graphite film in the range of 1.7 <I ₁₃₃₀ / I ₁₅₈₀ <2.5 is used as a negative electrode material for a lithium ion secondary battery, a lithium ion secondary battery having good battery characteristics can be obtained. .

If the strength ratio I ₁₃₃₀ / I ₁₅₈₀ is 1.5 or less, the ratio of the graphite-structured graphite material is large, and the strength of the film is reduced, so that electrode destruction occurs due to expansion / contraction of the electrode material during charge / discharge, The battery capacity decreases and the cycle performance during repeated use decreases. On the contrary, when the strength ratio I ₁₃₃₀ / I ₁₅₈₀ is 3.0 or more, the ratio of the diamond structure graphite material is increased, the conductivity is insufficient, and the cycle performance is lowered.

  The coated silicon oxide particles coated with the graphite agent having the above strength ratio are, for example, chemically vapor-deposited on the surface of the silicon oxide particles at 600 to 1100 ° C. under reduced pressure of 50 to 30000 Pa in an organic gas and / or vapor. Can be obtained. The pressure is preferably 100 to 20000 Pa, more preferably 1000 to 20000 Pa. When the degree of vacuum is less than 50 Pa, the proportion of the graphite material having a diamond structure increases, and when used as a negative electrode material for a lithium ion secondary battery, the conductivity is insufficient and the cycle performance may be reduced. On the other hand, if it is higher than 30000 Pa, the ratio of the graphite material having a graphite structure becomes too large, and when used as a negative electrode material for a lithium ion secondary battery, there is a possibility that the cycle performance may be lowered in addition to the reduction in battery capacity. As for the said temperature, 800-1050 degreeC is more preferable. When the processing temperature is lower than 600 ° C., a long-time processing may be required. On the other hand, if the temperature is higher than 1100 ° C., particles may be fused and aggregated by chemical vapor deposition, and a conductive film is not formed on the agglomerated surface, and when used as a negative electrode material for a lithium ion secondary battery, Performance may be reduced. Further, the disproportionation reaction of silicon oxide proceeds, and the signal ratio in the solid state NMR may exceed 1.1. The treatment time is appropriately selected according to the target graphite coating amount, treatment temperature, concentration (flow rate) of organic gas, introduction amount, etc., but usually 1 to 10 hours, particularly about 2 to 7 hours is economical. Is also efficient.

  The graphite coating amount is not particularly limited, but is preferably 1 to 50% by mass and more preferably 5 to 20% by mass in the coated silicon oxide particles. If the amount of carbon is large, the high battery capacity that is characteristic of silicon oxide may be reduced. On the other hand, if the amount of carbon is small, the carbon coating may vary, and sufficient conductivity may not be obtained.

  As an organic substance used as a raw material for generating an organic gas in the present invention, an organic substance that can be thermally decomposed at the above heat treatment temperature to generate carbon (graphite) is selected, particularly in a non-acidic atmosphere. For example, methane, ethane, A single or mixture of hydrocarbons such as ethylene, acetylene, propane, butane, butene, pentane, isobutane, hexane, benzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, indene, coumarone , Pyridine, anthracene, phenanthrene, and the like, and monocyclic to tricyclic aromatic hydrocarbons or a mixture thereof. In addition, gas gas oil, creosote oil, anthracene oil, and naphtha cracked tar oil obtained in the tar distillation step can be used alone or as a mixture.

  The average particle diameter of the coated silicon oxide particles is preferably from 0.1 to 50 μm, more preferably from 1 to 20 μm, like the silicon oxide particles. The average particle diameter is a value obtained by a laser diffraction / scattering particle size distribution measurement method similar to that for silicon oxide particles.

  The blending amount of the coated silicon oxide particles in the active material of the present invention is preferably 50 to 99% by mass, more preferably 70 to 95% by mass, and further preferably 70 to 90% by mass.

(A2) Silicon particles As the silicon, there are known single-crystal silicon, polycrystalline silicon, amorphous silicon due to the difference in crystallinity, and chemical grade silicon and metallurgical grade silicon called metal silicon due to differences in purity. Single crystal silicon is a crystal having regularity used in a semiconductor, and polycrystalline silicon is a crystal having partial regularity. Amorphous silicon, on the other hand, differs in that the Si atoms are arranged with little regularity and have a network structure, but amorphous silicon is made polycrystalline silicon by heat aging. be able to.

  The silicon particles of the present invention may be any of the above silicons, and may be used alone or in combination of two or more. Single crystal silicon or polycrystalline silicon with high purity is preferable, and polycrystalline silicon with relatively low price is preferable. There is also a method of obtaining polycrystalline silicon by rapidly cooling polycrystalline silicon or molten metal silicon produced by melting metal silicon and deflecting impurities by unidirectional solidification to improve purity. It is often cheaper than polycrystalline silicon produced from chlorosilane, and can be suitably used. Moreover, even chemical grade silicon with low purity can be used as a cheaper raw material because aluminum, iron, calcium, and the like, which are impurities, can be eluted and removed by acid treatment.

  The silicon particles may be carbon-deposited in the same manner as the silicon oxide particles, and by conducting carbon deposition, the conductivity is improved, and the cycle characteristics and battery capacity can be expected to be improved. Although the graphite coating amount is not particularly limited, it is preferably 0.1 to 20% by mass in the coated silicon particles, and more preferably 1 to 10% by mass.

Silicon particles are used after being pulverized to a desired particle size. The pulverization method can be carried out in the same manner as silicon oxide, but the particle diameter is preferably 0.1 to ₅₀ μm, more preferably 0.1 to 10 μm in median diameter D ₅₀ . If the particle diameter of the silicon particles is too large, the volume expansion may increase. The measurement method is the same as that for silicon oxide particles.

The compounding quantity of the silicon particle in the active material of this invention is 1-50 mass%, 5-30 mass% is preferable and 10-30 mass% is more preferable. Amount of the silicon particles in the active material is not observed the effect of the initial efficiency is less than 1 wt%, whereas, it is difficult to maintain more than 50 wt%, the low expansion coefficient after charging It becomes.

The amount of the active material (A) is preferably 50 to 98 wt% in the negative electrode material, more preferably 75 to 96 wt%, more preferably 80 to 96 wt%.

[Binder (B)]
As a binder used for this invention, a polyimide resin is preferable and an aromatic polyimide resin is more preferable. By using a polyimide resin as a binder, non-water is excellent in adhesion to the current collector, high in initial charge / discharge efficiency, relaxed in volume change during charge / discharge, and has good cycle characteristics and efficiency due to repetition. An electrolyte secondary battery is obtained. In addition, the aromatic polyimide resin is excellent in solvent resistance and can suppress separation from the current collector and separation of the active material. In addition, a binder can be used individually by 1 type or in combination of 2 or more types as appropriate.

  Aromatic polyimide resins are generally poorly soluble in organic solvents, and in particular need not swell or dissolve in the electrolyte, and generally only dissolve in high-boiling organic solvents such as cresol. is there. Therefore, the electrode paste is a precursor of polyimide and relatively easy to use in various organic solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, and dioxolane. It is good to add in the state of the melted polyamic acid and heat-treat at a temperature of 300 ° C. or higher for a long time, thereby dehydrating and imidizing to form a binder.

  In this case, the aromatic polyimide resin has a basic skeleton composed of tetracarboxylic dianhydride and diamine. Specific examples thereof include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride and biphenyltetra. Arocyclic tetracarboxylic dianhydrides such as aromatic tetracarboxylic dianhydrides such as carboxylic dianhydrides, cyclobutane tetracarboxylic dianhydrides, cyclopentane tetracarboxylic dianhydrides and cyclohexane tetracarboxylic dianhydrides And aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride can be used alone or in combination of two or more.

  Examples of the diamine include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminobenzophenone, 2,3-diaminonaphthalene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-di (4- Aminophenoxy) diphenyl sulfone, aromatic diamines such as 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, alicyclic diamines, aliphatic diamines, and the like are included, one kind alone or two kinds The above can be used in appropriate combination.

  As a method for synthesizing the polyamic acid intermediate, a solution polymerization method is usually used. Solvents used in the solution polymerization method include N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl Examples include sulfone, hexamethylphosphoramide, and butyrolactone, which can be used alone or in appropriate combination of two or more.

  The reaction temperature is usually in the range of −20 to 150 ° C., preferably in the range of −5 to 100 ° C. Furthermore, in order to convert the polyamic acid intermediate into a polyimide resin, a method of dehydrating and ring-closing by heating is usually employed. The heating and dehydration ring-closing temperature can be selected from 140 to 400 ° C, preferably 150 to 250 ° C. The time required for this dehydration and ring closure is 30 seconds to 10 hours, preferably 5 minutes to 5 hours, although it depends on the reaction temperature.

  Examples of such polyimide resin include polyimide resin powder and N-methylpyrrolidone solution of a polyimide precursor. For example, U-varnish A, U-varnish S, UIP-R, UIP-S (Ube) Kosan Co., Ltd.), KAYAFLEX KPI-121 (Nippon Kayaku Co., Ltd.), Rika Coat SN-20, PN-20, EN-20 (Shin Nihon Rika Co., Ltd.).

The amount of the binder is 1 to 20 mass% in the negative electrode material is preferably 3 to 15 mass%. When the amount of the binder is too small, the negative electrode active material is separated. When the amount is too large, the porosity is decreased and the insulating film becomes thick, which may inhibit the movement of Li ions.

[Negative electrode material for non-aqueous electrolyte secondary battery]
The negative electrode material for a non-aqueous electrolyte secondary battery contains an active material (A) composed of coated silicon oxide particles (A1) and silicon particles (A2), and a binder (B) of 1 to 20% by mass. A negative electrode material for a water electrolyte secondary battery, which can be obtained by mixing coated silicon oxide particles (A1), silicon particles (A2), and a binder (B). A mixture of the coated silicon oxide particles and the silicon particles may be previously dispersed in water or a solvent such as N-methyl-2-pyrrolidone, and then a binder may be blended. In the present invention, it is preferable that the silicon oxide particles and the coated silicon oxide particles are in an atmosphere of 1100 ° C. or lower, preferably 1050 ° C. or lower, in all steps from obtaining the negative electrode material from the silicon oxide particles.

  In addition to the above components, a conductive agent such as graphite can be added to the negative electrode material. In this case, the kind of the conductive agent is not particularly limited as long as it is an electron conductive material that does not cause decomposition or alteration in the configured battery. Specifically, metal powder and metal fibers such as Al, Ti, Fe, Ni, Cu, Zn, Ag, SnSi, natural graphite, artificial graphite, various coke powders, mesophase carbon, vapor grown carbon fiber, pitch-based carbon Fiber, PAN-based carbon fiber, graphite such as various resin fired bodies, and the like can be used. Since these conductive agents are prepared by adding a dispersion of water or a solvent such as N-methyl-2-pyrrolidone in advance, an electrode paste uniformly attached and dispersed on silicon particles can be prepared. It is preferable to add as the solvent dispersion. The conductive agent can be dispersed in the solvent using a known surfactant. The solvent used for the conductive agent is preferably the same as the solvent used for the binder.

  The upper limit of the amount of the conductive agent is preferably 50% by mass or less in the negative electrode material (the battery capacity per negative electrode material is approximately 1000 mAH / g or more), more preferably 1 to 30% by mass, and more preferably 1 to 10% by mass. Further preferred. When the amount of the conductive agent is small, the conductivity of the negative electrode material may be poor and the initial resistance tends to be high. On the other hand, an increase in the amount of conductive agent may lead to a decrease in battery capacity.

  In addition to the polyimide resin binder, carboxymethyl cellulose, polyacrylic acid soda, other acrylic polymers or fatty acid esters may be added as a viscosity modifier.

[Negative electrode]
The negative electrode material of the nonaqueous electrolyte secondary battery of the present invention can be made into a negative electrode (molded body) as follows, for example. A solvent suitable for dissolving and dispersing the binder such as N-methylpyrrolidone or water in the active material (A), the binder (B), if necessary, a conductive agent and other additives. Are mixed into a paste-like mixture, and this mixture is applied to the sheet of the current collector. In this case, as the current collector, any material that is usually used as a negative electrode current collector, such as a copper foil or a nickel foil, can be used without any particular limitation on thickness and surface treatment. In addition, the shaping | molding method which shape | molds a mixture into a sheet form is not specifically limited, A well-known method can be used. Negative electrode containing a negative electrode material of the present invention is preferably less than two times of charging before volume after charging, more preferably 1.0 to 1.8 times, more preferably 1.0 to 1.6 times. Negative little volume expansion after such charging can be achieved by using the negative electrode material of the present invention. The measurement conditions when less than twice the volume after charging in the present invention (V2) GaTakashi electrostatic previous volume (V1), that is the (V2) / (V1) is less than 2, described in Example This is the condition.

[Nonaqueous electrolyte secondary battery]
By using the negative electrode (molded body) thus obtained, a non-aqueous electrolyte secondary battery including a negative electrode for a non-aqueous electrolyte secondary battery, a positive electrode, a separator, and a non-aqueous electrolyte can be manufactured. A lithium ion secondary battery is preferable. The nonaqueous electrolyte secondary battery is characterized in that the negative electrode material is used, and other materials such as the positive electrode, the separator, and the nonaqueous electrolyte solution, the battery shape, and the like are not limited.

Examples of the positive electrode active material include oxides or sulfides capable of inserting and extracting lithium ions, and these can be used singly or in appropriate combination of two or more. Specifically, TiS ₂ , MoS ₂ , NbS ₂ , ZrS ₂ , VS ₂ , V ₂ O ₅ , MoO _3, Mg (V ₃ O ₈ ) ₂ or other metal sulfide or oxide not containing lithium, or Examples thereof include lithium and lithium composite oxides containing lithium, and composite metals such as NbSe ₂ are also used. Among these, in order to increase the energy density, a lithium composite oxide mainly composed of Li _p MetO ₂ is preferable. Met is preferably one or more of cobalt, nickel, iron and manganese, and p is usually a value in the range of 0.05 ≦ p ≦ 1.10. Specific examples of the lithium composite _{oxide, LiCoO 2, LiNiO 2, LiFeO} 2, Li q Ni r Co 1-r O 2 ( where, the values of q and r is a charge-discharge state of the battery having the layer structure Usually, 0 <q <1, 0.7 <r ≦ 1), spinel-structured LiMn ₂ O _4, orthorhombic LiMnO _{2, and the} like. Furthermore, LiMet _s Mn _1-s O ₄ (0 <s <1) is also used as a substituted spinel manganese compound for high voltage applications, where Met is titanium, chromium, iron, cobalt, nickel, copper and zinc. Etc.

  The lithium composite oxide is obtained by, for example, grinding lithium carbonate, nitrate, oxide or hydroxide, and transition metal carbonate, nitrate, oxide or hydroxide according to a desired composition. It can prepare by mixing and baking at the temperature within the range of 600-1,000 degreeC in oxygen atmosphere.

  Furthermore, an organic substance can also be used as the positive electrode active material. Illustrative examples include polyacetylene, polypyrrole, polyparaphenylene, polyaniline, polythiophene, polyacene, polysulfide compounds and the like.

  The above positive electrode active material is kneaded together with the conductive agent and binder used for the negative electrode mixture and applied to the current collector, and can be formed into a positive electrode (molded body) by a known method.

  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 in general, polyolefins such as polyethylene and polypropylene, copolymers thereof, Examples thereof include a porous sheet such as an aramid resin or a nonwoven fabric. These may be used as a single layer or multiple layers, and ceramics such as metal oxide may be laminated on the surface. Moreover, porous glass, ceramics, etc. are also used.

Examples of the non-aqueous electrolyte include a non-aqueous electrolyte solution containing an electrolyte salt and a non-aqueous solvent. Examples of the electrolyte salt include light metal salts. Examples of the light metal salts include alkali metal salts such as lithium salts, sodium salts, and potassium salts, alkaline earth metal salts such as magnesium salts and calcium salts, and aluminum salts. Can be used in appropriate combination. 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.

  The concentration of the electrolyte salt in the nonaqueous electrolyte 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 / cm or more, and is adjusted according to the type of electrolyte salt or its concentration.

  Furthermore, you may add various additives to a nonaqueous electrolyte solution 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.

As non-aqueous solvent, aprotic high dielectric constant solvent such as ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, dipropyl carbonate, diethyl ether, Acetic acid esters such as tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,3-dioxolane, sulfolane, methylsulfolane, acetonitrile, propionitrile, anisole, methyl acetate, or propionic acid esters Examples include aprotic low viscosity solvents. 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 non-aqueous electrolyte solvent described above.

  In addition, solid electrolytes, gel electrolytes, etc. can be used as non-aqueous electrolytes, and silicone polymers, silicone polyether gels, acrylic gels, silicone acrylic gels, acrylonitrile gels, poly (vinylidene fluoride), etc. are contained as polymer materials. Is possible. These may be polymerized in advance or may be polymerized after injection. These can be used individually by 1 type or in combination of 2 or more types.

  The shape of the nonaqueous electrolyte secondary battery is arbitrary and is not particularly limited. In general, a coin type battery in which an electrode punched into a coin shape and a separator are stacked, and a square type or cylindrical type battery in which an electrode sheet and a separator are wound in a spiral shape are included.

EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, “%” of the composition indicates mass%, and the particle diameter indicates the median diameter D ₅₀ measured by a particle size distribution measuring apparatus by a laser light diffraction method.

[Preparation Example 1: Coated silicon oxide particles 1]
Mixed particles in which silicon dioxide particles (BET specific surface area = 200 m ² / g) and chemical grade metal silicon particles (BET specific surface area = 4 m ² / g) are mixed at an equimolar ratio are mixed at 1350 ° C. and 10 Pa in a high temperature reduced pressure atmosphere. After heat treatment, the generated silicon oxide gas was deposited on a SUS substrate maintained at 800 ° C. Next, this precipitate was collected and then roughly crushed with a jaw crusher. The coarsely pulverized product was pulverized using a jet mill (AFG-100 manufactured by Hosokawa Micron Corporation) at a rotational speed of 9000 rpm of a classifier, and silicon oxide particles having a D ₅₀ = 7.6 μm and D ₉₀ = 11.9 μm (SiOx: x = 1.02) was recovered in a cyclone. When solid-state NMR ( ²⁹ Si-DDMAS) of the obtained particles was measured, the ratio of the signal area of broad silicon dioxide centered around −110 ppm to the signal area of diamond structure silicon around ₋₈₄ ppm (S ₋₈₄ / S ₋₁₁₀ ) was 0.69.
Furthermore, in the resulting silicon oxide particles a horizontal furnace, at 1000 ° C. / 2000 Pa conditions while operating the oil-rotary vacuum pump, a CH ₄ gas flow 0.5 NL / min, graphite coating treatment of 5 hours Went. After the operation, the system was cooled and black particles were collected.
The obtained black particles were conductive particles having an average particle diameter of 8.2 μm and a carbon content of 5% (in the black particles). When this particle was measured by solid-state NMR ( ²⁹ Si-DDMAS) (see FIG. 1), the ratio of the signal area of broad silicon dioxide centered around −110 ppm to the signal area of diamond structure silicon around −84 ppm ( S _-84 / S _-110) is 0.69, as a result of Raman analysis (see FIG. 4) has a spectrum in the vicinity of Raman shift 1330 cm ^-1 and 1580 cm ^-1, the intensity ratio I ₁₃₃₀ / I ₁₅₈₀ was 2.0.

[Comparative Preparation Example 1: Coated silicon oxide particles 2]
The silicon oxide particles used in Preparation Example 1 were subjected to graphite coating treatment at 1150 ° C. under normal pressure (Ar / CH ₄ = 2.0 / 0.5 NL / min mixed gas inflow) without operating the oil rotary vacuum pump. Otherwise, black particles were obtained in the same manner as in Preparation Example 1. The obtained black particles were conductive particles having an average particle diameter of 8.5 μm and a carbon content of 5% (in the black particles). The solid NMR ( ²⁹ Si-DDMAS) of this particle was measured (see FIG. 2). The ratio between the signal area of broad silicon dioxide centered around −110 ppm and the signal area of diamond structure silicon around −84 ppm. (S ₋₈₄ / S ₋₁₁₀ ) is 1.21, and as a result of microscopic Raman analysis (see FIG. 4), the Raman shift has spectra near 1330 cm ⁻¹ and 1580 cm ⁻¹ , and the intensity ratio I ₁₃₃₀ / I ₁₅₈₀ was 1.4.

[Comparative Preparation Example 2: Coated silicon oxide particles 3]
The black particles were prepared in the same manner as in Example 1 except that the silicon oxide particles used in Preparation Example 1 were added to the oil rotary vacuum pump and the mechanical booster pump was operated and the graphite coating treatment was performed under a reduced pressure of 30 Pa. Got. The obtained black particles were conductive particles having an average particle diameter of 8.5 μm and a carbon content of 4.5% (in the black particles). The solid NMR ( ²⁹ Si-DDMAS) of this particle was measured (see FIG. 3), and the ratio of the broad silicon dioxide signal area centered around −110 ppm to the diamond structured silicon signal area around −84 ppm. (S _-84 / S _-110) is 0.69, (see Fig. 4) results of Raman analysis, Raman spectrum, the Raman shift has a spectrum in the vicinity of 1330 cm ^-1 and 1580 cm ^-1 The intensity ratio I ₁₃₃₀ / I ₁₅₈₀ was 3.8.

[Preparation of silicon particles 1]
Metallic silicon lump (ELKEM) is pulverized using a jet mill (AFG-100 manufactured by Hosokawa Micron Corporation) at a rotational speed of a classifier of 7,200 rpm, and then classified by a classifier (TC-15 manufactured by Nisshin Engineering Co., Ltd.). As a result, silicon particles having D ₅₀ = 6.1 μm were obtained.

[Preparation of silicon particles 2]
A polycrystalline silicon lump produced by pyrolysis of trichlorosilane at 1,100 ° C. is crushed with a jaw crusher using a jet mill (AFG-100 manufactured by Hosokawa Micron Corporation) at a rotational speed of 7,200 rpm of a classifier. After pulverization, classification was performed with a classifier (TC-15 manufactured by Nissin Engineering Co., Ltd.) to obtain polycrystalline silicon particles having D ₅₀ = 5.5 μm.

[Preparation of silicon particles 3]
The silicon particles 2 were subjected to thermal CVD in a horizontal heating furnace under the conditions of 1100 ° C./1000 Pa and average residence time of about 2 hours under methane gas flow. After the operation, the system was cooled and black particles were collected.
The obtained black particles were conductive particles having an average particle size = 6.3 μm and a carbon content of 2% by mass (in the black particles).

[Examples 1-5, Comparative Examples 1-3]
The mixture of coated silicon oxide particles and silicon particles obtained in the above example was diluted with N-methylpyrrolidone. A polyimide resin (solid content: 18.1%) was added as a binder to the resulting slurry. This slurry was applied to a copper foil with a thickness of 12 μm using a 50 μm doctor blade, dried under reduced pressure at 200 ° C. for 2 hours, and then pressure-formed with a roller press at 60 ° C., and finally to 2 cm ² . Punched to obtain a molded negative electrode. The solid content composition in the negative electrode material is shown in Table 1.

<Battery characteristics>
In order to confirm the usefulness of the negative electrode material, the charge / discharge capacity and the volume expansion coefficient were measured by the following methods. Lithium foil was used for the negative electrode molded body obtained above and the counter electrode, and lithium bis (trifluoromethanesulfonyl) imide was used as a nonaqueous electrolyte in a 1 mol / L mixed solution of ethylene carbonate and diethyl carbonate (1 mol / L). Six lithium ion secondary batteries for evaluation each using a non-aqueous electrolyte solution dissolved at a concentration and a microporous polyethylene film having a thickness of 30 μm as a separator were prepared.

  The prepared lithium ion secondary battery was left overnight at room temperature, and then two were disassembled immediately after being left to measure the thickness, and the thickness was measured in the electrolyte swelling state to determine the volume (V1). . Note that the amount of increase in lithium due to the electrolyte and charging was not included. The next two batteries were charged with a constant current of 0.05 c until the voltage of the lithium ion secondary battery reached 5 mV using a secondary battery charge / discharge test device (manufactured by Nagano Co., Ltd.), and after reaching 5 mV Were charged by decreasing the current so as to keep the cell voltage at 5 mV. And charge was complete | finished when the electric current value fell below 0.02c. Note that c is a current value for charging the theoretical capacity of the negative electrode in one hour, and 1c = 15 mA. After completion of charging, the lithium ion secondary battery was disassembled, and the volume during charging was obtained by measuring the thickness (V2). From the results of V1 and V2, the volume change magnification after charging was calculated by V2 / V1. did. The remaining two were charged by the above method, and then discharged at a constant current of 0.05 c until reaching 1500 mV, thereby calculating the charge / discharge capacity and obtaining the initial charge / discharge efficiency (%). The charge / discharge capacity is the capacity per active material excluding the binder, and the initial charge / discharge efficiency (%) is expressed as a percentage of the discharge capacity with respect to the charge capacity (discharge capacity / charge capacity × 100). The results are shown in Table 1.

＊ポリイミド樹脂 Ｕ−ワニスＡ（宇部興産（株）製）

* Polyimide resin U-Varnish A (manufactured by Ube Industries)

  Comparing the negative electrode materials of Example 1 and Comparative Examples 1 and 2 using Preparation Example 1 and Comparative Preparation Examples 1 and 2, even if the negative electrode material of the present invention has the same capacity and discharge efficiency, the volume change after charging The magnification was low. Moreover, compared with the comparative example 3 which does not mix | blend a silicon particle as an active material, Example 1-5 which is a negative electrode material of this invention has improved the first time charge / discharge efficiency, and the increase in charge / discharge capacity was recognized. On the other hand, despite the increase in charge / discharge capacity, the volume change magnification has hardly changed.

<Check cycle characteristics>
Using the negative electrode materials of Example 1 and Comparative Examples 1 to 3, a negative electrode molded body was produced by the above method. In order to evaluate the cycle characteristics of the obtained molded negative electrode, a single-layer sheet using LiCoO ₂ as an active material as a positive electrode material and aluminum foil as a current collector (trade name: Pioxel C-, manufactured by Pionics Corporation) 100) was used. The non-aqueous electrolyte uses a non-aqueous electrolyte solution in which lithium hexafluorophosphate is dissolved in a 1/1 (volume ratio) mixture of ethylene carbonate and diethyl carbonate at a concentration of 1 mol / L, and the separator is made of polyethylene having a thickness of 30 μm. A coin-type lithium ion secondary battery using a microporous film was produced.

  The produced coin-type lithium ion secondary battery was allowed to stand at room temperature for two nights, and then used a secondary battery charge / discharge test apparatus (manufactured by Nagano Co., Ltd.), and 1.2 mA until the test cell voltage reached 4.2V. The battery was charged with a constant current of 0.25c (positive electrode reference), and after reaching 4.2V, the battery was charged by decreasing the current so as to keep the cell voltage at 4.2V. The charging was terminated when the current value was less than 0.3 mA. The discharge was performed at a constant current of 0.6 mA, and when the cell voltage reached 2.5 V, the discharge was terminated and the discharge capacity was determined. This was continued for 50 cycles. The percentage of the discharge capacity at the 50th cycle with respect to the initial discharge capacity (discharge capacity at the 50th cycle / initial discharge capacity × 100) was calculated as the discharge capacity retention rate (%). The results are shown in Table 2. In contrast to Comparative Examples 1 to 3, Example 1 shows almost the same cycle characteristics as before the addition of silicon particles, despite the increase in initial efficiency and battery capacity, and the coated silicon oxide of Comparative Examples 1 and 2 Better values were obtained than when particles were used.

2 is a solid state NMR ( ²⁹ Si-DDMAS) of coated silicon oxide particles 1 of Preparation Example 1. 3 is a solid state NMR ( ²⁹ Si-DDMAS) of coated silicon oxide particles 2 of Comparative Preparation Example 1. 3 is a solid state NMR ( ²⁹ Si-DDMAS) of coated silicon oxide particles 3 of Comparative Preparation Example 2. It is a Raman spectrum of Preparation Example 1 and Comparative Preparation Examples 1 and 2.

Claims (9)

Non-water containing active material (A) composed of coated silicon oxide particles (A1) and silicon particles (A2) whose surfaces are coated with a graphite film, and binder (B) 1 to 20% by mass A negative electrode material for an electrolyte secondary battery,
Graphite coating of the coated silicon oxide particles (A1) is, in the Raman spectrum analysis, have a scattering peak at 1330 cm ^-1 and 1580 cm ^-1, their intensity ratio I ₁₃₃₀ / I ₁₅₈₀ is 1.5 <I ₁₃₃₀ / I _In the solid state NMR ( ²⁹ Si-DDMAS) measurement of the coated silicon oxide particles (A1) with ₁₅₈₀ <3.0, the ratio S between the broad signal area centered around −110 ppm and the signal area around −84 ppm ₋₈₄ / S ₋₁₁₀ is 0.5 <S ₋₈₄ / S ₋₁₁₀ <1.1, the ratio of the coated silicon oxide particles (A1) in the active material (A) is 70 to 95% by mass, A negative electrode material for a nonaqueous electrolyte secondary battery, wherein the ratio of silicon particles (A2) is 5 to 30 % by mass.   The non-aqueous electrolyte according to claim 1, wherein the silicon oxide particles are obtained by precipitating a silicon oxide gas obtained by heating a mixture of silicon dioxide and metal silicon to 1000 to 1500 ° C under reduced pressure at 500 to 1100 ° C. Secondary battery negative electrode material.   The negative electrode material for a nonaqueous electrolyte secondary battery according to claim 1 or 2, wherein the silicon particles (A2) are coated silicon particles whose surfaces are coated with a graphite film.   The negative electrode material for a nonaqueous electrolyte secondary battery according to claim 1, 2 or 3, wherein the binder (B) is a polyimide resin. The manufacturing method of the negative electrode material for nonaqueous electrolyte secondary batteries of Claim 1 including following process (I) and (II).
(I) The silicon oxide particles are chemically vapor-deposited at 600 to 1100 ° C. under reduced pressure of 50 to 30000 Pa in an organic gas and / or vapor to prepare a coated silicon oxide particle (A1). The process of
(II) A step of mixing the coated silicon oxide particles (A1), the silicon particles (A2), and the binder (B) obtained in step (I) to prepare a negative electrode material for a nonaqueous electrolyte secondary battery.   6. The nonaqueous electrolyte secondary battery according to claim 5, wherein the silicon oxide particles and the coated silicon oxide particles are in an atmosphere of 1100 ° C. or lower in all steps in which the negative electrode material for a nonaqueous electrolyte secondary battery is obtained from step (I). Manufacturing method of negative electrode material. A negative electrode including a non-aqueous electrolyte secondary battery negative electrode material of any one of claims 1 to 4, a non-aqueous, characterized in that the volume after charging is less than 2 times the previous charging Negative electrode for electrolyte secondary battery.   A nonaqueous electrolyte secondary battery comprising the negative electrode for a nonaqueous electrolyte secondary battery according to claim 7, a positive electrode, a separator, and a nonaqueous electrolyte.   The nonaqueous electrolyte secondary battery according to claim 8, wherein the nonaqueous electrolyte secondary battery is a lithium ion secondary battery.

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