JP6476814B2 - Non-aqueous secondary battery negative electrode carbon material, non-aqueous secondary battery negative electrode and non-aqueous secondary battery using the same - Google Patents

Description

  The present invention relates to a carbon material for a non-aqueous secondary battery negative electrode used for a non-aqueous secondary battery, a negative electrode formed using the carbon material, and a non-aqueous secondary battery including the negative electrode.

A nonaqueous secondary battery comprising a positive electrode and a negative electrode capable of inserting and extracting lithium ions, and a nonaqueous electrolyte solution in which lithium salts such as LiPF ₆ and LiBF ₄ are dissolved has been developed and put into practical use.
Various types of negative electrode materials have been proposed for this battery. From the viewpoint of high capacity and excellent discharge potential flatness, artificial graphite obtained by graphitization of natural graphite, coke, etc. Graphite carbon materials such as graphitized mesophase pitch and graphitized carbon fiber are used as the negative electrode material.

  On the other hand, the application development of non-aqueous secondary batteries, especially lithium ion secondary batteries, has been attempted recently. In addition to conventional notebook PCs, mobile communication devices, portable cameras, portable game machines, etc., electric tools, Applications for electric vehicles are also being developed. As a result, there is a demand for a lithium ion secondary battery that has a rapid charge / discharge property that has been increased as compared with the prior art and that has a high capacity and also has high cycle characteristics.

However, while a high capacity is desired in this way, in a carbon-centered negative electrode, the theoretical capacity of carbon is 372 mAh, so it is impossible to desire a capacity higher than this. Therefore, application of various high capacity materials, particularly metal particles to the negative electrode has been studied.
For example, Patent Document 1 proposes a method for producing Si composite carbon particles by firing a mixture of fine powder of a Si compound, graphite, and a pitch of carbonaceous material precursor.

  Patent Document 2 proposes to use a mixture of Si composite carbon particles obtained by coating Si compound particles with a carbon material and a carbon material. Thus, it has been reported that a non-aqueous secondary battery having a high capacity and excellent cycle characteristics can be provided.

Japanese Patent Laid-Open No. 2003-223892 JP 2003-331832 A

  However, according to the study by the present inventors, the technique described in Patent Document 1 is Si composite carbon particles obtained by combining graphite and Si compound fine powder with a carbonaceous material composed of carbon. In carbon particles, lithium migration is hindered by differences in connectivity during charging and discharging, and due to a decrease in conductivity inside and outside the particles accompanying expansion. As a result, there is a problem that sufficient performance cannot be obtained (low output) by charging and discharging at high speed, and the Si composite carbon particles have not reached a practical level in non-aqueous secondary batteries. In addition, due to the volume expansion of the Si compound fine powder that accompanies charging and discharging, the Si composite carbon particles are peeled off from the electrode plate, causing problems such as cycle deterioration, and the practical level has not been reached.

On the other hand, according to the technique described in Patent Document 2, it is described that the conduction path breakage due to the volume expansion of the Si composite carbon particles accompanying charge / discharge can be improved by mixing the carbon material, and cycle deterioration can be suppressed. . However, the problem of insufficient performance (low output) cannot be solved in charge and discharge at high speed, and electrode plate peeling cannot be sufficiently suppressed.
The present invention solves the above-described problems of the prior art, and has a high capacity, high output, excellent cycle characteristics, low irreversible capacity, and a non-aqueous secondary battery negative electrode carbon material obtained by using the carbon material. It aims at providing the non-aqueous secondary battery provided with the negative electrode for secondary batteries, and the said negative electrode.

  As a result of intensive studies to solve the above problems, the present inventors have obtained composite carbon particles (A) containing at least graphite particles and silicon element (hereinafter, sometimes referred to as Si composite carbon particles (A)), By mixing at least graphite particles, carbonaceous particles, and composite carbon particles (B) containing carbonaceous material (hereinafter, sometimes referred to as composite carbon particles (B)), the capacity is high and the cycle characteristics are excellent. It has been found that a non-aqueous secondary battery with low irreversible capacity can be produced.

Although the mechanism by which the carbon material for a non-aqueous secondary battery negative electrode of the present invention exhibits excellent battery characteristics has not been clarified, it is possible to have a high capacity derived from Si by using Si composite carbon particles (A). It becomes. In addition, since the composite carbon particles (B) enter between the Si composite carbon particles (A), a large flow path and a filling property of the electrolyte are ensured, thereby causing a path caused by expansion and contraction during charge and discharge. It is considered that cutting is suppressed and cycle characteristics are improved. Since the composite carbon particles (B) have fine irregularities of carbonaceous particles on the surface, it is considered that a fine flow path for the electrolyte is secured and the input / output characteristics at low temperatures are improved. Further, it is considered that the contact points between the particles are increased by the fine unevenness of the composite carbon particles (B), and the electrode plate strength is improved. For this reason, it is considered that a carbon material for a negative electrode of a non-aqueous secondary battery having high capacity, excellent cycle characteristics, and low irreversible capacity could be obtained.

That is, the gist of the present invention is a carbon material for a non-aqueous secondary battery negative electrode containing composite carbon particles (A) and composite carbon particles (B), wherein the composite carbon particles (A) include at least graphite particles and The composite carbon particle (B) contains a silicon element, and is present in a carbon material for a non-aqueous secondary battery negative electrode characterized by containing at least graphite particles, carbonaceous particles, and carbonaceous materials.
Another gist of the present invention resides in a negative electrode for a non-aqueous secondary battery, characterized by being formed using the carbon material for a non-aqueous secondary battery negative electrode.

  Another aspect of the present invention is a non-aqueous secondary battery comprising a positive electrode and a negative electrode capable of inserting and extracting lithium ions, and an electrolyte, wherein the negative electrode is the negative electrode for a non-aqueous secondary battery. Next battery.

  According to the present invention, a carbon material for a negative electrode of a nonaqueous secondary battery having excellent stability, high capacity, high output, small irreversible capacity and excellent cycle characteristics, and a nonaqueous secondary battery using the same are provided. can do.

The contents of the present invention will be described in detail below. In addition, description of the invention structural requirements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to these forms unless it exceeds the gist.
The carbon material for a non-aqueous secondary battery negative electrode of the present invention contains Si composite carbon particles (A) and composite carbon particles (B), and the Si composite carbon particles (A) include at least graphitic particles and silicon elements, The carbon particles (B) include at least graphite particles, carbonaceous particles, and carbonaceous materials.
Hereinafter, the Si composite carbon particles (A) and the composite carbon particles (B) used in the present invention will be described.

[Si composite carbon particles (A)]
The Si composite carbon particles (A) in the present invention will be described below.
The Si composite carbon particle (A) of the present invention is not particularly limited as long as it is a material containing at least graphite particles and silicon element.

(A) Volume-based average particle diameter (d50) of Si composite carbon particles (A)
The volume-based average particle diameter (d50) (hereinafter also referred to as average particle diameter d50) of the Si composite carbon particles (A) is usually 1 μm or more, preferably 4 μm or more, more preferably 7 μm or more, and usually 50 μm or less. The thickness is preferably 40 μm or less, more preferably 30 μm or less, and still more preferably 25 μm or less. If the average particle diameter d50 is too large, the total particles are reduced, and the abundance ratio of the Si composite carbon particles (A) in the carbon material of the present invention is reduced. Therefore, it is difficult to obtain the effect of containing the composite graphite particles (B). Tend to be. On the other hand, if the average particle diameter d50 is too small, the specific surface area increases, so the decomposition of the electrolytic solution increases, and the nonaqueous secondary battery (hereinafter referred to as “nonaqueous secondary battery”) obtained using the carbon material of the present invention, The initial efficiency of “battery”) tends to decrease.

  In addition, the measuring method of average particle diameter d50 is as follows. 0.01 g of a sample is suspended in 10 mL of a 0.2% by mass aqueous solution of polyoxyethylene sorbitan monolaurate, which is a surfactant, and introduced into a commercially available laser diffraction / scattering particle size distribution analyzer, and ultrasonic waves of 28 kHz are used. Is measured as a volume-based median diameter in a measuring apparatus after being irradiated for 1 minute at an output of 60 W, which is defined as a volume-based average particle diameter (d50) in the present invention.

(B) Aspect ratio of Si composite carbon particles (A) The aspect ratio of the Si composite carbon particles (A) is usually 1 or more, preferably 1.3 or more, more preferably 1.4 or more, and still more preferably 1.5. As described above, it is usually 4 or less, preferably 3 or less, more preferably 2.5 or less, and further preferably 2 or less.
If the aspect ratio is too large, the particles tend to be aligned in the direction parallel to the current collector when used as an electrode, so that there are not enough continuous voids in the thickness direction of the electrode, and lithium ion mobility in the thickness direction. However, the rapid charge / discharge characteristics of the non-aqueous secondary battery tend to be reduced. The aspect ratio is determined by grinding a resin embedding or electrode plate of particles perpendicularly to a flat plate, taking a cross-sectional photograph thereof, extracting 50 or more particles at random, and extracting the longest diameter of the particles (on the flat plate). It can be measured by measuring the parallel direction) and the shortest diameter (perpendicular to the flat plate) by image analysis and taking the average of the longest diameter / shortest diameter. Since particles embedded in a resin or made into an electrode plate usually tend to have the thickness direction of the particles aligned perpendicular to a flat plate, the above-mentioned method can obtain the longest and shortest diameters characteristic of the particles. I can do it.

(C) Circularity of Si composite carbon particles (A) The circularity of the Si composite carbon particles (A) is usually 0.85 or more, preferably 0.88 or more, more preferably 0.89 or more, and still more preferably 0. .90 or more. The circularity is usually 1 or less, preferably 0.99 or less, more preferably 0.98 or less, and still more preferably 0.97 or less. In addition, the spherical shape in this specification can also be expressed in the range of the circularity.

If the circularity is too small, particles tend to be aligned in parallel with the current collector when used as an electrode, so that there is not enough continuous void in the thickness direction of the electrode, and lithium ion mobility in the thickness direction However, the rapid charge / discharge characteristics of the non-aqueous secondary battery tend to be reduced. If the circularity is too large, there is a tendency that the effect of suppressing the conduction path breakage is reduced and the cycle characteristics are lowered.
In the present invention, the circularity is defined by the following formula (1), and when the circularity is 1, a theoretical sphere is obtained.

Formula (1)
Circularity = (perimeter of equivalent circle having the same area as the particle projection shape) / (actual circumference of particle projection shape)
For the circularity value, a flow type particle image analyzer (for example, FPIA manufactured by Sysmex Industrial Co.) is used, polyoxyethylene (20) monolaurate is used as a surfactant, and ion-exchanged water is used as a dispersion medium. The degree of circularity is calculated by the equivalent circle diameter. The equivalent circle diameter is the diameter of a circle (equivalent circle) having the same projected area as the photographed particle image, and the circularity is the circumference of the equivalent particle as a molecule and the circumference of the photographed particle projection image. The ratio is the denominator. The circularity of particles having a measured equivalent diameter in the range of 10 to 40 μm is averaged to obtain the circularity in the present invention.

(D) Interplanar spacing (d ₀₀₂ ) and crystallite size (Lc) of Si composite carbon particles (A)
The interplanar spacing (d ₀₀₂ ) of the 002 plane by the X-ray wide angle diffraction method of the Si composite carbon particles (A) is usually 0.337 nm or less, preferably 0.336 nm or less. When the d value is too large, the crystallinity is lowered, and the discharge capacity of the nonaqueous secondary battery tends to be lowered. On the other hand, the lower limit is 0.3356 nm, which is the theoretical value of graphite.
The crystallite size (Lc) of the Si composite carbon particles (A) is usually in the range of 30 nm or more, preferably 50 nm or more, more preferably 100 nm or more. Below this range, the crystallinity decreases and the discharge capacity of the battery tends to decrease.

(E) Si Raman R value of the Raman R value Si composite carbon particles (A) of the composite carbon particles (A), in the Raman spectrum of Si composite carbon particles (A), the intensity of the maximum peak _{P A} around 1580 cm ^-1 I _A and the intensity I _B of the maximum peak P _B near 1360 cm ⁻¹ are measured, and the intensity ratio R (R = I _B / I _A ) is calculated and defined. The value is usually 1 or less, preferably 0.8 or less, more preferably 0.6 or less, still more preferably 0.5 or less, and usually 0.05 or more, preferably 0.1 or more, more preferably 0. 2 or more, more preferably 0.25 or more. If the Raman R value is less than this range, the crystallinity of the particle surface becomes too high, the number of Li insertion sites decreases, and the rapid charge / discharge characteristics of the nonaqueous secondary battery tend to be reduced. On the other hand, if it exceeds this range, the crystallinity of the particle surface will be disturbed, the reactivity with the electrolyte will increase, and the charge / discharge efficiency will tend to decrease and the gas generation will increase.

The Raman spectrum can be measured with a Raman spectrometer. Specifically, the sample particles are naturally dropped into the measurement cell to fill the sample, and the measurement cell is rotated in a plane perpendicular to the laser beam while irradiating the measurement cell with an argon ion laser beam. Measure.
Argon ion laser light wavelength: 514.5 nm
Laser power on sample: 25 mW
Resolution: 4cm ^-1
Measurement range: 1100 cm ^{−1 to} 1730 cm ⁻¹
Peak intensity measurement, peak half-width measurement: background processing, smoothing processing (convolution 5 points by simple average)

(F) Surface functional group amount of Si composite carbon particle (A) The Si composite carbon particle (A) has a surface functional group amount O / C value represented by the following formula (2) of usually 0.1% or more. , Preferably 1% or more, more preferably 2% or more, while usually 30% or less, preferably 20% or less, more preferably 15% or less. If the surface functional group amount O / C value is too small, the desolvation reactivity of the Li ion and the electrolyte solvent on the negative electrode active material surface tends to decrease, and the large current charge / discharge characteristics of the nonaqueous secondary battery tend to decrease. When O / C is too large, the reactivity with the electrolytic solution increases, and the charge / discharge efficiency tends to decrease.

Formula (2)
O / C value (%)
= {(O atom concentration determined based on peak area of O1s spectrum in X-ray photoelectron spectroscopy (XPS) analysis) / (C atom concentration determined based on peak area of C1s spectrum in XPS analysis)} × 100
The surface functional group amount O / C value in the present invention can be measured using X-ray photoelectron spectroscopy (XPS) as follows.

  Using an X-ray photoelectron spectrometer, the object to be measured is placed on a sample stage so that the surface is flat, and aluminum Kα rays are used as an X-ray source, and C1s (280 to 300 eV) and O1s (525 to 545 eV) are obtained by multiplex measurement. ) Spectrum. The obtained C1s peak top is corrected to be 284.3 eV, the peak areas of the C1s and O1s spectra are obtained, and the device sensitivity coefficient is multiplied to calculate the surface atomic concentrations of C and O, respectively. The obtained ratio of the atomic concentration of O and C, O / C (O atomic concentration / C atomic concentration), expressed as a percentage, is defined as the surface functional group amount of the sample (Si composite carbon particles (A)). .

(G) BET specific surface area (SA) of Si composite carbon particles (A)
About the specific surface area measured by BET method of Si composite carbon particle (A), it is 0.1 m < ² > / g or more normally, Preferably it is 0.7 m < ² > / g or more, More preferably, it is 1 m < ² > / g or more. Moreover, it is 40 m < ² > / g or less normally, Preferably it is 30 m < ² > / g or less, More preferably, it is 20 m < ² > / g or less, More preferably, it is 18 m < ² > / g or less, Most preferably, it is 17 m < ² > / g or less.

If the specific surface area is too small, the number of sites where lithium ions enter and exit is small, and the high-speed charge / discharge characteristics and output characteristics are inferior. Therefore, there is a tendency that a high-capacity non-aqueous secondary battery cannot be manufactured.
The BET specific surface area is measured by a BET one-point method using a specific surface area measuring device by a nitrogen gas adsorption flow method.

(H) Tap density of Si composite carbon particles (A) The tap density of Si composite carbon particles (A) is usually 0.5 g / cm ³ or more, preferably 0.6 g / cm ³ or more, more preferably 0. .8g / cm ³ or more, more preferably 0.85 g / cm ³ or more, particularly preferably 0.9 g / cm ³ or more and usually less than 1.3 g / cm ^3, preferably 1.2 g / cm ³ or less Yes, more preferably 1.1 g / cm ³ or less. When the tap density is too low, the high-speed charge / discharge characteristics of the non-aqueous secondary battery are inferior. When the tap density is too high, the cycle characteristics may be deteriorated due to the disconnection of the conductive path due to the decrease in particle contactability.

In the present invention, the tap density is measured by dropping a sample (Si composite carbon particles (A)) through a sieve having a mesh size of 300 μm through a cylindrical tap cell having a diameter of 1.6 cm and a volume capacity of 20 cm ³ using a powder density measuring device. Then, after the cell is fully filled, a tap having a stroke length of 10 mm is performed 1000 times, and the density is defined as the density obtained from the volume at that time and the weight of the sample.
In the present invention, the tap density is measured by dropping a sample (Si composite carbon particles (A)) through a sieve having a mesh size of 300 μm through a cylindrical tap cell having a diameter of 1.6 cm and a volume capacity of 20 cm ³ using a powder density measuring device. After the cell is fully filled, a tap with a stroke length of 10 mm is performed 1000 times, and the density obtained from the volume at that time and the weight of the sample is defined as the tap density.

(I) DBP oil absorption of Si composite carbon particles (A) The DBP (dibutyl phthalate) oil absorption of Si composite carbon particles (A) is usually 65 ml / 10.
0 g or less, preferably 62 ml / 100 g or less, more preferably 60 ml / 100 g or less, still more preferably 57 ml / 100 g or less. Moreover, it is 30 ml / 100g or more normally, Preferably it is 40 ml / 100g or more, More preferably, it is 50 ml / 100g or more. If the DBP oil absorption is too large, it tends to cause streaking during the application of the slurry containing the carbon material of the present invention when forming the negative electrode, and if it is too small, there is almost no pore structure in the particles. There is a possibility that it has not, and there is a tendency for the reaction surface to decrease.

  The DBP oil absorption amount in the present invention is defined by measured values when 40 g of a measurement material is added, the dropping speed is 4 ml / min, the rotation speed is 125 rpm, and the set torque is 500 N · m in accordance with JIS K6217. For the measurement, an Asahi Research Institute absorption meter (S-500) or the like can be used.

(J) Aspect of silicon element in Si composite carbon particle (A) As an aspect of silicon element contained in the Si composite carbon particle (A) in the present invention, Si, SiOx, SiNx, SiCx, SiZxOy (Z = C, N) and the like, and these are collectively referred to as Si compounds in the present invention. Among these, Si and SiOx are preferable from the viewpoint of the capacity of the nonaqueous secondary battery. The compound of the general formula SiOx is obtained using Si dioxide (SiO ₂ ) and metal Si (Si) as raw materials, and the value of x is usually 0 <x <2, preferably 0.2 or more and 1. It is 8 or less, more preferably 0.4 or more and 1.6 or less, and still more preferably 0.6 or more and 1.4 or less. Within this range, the non-aqueous secondary battery has a high capacity, and at the same time, the irreversible capacity due to the combination of Li and oxygen can be reduced.

As an aspect of the silicon element in the Si composite carbon particles (A) in the present invention, an aspect of Si compound particles in which the Si compound is formed into particles is preferable from the viewpoint of the capacity of the non-aqueous secondary battery.
Further, the content of silicon element in the Si composite carbon particles (A) in the present invention is usually 0.5% by mass or more, preferably 1% by mass or more, more preferably 2% with respect to the Si composite carbon particles (A). It is at least 5% by mass, more preferably at least 5% by mass, particularly preferably at least 10% by mass. Moreover, it is 99 mass% or less normally, Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 25 mass% or less, Most preferably, it is 20 mass% or less. This range is preferable in that a non-aqueous secondary battery having a sufficient capacity can be obtained.

  In addition, the measuring method of content of the silicon element in Si composite carbon particle (A) is as follows. After completely melting the sample with alkali, the sample is dissolved and fixed in water, measured with an inductively coupled plasma emission analyzer (Horiba, Ltd. ULTIMA2C), and the amount of silicon element is calculated from the calibration curve. Thereafter, the silicon element content in the Si composite carbon particles (A) can be calculated by dividing the silicon element amount by the weight of the Si composite carbon particles (A).

(K) The silicon element abundance ratio in the Si composite carbon particles (A) The silicon element abundance ratio calculated by the following measurement method in the Si composite carbon particles (A) used in the present invention is usually 0.8. 2 or more, preferably 0.3 or more, more preferably 0.4 or more, further preferably 0.5 or more, particularly preferably 0.6 or more, and usually 1.5 or less, preferably 1. 2 or less, more preferably 1.0 or less. The higher this value, the more silicon element present inside the Si composite carbon particles (A) compared to the silicon element present outside the Si composite carbon particles (A), and the negative electrode was formed. At this time, there is a tendency that a decrease in charge / discharge efficiency due to the disconnection of the conductive path between particles can be suppressed.

The abundance ratio of silicon element in the Si composite carbon particles (A) is calculated as follows. First, a coating film of Si composite carbon particles (A) or Si composite carbon particles (A) is embedded in a resin to produce a thin piece of resin, and a cross section of the particle is cut out by focused ion beam (FIB) or ion milling. Then, it observes by observation methods, such as particle | grain cross-section observation by SEM (scanning electron microscope).
The accelerating voltage when observing the cross section of one Si composite carbon particle (A) with an SEM (scanning electron microscope) is preferably 1 kV or more, more preferably 2 kV or more, and further preferably 3 kV or more. 10 kV or less, more preferably 8 kV or less, still more preferably 5 kV or less. Within this range, the graphite particles and the Si compound can be easily identified due to the difference in the reflected secondary electron image in the SEM image. The imaging magnification is usually 500 times or more, more preferably 1000 times or more, still more preferably 2000 times or more, and usually 10000 times or less. If it is said range, the whole image of 1 particle | grains of Si composite carbon particle (A) is acquirable. The resolution is 200 dpi (ppi) or more, preferably 256 dpi (ppi) or more. The number of pixels is preferably evaluated at 800 pixels or more. Next, while observing the image, the graphite and silicon elements are identified by the energy dispersion type (EDX) and the wavelength dispersion type (WDX).

One Si composite carbon particle (A) particle is extracted from the acquired image, and the area (a) of the Si compound in the particle is calculated. Next, after binarizing the extracted 1 particle and the background other than the 1 particle, the shrinking process is repeated on the particle, and a figure with an area of 70% of the extracted 1 particle is extracted. The area (b) of the silicon element present is calculated. In addition, in the area when the reduction process is repeatedly performed, when the value of 70% cannot be accurately shown, the value closest to 70% in the value of 70% ± 3% is 70% in the present invention. A figure. The extraction of one particle, the calculation of the area, the binarization process, and the reduction process can be performed by using general image processing software. Examples of the software include “Image J” and “Image-Pro plus”. Etc.
The value obtained by dividing the area (b) calculated above by the area (a) is measured with arbitrary three particles, and the value obtained by averaging the values of these three particles is the silicon element in the Si composite carbon particles (A). The abundance ratio.

(Aspect of Si composite carbon particles (A))
The aspect of the Si composite carbon particles (A) described above is not particularly limited as long as it is a carbon material containing a silicon element.
(I) Si compound particles dispersed in a granulated body made of a carbon material,
(B) Si compound particles are attached or coated on the outer periphery of the carbon material serving as a nucleus,
(C) Si compound particles dispersed inside a spheroidized carbon material,
(D) A carbonaceous material attached or coated on the outer periphery of the Si compound particles as the core,
(E) A combination of these may be used.

  By encapsulating Si compound particles inside the Si composite carbon particles (A), by suppressing the stress due to volume expansion associated with charge and discharge of the Si compound, particle breakage and the accompanying conduction path interruption are suppressed, (C) Because non-aqueous secondary batteries tend to exhibit high capacity and high cycle characteristics, and tend to exhibit high initial efficiency by inhibiting side reactions by preventing contact with the electrolyte. A material in which Si compound particles are dispersed inside a spheroidized carbon material is preferable. At this time, it is preferable that at least one of the Si compound particles is in contact with the carbon material from the viewpoint of suppressing an increase in irreversible capacity.

  In the present specification, the term “adhesion” refers to a state in which Si compound particles are attached to, adhered to, or combined with the surface of the carbon material, and these states include, for example, a field emission scanning electron microscope-energy dispersive type. This can be confirmed by observing the cross section of the particle using techniques such as X-ray (SEM-EDX) analysis and X-ray photoelectron spectroscopy (XPS) analysis.

<Method for producing Si composite carbon particles (A)>
(Raw material for Si composite carbon particles (A))
The Si composite carbon particles (A) described above are not particularly limited as long as they are Si composite carbon particles in which a silicon element and a carbon material are composited. For example, carbon materials, Si compound particles, and organic substances that become carbonaceous materials are used. It can be produced using a compound.

-Carbon material The carbon material used as a raw material is not particularly limited, but when producing the Si composite carbon particles (A) of (a) or (c) above, graphite particles such as natural graphite, artificial graphite, or the like Examples thereof include a fired material made of a material selected from the group consisting of coal-based coke, petroleum-based coke, furnace black, acetylene black, and pitch-based carbon fiber having slightly lower crystallinity. These may be used individually by 1 type and may be used in combination of 2 or more type.

Among these, natural graphite is classified into flake graphite (FlakeGraphite), scaly graphite (CrystalLine (Vein) Graphite), and soil graphite (Amorphous Graphite). ) Graphite section of Industrial Technology Center, published in 1974), and "HANDBOOKOF
CARBON, GRAPHITE, DIAMOND AND FULLLINES "(N
(see publishes oysPublications)). Graphite crystallinity (degree of graphitization) is the highest at 100% for scaly graphite, followed by 99.9% for scaly graphite. Therefore, it is preferable to use these graphites.

The production area of scaly graphite, which is natural graphite, is Madagascar, China, Brazil, Ukraine, Canada, etc., and the production area of scaly graphite is mainly Sri Lanka. The main producers of soil graphite are the Korean Peninsula, China and Mexico.
Among these natural graphites, scaly graphite and scaly graphite have advantages such as high graphite crystallinity and a low amount of impurities, and therefore can be preferably used in the present invention, and scaly graphite is more preferable. Visual methods for confirming that graphite is scaly include particle surface observation with a scanning electron microscope, embedding particles in a resin to produce a thin piece of resin, and cutting out the particle cross section, or coating consisting of particles Examples of the method include a method of observing a particle cross section with a scanning electron microscope after preparing a cross section of a coating film with a cross section polisher and cutting out the particle cross section.

Scaly graphite and scaly graphite have natural graphite that is highly purified so that the crystallinity of graphite is almost completely crystallized, and artificially formed graphite. Natural graphite is soft and folded. It is preferable in that it is easy to fabricate the structure.
In addition, when producing the Si composite carbon particles (A) of (b) above, graphite particles obtained by spheroidizing by applying mechanical stress to, for example, flaky graphite, etc., from the point that the shape can be maintained as the core of the particles, or graphite and carbon It is preferable to use graphite particles obtained by mixing and granulating an organic compound that becomes a material.

In addition, what shows the following physical properties for the carbon material used as a raw material in this invention is preferable.
The volume-based average particle diameter (d50) of the carbon material used as a raw material is not particularly limited, but is usually 1 μm or more and 120 μm or less, preferably 3 μm or more and 100 μm or less, more preferably 5 μm or more and 90 μm or less. If the average particle diameter d50 of the carbon material used as a raw material is too large, the particle diameter of the Si composite carbon particles (A) becomes large, and the negative electrode active material mixed with the Si composite carbon particles (A) is applied in a slurry form. In this process, streaks or irregularities due to large particles may occur. If the flat body particle size d50 is too small, it is difficult to form a composite, and it may be difficult to produce the Si composite carbon particles (A).

The tap density of the carbon material used as a raw material is usually less than 0.1 g / cm ³ or more 1.0 g / cm ^3, preferably 0.13 g / cm ³ or more 0.8 g / cm ³ or less, more preferably 0 .15 g / cm ³ or more and 0.6 g / cm ³ or less. When the tap density is within the above range, minute voids are easily formed in the Si composite carbon particles (A), and thus the destruction of the Si composite carbon particles (A) due to the expansion and contraction of the Si compound particles can be suppressed.

BET specific surface area of the carbon material used as a raw material is usually ^{1 m} 2 / g or more ^{40 m} 2 / g or less, preferably less ^2m 2 / g or more ^{35m 2 / g, 3m 2 /} g or more ^{30 m} 2 / g The following is more preferable. The specific surface area of the carbon material used as a raw material is reflected in the specific surface area of the Si composite carbon particles (A), and the battery capacity due to an increase in the irreversible capacity of the Si composite carbon particles (A) by being 40 m ² / g or less. Can be prevented.

The interplanar spacing (d ₀₀₂ ) of the 002 plane according to the X-ray wide angle diffraction method of the carbon material used as a raw material is usually 0.337 nm or less. Meanwhile _{d 002} is usually 0.334nm more. The carbon material used as a raw material has an Lc of 90 nm or more, preferably 95 nm or more by X-ray wide angle diffraction. When the interplanar spacing (d ₀₀₂ ) of the 002 plane is 0.337 nm or less, it indicates that the carbon material used as a raw material has high crystallinity, and provides a high capacity non-aqueous secondary battery (A) Can be obtained. In addition, when Lc is 90 nm or more, Si composite carbon particles (A) exhibiting high crystallinity and having a high capacity for the nonaqueous secondary battery can be obtained.

-Si compound particle | grains As a Si compound particle | grain used as a raw material of Si composite carbon particle (A) in this invention, what shows the following physical properties is preferable.
The volume average particle diameter (d50) of the Si compound particles used as a raw material is usually 0.005 μm or more, preferably 0.01 μm or more, more preferably 0.02 μm or more, and further preferably 0.03 μm, from the viewpoint of cycle life. These are usually 10 μm or less, preferably 9 μm or less, more preferably 8 μm or less. When the average particle diameter (d50) is within the above range, volume expansion associated with charge / discharge of the nonaqueous secondary battery is reduced, and good cycle characteristics can be obtained while maintaining the charge / discharge capacity.

The specific surface area by the BET method of the Si compound particles used as a raw material is usually 0.5 m ² / g or more and 120 m ² / g or less, and preferably 1 m ² / g or more and 100 m ² / g or less. It is preferable that the specific surface area is within the above range because the charge / discharge efficiency and discharge capacity of the non-aqueous secondary battery are high, lithium is taken in and out quickly during high-speed charge / discharge, and the rate characteristics are excellent.
Although there is no restriction | limiting in particular in the oxygen content of Si compound particle | grains used as a raw material, Usually, 0.01 mass% or more and 12 mass% or less are preferable and they are 0.05 mass% or more and 10 mass% or less.

The oxygen distribution state in the Si compound particles may be present in the vicinity of the surface, in the particle, or uniformly in the particle, but is preferably present in the vicinity of the surface. It is preferable for the oxygen content of the particles to be in the above-mentioned range because the volume expansion associated with charge / discharge is suppressed due to strong bonding between Si and O, and the cycle characteristics of the nonaqueous secondary battery are excellent.
The crystallite size of the Si compound particles used as a raw material is not particularly limited, but is usually 0.05 nm or more, preferably 1 nm or more in the (111) plane crystallite size calculated from XRD. It is 100 nm or less, and preferably 50 nm or less. It is preferable that the crystallite size of the particles is in the above range because the reaction between Si and Li ions proceeds rapidly and is excellent in battery input / output.
In addition, it is preferable that Si compound particle | grains in Si composite carbon particle (A) have the property similar to the physical property of Si compound particle | grains used as a raw material.

-Organic compound used as carbonaceous material As an organic compound used as a carbonaceous material used as a raw material of Si composite carbon particles (A) in the present invention, a carbon material described in the following (a) or (b) is preferable.
(A) Coal heavy oil, DC heavy oil, cracked heavy oil, aromatic hydrocarbon, N ring compound, S ring compound, polyphenylene, organic synthetic polymer, natural polymer, thermoplastic resin and Carbonizable organic substance selected from the group consisting of thermosetting resins

(B) What dissolved carbonizable organic substance in low molecular organic solvent As said coal type heavy oil, coal tar pitch from a soft pitch to a hard pitch, dry distillation liquefied oil, etc. are preferable, The said DC type heavy oil As preferred, atmospheric residual oil, reduced pressure residual oil, etc., the cracked petroleum heavy oil is preferably ethylene tar produced as a by-product during thermal decomposition of crude oil, naphtha, etc., and the aromatic hydrocarbon is Acenaphthylene, decacyclene, anthracene, phenanthrene and the like are preferable, the N ring compound is preferably phenazine, acridine and the like, the S ring compound is preferably thiophene, bithiophene and the like, and the polyphenylene is biphenyl, terphenyl and the like. Preferably, the organic synthetic polymer includes polyvinyl chloride, polyvinyl alcohol, polyvinyl Preferred are tyral, insolubilized products of these, polyacrylonitrile, polypyrrole, polyallylamine, polyvinylamine, polyethyleneimine, urethane resin, urea resin, and other nitrogen-containing polymers, polythiophene, polystyrene, polymethacrylic acid, etc. Is preferably a polysaccharide such as cellulose, lignin, mannan, polygalacturonic acid, chitosan, saccharose, etc., and the thermoplastic resin is preferably polyphenylene sulfide, polyphenylene oxide or the like, and the thermosetting resin is Furyl alcohol resin, phenol-formaldehyde resin, imide resin and the like are preferable.

Further, the carbonizable organic substance may be a carbide such as a solution dissolved in a low-molecular organic solvent such as benzene, toluene, xylene, quinoline, and n-hexane.
Moreover, these may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations.
In addition, as a carbonaceous material in Si composite carbon particle (A), the thing (amorphous thing) whose graphite crystallinity is lower than a graphite particle is preferable. Specifically, what shows the following physical properties is preferable.

The interplanar spacing (d ₀₀₂ ) of the (002) plane of the carbonaceous material powder by X-ray wide angle diffraction method is usually 0.340 nm or more, preferably 0.342 nm or more. Moreover, it is less than 0.380 nm normally, Preferably it is 0.370 nm or less, More preferably, it is 0.360 nm or less. If the d ₀₀₂ value is too large, it indicates that the crystallinity is low, and the cycle characteristics of the non-aqueous secondary battery tend to deteriorate. If the d ₀₀₂ value is too small, the effect of combining carbonaceous materials is obtained. hard.

  The crystallite size (Lc (002)) of the carbonaceous material obtained by X-ray diffraction based on the Gakushin method of the carbonaceous material powder is usually 5 nm or more, preferably 10 nm or more, more preferably 20 nm or more. Moreover, it is 300 nm or less normally, Preferably it is 200 nm or less, More preferably, it is 100 nm or less. If the crystallite size is too large, the cycle characteristics of the non-aqueous secondary battery tend to decrease.If the crystallite size is too small, the charge / discharge reactivity decreases, resulting in increased gas generation and high current during high-temperature storage. There is a risk of deterioration of charge / discharge characteristics.

<Type of manufacturing method>
The Si composite carbon particles (A) described above are not particularly limited as long as they are Si composite carbon particles in which a silicon element and a carbon material are combined. For example, the following methods (i) to (iii) are used. Can be manufactured by.

(Method (i))
(B) Si compound carbon particles (A) in which Si compound particles are dispersed in the granulated body made of carbon material (A) and (b) Si compound particles are attached or coated on the outer periphery of the carbon material that becomes the nucleus. S
In order to manufacture i composite carbon particle (A), the method of mixing and granulating the carbon material, Si compound particle | grains, and the organic compound used as a carbonaceous material is mentioned, for example.

As a concrete process in the method,
(1) A step of mixing Si compound particles, a carbon material, and an organic compound to be a carbonaceous material, and (2) a step of firing the mixture obtained in (1).
Si composite carbon particles (A) can be produced by a method including at least the steps (1) to (2). Hereinafter, the steps (1) and (2) will be described.

(1) Step of mixing Si compound particles, carbon material, and organic compound that becomes carbonaceous material Mixing Si compound particles, carbon material, and organic compound that becomes carbonaceous material, and if a mixture can be obtained, in order to prepare the raw materials in particular Although there is no restriction, for example, a method of mixing an organic compound that becomes a carbonaceous material after mixing a carbon material with Si compound particles, a method of mixing an Si compound particle with an organic compound that becomes a carbonaceous material, and Si Examples thereof include a method of mixing a carbon material after mixing an organic compound that becomes a carbonaceous material into compound particles, a method of mixing an Si compound particle, a carbon material, and an organic compound that becomes a carbonaceous material at once.

  In the method of mixing an organic compound that becomes a carbonaceous material after mixing a carbon material with Si compound particles, the carbonaceous material is adhered to the surface and / or inside of the carbon material by mechanical treatment. You may mix the organic compound which becomes. The mechanical treatment here is not particularly limited, but for example, a dry ball mill, a wet bead mill, a planetary ball mill, a vibrating ball mill, a mechano-fusion system, an agromaster (Hosokawa Micron Corporation), a hybridization system, a micros, a mirror ( (Nara Machinery Co., Ltd.) and the like.

Among the mixing methods described above, the method of mixing an organic compound that becomes a carbonaceous material after mixing a carbon material with Si compound particles mixes the Si compound particles and the carbon material in a powder state, so that the dispersibility is good. It is preferable in that it is.
Specific mixing methods in the method of mixing the Si compound particles, the carbon material, and the organic compound that becomes the carbonaceous material include, for example, a powder mixing method, a melt mixing method, and a solution mixing method.

  The mixing temperature in these methods is usually from room temperature to 300 ° C., and can be appropriately determined depending on the type of organic compound to be a carbonaceous material. The mixing time is usually 10 minutes or more and 1 hour or less. In addition, the solvent used in the solution mixing method with the Si compound particles, the carbon material, and the organic compound that becomes the carbonaceous material can be appropriately selected from water or an organic solvent in which the organic compound is dissolved or dispersed. Two or more different solvents may be mixed and used.

When a solution mixing method with Si compound particles, a carbon material, and an organic compound that becomes a carbonaceous material is used, drying is usually performed in a range of 40 ° C. or more and 300 ° C. or less. Although drying time can be suitably determined according to the kind of solvent used, it is normally 1 hour or more and 24 hours or less. Vacuum drying can be selected as appropriate.
The mixing of the Si compound particles, the carbon material, and the organic compound that becomes the carbonaceous material is usually performed under normal pressure, but can be performed under reduced pressure or under pressure if desired. Mixing can be carried out either batchwise or continuously. In any case, mixing efficiency can be improved by using a combination of an apparatus suitable for rough mixing and an apparatus suitable for fine mixing.

Batch-type mixing devices include high-speed mixers, homogenizers, ultrasonic homogenizers, mixers with a structure in which two frame types rotate and revolve, dissolvers that are high-speed, high-shear mixers, and butterfly mixers for high viscosity. A single blade stirs in the tank
Dispersing device, so-called kneader-type device having a structure in which a sigma-type stirring blade rotates along the side surface of a semi-cylindrical mixing tank, a trimix-type device with three stirring blades, and a container A so-called bead mill type apparatus having a rotating disk and a dispersion medium inside is used.

  It also has a container with a paddle that is rotated by a shaft, and the inner wall surface of the container is formed substantially along the outermost line of rotation of the paddle, preferably in a long twin cylinder shape, and the paddle has side surfaces facing each other. A device having a structure in which many pairs are arranged in the axial direction of the shaft so as to be slidably engaged (for example, KRC reactor manufactured by Kurimoto Iron Works, SC processor, TEM manufactured by Toshiba Machine Celmac, TEX-K manufactured by Nippon Steel Works) Etc.), and a container having a plurality of pavement or sawtooth paddles fixed to the shaft and arranged in multiple phases, the inner wall surface of which is the outermost line of rotation of the paddle Substantially along the (externally heated) device, preferably in the form of a cylinder (for example, a Redige mixer manufactured by Redige, a flow share mixer manufactured by Taiyo Kiko Co., Ltd., a Tsukishima Machine Co., Ltd. T dryer, etc.) can also be used.

In order to perform mixing in a continuous manner, a pipeline mixer, a continuous bead mill, or the like may be used.
The mixing ratio of the Si compound particles with respect to the total of the Si compound particles, the carbon material, and the organic compound as the carbonaceous material is usually 1% by mass or more, preferably 1.5% by mass or more, more preferably 2% by mass or more, and still more preferably. Is 2.5% by mass or more. Moreover, it is 50 mass% or less normally, Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less. When there are too many Si compound particles, the volume expansion accompanying charging / discharging will become large in a non-aqueous secondary battery, and there exists a tendency for capacity deterioration to become remarkable. Moreover, when there are too few Si compound particles, there exists a tendency for sufficient capacity | capacitance not to be obtained.

  The mixing ratio of the carbon material to the total of the Si compound particles, the carbon material, and the organic compound as the carbonaceous material is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass. That's it. Moreover, it is 95 mass% or less normally, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less. If the carbon material is too much, the amount of voids formed by the carbon material increases, and it tends to be difficult to increase the electrode density. Moreover, when there are too few carbon materials, the space | gap which suppresses volume expansion cannot be formed, it becomes difficult to take a conductive path, and there exists a tendency for the effect which improves the cycling characteristics of a non-aqueous secondary battery not fully acquired.

  The mixing ratio of the organic compound that becomes the carbonaceous material to the total of the organic compound that becomes the Si compound particles, the carbon material and the carbonaceous material is usually 1% by mass or more, preferably 1.5% with respect to the total mass of the carbon material and the Si compound particles. It is at least 2 mass%, more preferably at least 2.5 mass%. Moreover, it is 60 mass% or less normally, Preferably it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less. When there are too many organic compounds used as a carbonaceous material, there exists a tendency for active material to aggregate easily in a baking process. Moreover, when there are too few organic compounds used as a carbonaceous material, there exists a tendency for sufficient effect not to be acquired in progress of a reductive reaction, or aggregation suppression of an active material.

(2) The step of firing the mixture obtained in (1) In this step, the mixture containing the Si compound particles, the carbon material, and the organic compound that becomes the carbonaceous material obtained in the step (1) is fired.
The atmosphere at the time of firing is a non-oxidizing atmosphere, and preferably firing is performed in a non-oxidizing atmosphere by circulating nitrogen, argon, carbon dioxide, ammonia, hydrogen, or the like.

The reason for firing in a non-oxidizing atmosphere is that it is necessary to prevent oxidation of Si compound particles, a carbon material, and an organic compound that becomes a carbonaceous material.
The firing temperature varies depending on the firing atmosphere and the organic compound that becomes the carbonaceous material, but as an example, the firing temperature is usually 500 ° C. or higher, preferably 800 ° C. or higher, more preferably 850 ° C. or higher in a nitrogen circulation atmosphere. Further, it is usually at most 3000 ° C., preferably 2000 ° C. or less, more preferably 1500 ° C. or less, even if it is high. If the firing temperature is too low, carbonization does not proceed sufficiently, and the irreversible capacity at the beginning of charge / discharge of the non-aqueous secondary battery may increase, and the reduction rate of the Si compound decreases, so the firing time is increased. Need arises. However, the reduction rate can be increased even at a low temperature by setting the firing atmosphere to a stronger reducing atmosphere such as a hydrogen atmosphere.

On the other hand, if the firing temperature is too high, the carbonized organic compound carbide will reach a crystal structure equivalent to the crystal structure of the raw material carbon material in the mixture, making it difficult to obtain the coating effect, and vaporizing the silicon element. This tends to reduce the yield and increase the manufacturing cost.
In the firing treatment conditions, the heat history temperature condition, the temperature rise rate, the cooling rate, the heat treatment time, etc. are appropriately set. Further, after heat treatment in a relatively low temperature region, the temperature can be raised to a predetermined temperature.

  In addition, the reactor used for this process may be a batch type or a continuous type, and may be one or more. The furnace used for firing is not particularly limited as long as the above requirements are satisfied. For example, a reactor such as a shuttle furnace, a tunnel furnace, a lead hammer furnace, a rotary kiln, an autoclave, a coker (heat treatment tank for coke production), a Tamman furnace, The Atchison furnace can be mentioned. As the heating method, high-frequency induction heating, direct resistance heating, indirect resistance heating, direct combustion heating, radiant heat heating, or the like can be used. During the treatment, stirring may be performed as necessary.

Other Steps The composite carbon material that has undergone the above steps is subjected to powder processing such as pulverization, crushing, and classification to obtain Si composite carbon particles (A).
There are no particular restrictions on the apparatus used for pulverization and pulverization, for example, the coarse pulverizer includes a shearing mill, jaw crusher, impact crusher, cone crusher, etc., and the intermediate pulverizer includes roll crusher, hammer mill, etc. Examples of the pulverizer include a ball mill, a vibration mill, a pin mill, a stirring mill, and a jet mill.

There is no particular limitation on the apparatus used for classification, but for example, in the case of dry sieving, a rotary sieving, a swaying sieving, a rotating sieving, a vibrating sieving, etc. can be used. In this case, gravity classifier, inertial classifier, centrifugal classifier (classifier, cyclone, etc.) can be used, wet sieving, mechanical wet classifier, hydraulic classifier, sedimentation classifier A centrifugal wet classifier or the like can be used.
Si composite carbon particles (A) can be produced by the production method as described above. However, Si composite carbon particle (A) is not limited to what was manufactured with the said manufacturing method.

(Method (ii))
Examples of the method for producing the Si composite carbon particles (A) in which the Si compound particles are dispersed inside the spheroidized carbon material described above are, for example, mixing the carbon material and the Si compound particles, and then spherical An example is a method of encapsulating Si compound particles inside Si composite carbon particles by performing a chemical treatment. In addition, the carbon material as a raw material in the method (ii), the Si compound particles, and the organic compound that becomes the carbonaceous material used in the step (3) described later are not particularly limited, and the method (i) and The same can be used.

A preferable production method includes the following steps.
(1) Step of mixing and fixing the carbon material and Si compound particles (2) Step of applying a spheroidizing treatment to the product obtained in (1) (1) Mixing and fixing the carbon material and Si compound particles The mixing ratio of the Si compound particles to the total of the Si compound particles and the carbon material is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, particularly preferably. Is 10% by mass or more. Moreover, it is 95 mass% or less normally, Preferably it is 70 mass% or less, More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less, Most preferably, it is 40 mass% or less, Most preferably, it is 35 mass% or less. This range is preferable in that a sufficient capacity can be obtained in the non-aqueous secondary battery.

  There is no particular limitation on the method for mixing and fixing the carbon material and the Si compound particles. For example, there is a method in which a Si slurry in which Si compound particles are dispersed in a solvent is used and mixed with a carbon material so that the wet Si compound particles are not dried. Since such Si slurry suppresses aggregation of Si compound particles, it is preferable because the Si compound particles are easily fixed on the surface of the carbon material.

  Examples of the dispersion solvent for the Si compound particles include a nonpolar compound having an aromatic ring and an aprotic polar solvent. The type of the nonpolar compound having an aromatic ring is not particularly limited, but reacts with the Si compound. It is more preferable if it does not have the property. For example, aromatic compounds such as benzene, toluene, xylene, cumene, and methylnaphthalene that are liquid at room temperature, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl, petrochemicals such as light oil and heavy oil Residual oil in coal chemistry. Among these, xylene is preferred, methylnaphthalene is more preferred, and heavy oil is more preferred because of its high boiling point. In wet pulverization, heat generation tends to occur when the pulverization efficiency is increased. A solvent having a low boiling point may volatilize and become a high concentration. On the other hand, as the aprotic polar solvent, NMP (N-methyl-2-pyrrolidone), GBL (γ-butyrolactone), DMF (NN dimethylformamide) and the like which dissolve not only water but also organic solvents are preferable. NMP (N-methyl-2-pyrrolidone) is preferred because it is difficult to resist and has a high boiling point.

The mixing ratio of the Si compound particles and the dispersion solvent is a ratio of usually 10% by mass or more, preferably 20% by mass or more, usually 50% by mass or less, preferably 40% by mass or less as the ratio of the Si compound particles in the resulting mixture. It is.
If the mixing ratio of the dispersion solvent is too high, the cost tends to increase, and if the mixing ratio of the dispersion solvent is too low, uniform dispersion of the Si compound particles tends to be difficult.

  The Si compound particles are preferably uniformly dispersed on the surface of the carbon material. For this purpose, the dispersion solvent used in wet pulverization of the Si compound particles may be added excessively during mixing. In the present specification, when mixing the Si compound particles into the carbon material as a slurry, the solid content of the Si compound particles is usually 10% or more, preferably 15% or more, more preferably 20% or more. Usually, it is 90% or less, preferably 85% or less, more preferably 80% or less. If the ratio of the solid content is too large, the fluidity of the slurry is lost, and the Si compound particles tend to be difficult to disperse in the carbon material. If the ratio is too small, the process tends to be difficult to handle.

And after mixing, Si compound particle | grains can be fix | immobilized on a carbon material by evaporating and removing a dispersion solvent using an evaporator, a dryer, etc. and drying.
Alternatively, mixing and fixing may be performed while evaporating the dispersion solvent while heating in a high-speed stirrer without adding an excessive dispersion solvent. At this time, in order to immobilize the Si compound particles on the carbon material, a buffer material such as resin or pitch can be used, and it is preferable to use the resin among them. This resin is considered not only to play a role of immobilizing the Si compound particles to the carbon material but also to prevent the Si compound particles from being detached from the carbon material during the spheronization process. In addition, when adding a buffering material, you may add at this stage and may add at the time of the wet grinding | pulverization of Si compound particle | grains.

  The resin that can be used as the buffer material in the step (1) is not particularly limited, but may be a resin corresponding to the organic compound that becomes the carbonaceous material described above, preferably polystyrene, polymethacrylic acid, Polyacrylonitrile. Polyacrylonitrile can be particularly preferably used because it has a large amount of residual carbon during firing and a relatively high decomposition temperature. The decomposition temperature of the resin can be measured in an inert gas atmosphere by differential scanning calorimetry (DSC). The decomposition temperature of the resin is preferably 50 ° C. or higher, more preferably 75 ° C. or higher, and still more preferably 100 ° C. or higher. When the decomposition temperature is too high, there is no particular problem. However, when the decomposition temperature is too low, there is a possibility of decomposition in the drying step described below.

The buffer material may be used in a state where it is dispersed in a solvent or in a dry state, but when a solvent is used, the same solvent as the dispersion solvent of the Si compound particles can be used.
Mixing is usually carried out under normal pressure, but if desired, it can also be carried out under reduced pressure or under pressure. Mixing can be carried out either batchwise or continuously. In any case, mixing efficiency can be improved by using a combination of an apparatus suitable for rough mixing and an apparatus suitable for fine mixing. Moreover, you may utilize the apparatus which performs mixing and fixation (drying) simultaneously. Drying can usually be carried out under reduced pressure or under pressure, and preferably dried under reduced pressure.

The drying time is usually 5 minutes or longer, preferably 10 minutes or longer, more preferably 20 minutes or longer, more preferably 30 minutes or longer, and usually 5 hours or shorter, preferably 3 hours or shorter, more preferably 1 hour or shorter. . If the time is too long, the cost increases. If the time is too short, uniform drying tends to be difficult.
Although drying temperature changes with solvents, it is preferable that it is time which can implement | achieve the said time. Moreover, it is preferable that it is below the temperature which resin does not modify | denature.

  As a batch-type mixing device, a mixer with a structure in which two frame molds rotate and revolve; a blade such as a dissolver that is a high-speed high-shear mixer and a butterfly mixer for high viscosity is placed in the tank. A device having a structure for stirring and dispersing; a so-called kneader-type device having a structure in which a stirring blade such as a sigma type rotates along the side surface of a semi-cylindrical mixing tank; a trimix type device having three stirring blades A so-called bead mill type apparatus having a rotating disk and a dispersion solvent body in a container is used.

  It also has a container with a paddle that is rotated by a shaft, and the inner wall surface of the container is formed substantially along the outermost line of rotation of the paddle, preferably in a long twin cylinder shape, and the paddle has side surfaces facing each other. A device having a structure in which many pairs are arranged in the axial direction of the shaft so as to be slidably engaged (for example, KRC reactor manufactured by Kurimoto Iron Works, SC processor, TEM manufactured by Toshiba Machine Celmac, TEX-K manufactured by Nippon Steel Works) Furthermore, it has a container in which a single inner shaft and a plurality of pavement or sawtooth paddles fixed to the shaft are arranged in different phases, and the inner wall surface is the outermost line of rotation of the paddle (External heat type) apparatus (for example, a Redige mixer manufactured by Redige Co., Ltd., a flow share mixer manufactured by Taiyo Koki Co., Ltd., and Tsukishima Kikai Co., Ltd.) DT dryers, etc.) can also be used. In order to perform mixing in a continuous manner, a pipeline mixer, a continuous bead mill, or the like may be used. It is also possible to homogenize by means such as ultrasonic dispersion.

(2) A step of spheroidizing the product obtained in (1) Through this step (2), a structure in which a carbon material is folded is observed, and a gap in the folded structure is observed. Si composite carbon particles (A) in which Si compound particles are present can be produced. Note that the above structure is obtained by using, for example, a technique such as field emission scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis or X-ray photoelectron spectroscopy (XPS) analysis.
This can be confirmed by observing the particle cross section of the composite carbon particle (A).

  That is, in the production method for obtaining the Si composite carbon particles (A), a composite in which Si compound particles are immobilized on the surface of the carbon material before being folded obtained in the step (1) (hereinafter referred to as the composite material) In the present invention, the spheroidizing treatment is performed. In particular, in the present invention, the Si compound particles within a predetermined range are present in the gaps in the folded structure as described later. It is preferable to set conditions appropriately.

  The spheronization process is basically a process using mechanical energy (mechanical action such as impact compression, friction and shear force), and specifically, a process using a hybridization system is preferable. The system has a rotor having a large number of blades that apply mechanical actions such as impact compression, friction and shearing force, and a large air flow is generated by the rotation of the rotor, and thus obtained in step (1) above. A large centrifugal force is applied to the carbon material in the composite, the carbon materials in the composite obtained in the step (1), and the carbon material, the wall and the blade in the composite obtained in the (1) step. The carbon material in the composite obtained in the step (1) can be neatly folded.

  As an apparatus used for the spheroidization treatment, for example, a rotor having a large number of blades installed in a casing, and the rotor is rotated at a high speed, whereby the composite obtained in the step (1) introduced into the interior is used. A device for applying a mechanical action such as impact compression, friction, shearing force, etc. to the carbon material and performing a surface treatment can be used. For example, dry ball mill, wet bead mill, planetary ball mill, vibrating ball mill, mechano-fusion system, Agromaster (Hosokawa Micron Corporation), hybridization system, Micros, Miraro (manufactured by Nara Machinery Co., Ltd.), CF mill (Ube) And theta composer (manufactured by Deoksugaku Kogyo Co., Ltd.). Preferred examples of the apparatus include a dry ball mill, a wet bead mill, a planetary ball mill, a vibration ball mill, a mechano-fusion system, an agromaster (Hosokawa Micron ( Co., Ltd.), hybridization system, Micros, Miraro (manufactured by Nara Machinery Co., Ltd.), CF mill (manufactured by Ube Industries, Ltd.), theta composer (manufactured by Tokuju Kosakusho Co., Ltd.), pulperizer and the like. Among these, a hybridization system manufactured by Nara Machinery Co., Ltd. is particularly preferable.

Note that the carbon material in the composite obtained in the step (1) to be subjected to the spheronization treatment may have already been subjected to a certain spheronization treatment under the conditions of the conventional method. Moreover, you may give a mechanical action repeatedly by circulating the composite_body | complex obtained at the said (1) process, or passing through this process in multiple times.
A spheronization process is performed using such an apparatus. In this process, the rotation speed of the rotor is usually 2000 rpm or more and 8000 rpm or less, preferably 4000 rpm or more and 7000 rpm or less, and usually in a range of 1 minute or more and 60 minutes or less. Then, the spheronization process is performed.

  In addition, if the number of rotations of the rotor is too small, the process of forming a sphere is weak, and the tapping density of the resulting Si composite carbon particles (A) may not be sufficiently increased. This may increase the effect, and the particles may collapse to reduce the tapping density. Further, if the spheroidizing time is too short, the particle size is sufficiently reduced and a high tapping density cannot be achieved. On the other hand, if it is too long, the carbon material in the composite obtained in the step (1) is used. May be shattered.

Classification processing may be performed on the obtained Si composite carbon particles (A). In addition, when the obtained Si composite carbon particle (A) is not in the physical property range defined in the present invention, desired physical properties are obtained by repeated (usually 2 to 10 times, preferably 2 to 5 times) classification treatment. Can range. Examples of the classification include dry (aerodynamic classification, sieving), wet classification, and the like, but dry classification, particularly aerodynamic classification is preferable from the viewpoint of cost and productivity.

(3) The step of coating the Si composite carbon particles (A) obtained in (2) with a carbonaceous material The Si composite carbon particles (A) are obtained as in the above step (2). (A) preferably contains a carbonaceous material, and as a more specific embodiment, it is more preferable that at least a part of the surface thereof is coated with the carbonaceous material (hereinafter, such Si composite carbon particles ( A) is also referred to as a carbonaceous material-coated Si composite carbon particle). In the present specification, the carbonaceous material-coated Si composite carbon particles are described separately from the Si composite carbon particles (A) for convenience, but in this specification, the carbonaceous material-coated Si composite carbon particles are also referred to as Si composite carbon particles (A). ) To be interpreted.

In the coating treatment, an organic compound that becomes a carbonaceous material is used as a coating material for the Si composite carbon particles (A) described above, and these are mixed and fired to obtain carbonaceous material-coated Si composite carbon particles.
When the firing temperature is usually 600 ° C. or higher, preferably 700 ° C. or higher, more preferably 900 ° C. or higher, usually 2000 ° C. or lower, preferably 1500 ° C. or lower, more preferably 1200 ° C. or lower, an amorphous material is obtained as a carbonaceous material. When a heat treatment is usually performed at 2000 ° C. or higher, preferably 2500 ° C. or higher and usually 3200 ° C. or lower, a graphite material is obtained as a carbonaceous material. The amorphous material is carbon with low crystallinity, and the graphite material is carbon with high crystallinity.

  In the coating treatment, the above-mentioned Si composite carbon particles (A) are used as a core material, an organic compound that becomes a carbonaceous material is used as a coating material, and these are mixed and fired to obtain carbonaceous material-coated Si composite carbon particles. The coating layer may contain Si compound particles and carbon fine particles. The shape of the carbon fine particles is not particularly limited, and may be any of granular, spherical, chain-like, needle-like, fibrous, plate-like, and scale-like shapes.

  Specifically, the carbon fine particles are not particularly limited, but examples thereof include coal fine powder, vapor phase carbon powder, carbon black, ketjen black, and carbon nanofiber. Among these, carbon black is particularly preferable. Carbon black has the advantage that non-aqueous secondary batteries have high input / output characteristics even at low temperatures, and at the same time are inexpensive and easily available.

The average particle diameter d50 of the carbon fine particles is usually 0.01 μm or more and 10 μm or less, preferably 0.05 μm or more, more preferably 0.07 μm or more, further preferably 0.1 μm or more, preferably 8 μm or less, more Preferably it is 5 micrometers or less, More preferably, it is 1 micrometer or less.
When the carbon fine particles have a secondary structure in which primary particles are aggregated and aggregated, other physical properties and types are not particularly limited as long as the primary particle size is 3 nm or more and 500 nm or less, but the primary particle size is preferable. Is at least 3 nm, more preferably at least 15 nm, even more preferably at least 30 nm, particularly preferably at least 40 nm, preferably at most 500 nm, more preferably at most 200 nm, still more preferably at most 100 nm, particularly preferably at most 70 nm. It is. The primary particle size of the carbon fine particles can be measured by observation with an electron microscope such as SEM or a laser diffraction particle size distribution analyzer.

(Physical properties of carbonaceous material-coated Si composite carbon particles)
The carbonaceous material-covered Si composite carbon particles exhibit the same physical properties as the Si composite carbon particles (A) described above, but the preferred physical properties of the carbonaceous material-coated Si composite carbon particles that vary depending on the coating treatment are described below.

-(002) plane spacing (d ₀₀₂ )
The interplanar spacing (d ₀₀₂ ) of the (002) plane of the carbonaceous material-coated Si composite carbon particles by X-ray wide angle diffraction method is usually 0.336 nm or more, preferably 0.337 nm or more, more preferably 0.340 nm or more, and still more preferably. 0.342 nm or more. Moreover, it is less than 0.380 nm normally, Preferably it is 0.370 nm or less, More preferably, it is 0.360 nm or less. If the d ₀₀₂ value is too large, it indicates that the crystallinity is low, and the cycle characteristics of the non-aqueous secondary battery tend to deteriorate. If the d ₀₀₂ value is too small, the effect of combining carbonaceous materials is obtained. hard.

-Content The carbonaceous material-coated Si composite carbon particles contain an amorphous material or a graphite material, and among them, the amorphous carbonaceous material is contained from the point of acceptability of lithium ions. preferable. The content of the amorphous carbonaceous material is usually 0.5% by mass or more and 30% by mass or less, preferably 1% by mass or more and 25% by mass or less, more preferably 2% by mass or more and 20% by mass or less. When this content is too large, the amorphous material portion of the negative electrode material increases, and the reversible capacity when the battery is assembled tends to be small. On the other hand, if the content is too small, the amorphous Si compound carbon particles (A) that are the core are not uniformly coated and strong granulation is not performed, and the particle size becomes too small when pulverized after firing. Tend.

In addition, content (coverage) of the amorphous substance derived from the organic compound finally obtained was based on the amount of Si composite carbon particles (A) to be used, the amount of organic compound to be a carbonaceous material, and JIS K 2270. It can be calculated by the following formula (3) based on the residual carbon ratio measured by the micro method.
Formula (3)
Carbonaceous material content (% by mass)
= (Mass of organic compound that becomes carbonaceous material × residual carbon ratio × 100) / {sample (Si composite carbon particles (
A)) Total mass of graphite particles and Si compound particles + (mass of organic compound to be carbonaceous material x residual carbon ratio)}
The method (ii) may include a pulverization process, a particle size classification process, and a mixing process with another negative electrode active material in addition to the above-described carbonaceous material coating process.

(Method (iii))
Examples of the method for producing the Si composite carbon particles (A) in which the carbon compound is attached to or coated on the outer periphery of the Si compound particles as the nucleus described above (solid phase reaction, liquid phase reaction, sputtering, chemical vapor deposition, etc.) The method using is mentioned.
Here, a synthesis method using a solid phase reaction will be described. The solid phase reaction is a method of synthesizing composite particles by weighing and mixing solid raw materials such as powders so as to have a predetermined composition and then performing a heat treatment. With respect to the Si composite carbon particles (A) in the present invention, for example, a method in which an Si compound particle and an organic compound that becomes a carbonaceous material are brought into contact with each other at a high temperature to cause a reaction is applicable.

The contact between the Si compound particles and the carbonaceous organic compound in the solid phase reaction step is performed under an oxygen-free (low oxygen) environment at a high temperature of 1000 ° C. or higher, and thus an apparatus capable of setting such an environment. For example, the process can be performed using a high-frequency induction heating furnace, a graphite furnace, an electric furnace, or the like. The temperature conditions in the solid phase reaction step are not particularly limited, but are usually higher than the melting temperature of the Si compound particles, preferably 10 ° C. or higher, more preferably 30 ° C. higher than the melting temperature of the Si compound particles. It is. The specific temperature is usually 1420 ° C. or higher, preferably 1430 ° C. or higher, more preferably 1450 ° C. or higher, and usually 2000 ° C. or lower, preferably 1900 ° C. or lower, more preferably 1800 ° C. or lower. The oxygen-free (low oxygen) environment is preferably performed under an inert atmosphere such as argon and under reduced pressure (vacuum). When performed under reduced pressure (vacuum), the pressure is usually 2000 Pa or less, preferably 1000 Pa or less. More preferably, it is 500 Pa or less. Further, the treatment time is usually 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1 hour or longer, and usually 3 hours or shorter, preferably 2.5 hours or shorter, more preferably 2 hours or shorter.

The technique (iii) may include a pulverization process, a particle size classification process, and a mixing process with another negative electrode active material, in addition to the solid phase reaction process described above.
Examples of the coarse pulverizer used in the pulverization process include a jaw crusher, an impact crusher, and a cone crusher. Examples of the intermediate pulverizer include a roll crusher and a hammer mill. Examples of the fine pulverizer include a ball mill, A vibration mill, a pin mill, a stirring mill, a jet mill, etc. are mentioned.

Among these, a ball mill, a vibration mill, and the like are preferable from the viewpoint of processing speed because of a short grinding time.
The grinding speed is appropriately set depending on the type and size of the apparatus. For example, in the case of a ball mill, it is usually 50 rpm or more, preferably 100 rpm or more, more preferably 150 rpm or more, and further preferably 200 rpm or more. Moreover, it is 2500 rpm or less normally, Preferably it is 2300 rpm or less, More preferably, it is 2000 rpm or less. If the speed is too high, control of the particle size tends to be difficult, and if the speed is too low, the processing speed tends to be slow.

The grinding time is usually 30 seconds or longer, preferably 1 minute or longer, more preferably 1 minute 30 seconds or longer, and further preferably 2 minutes or longer. Moreover, it is usually 3 hours or less, preferably 2.5 hours or less, more preferably 2 hours or less. If the pulverization time is too short, particle size control tends to be difficult, and if the pulverization time is too long, the productivity of the Si composite carbon particles (A) tends to decrease.
In the case of a vibration mill, the grinding speed is usually 50 rpm or more, preferably 100 rpm or more, more preferably 150 rpm or more, and still more preferably 200 rpm or more. Moreover, it is 2500 rpm or less normally, Preferably it is 2300 rpm or less, More preferably, it is 2000 rpm or less. If the speed is too high, control of the particle size tends to be difficult, and if the speed is too low, the processing speed tends to be slow.

The grinding time is usually 30 seconds or longer, preferably 1 minute or longer, more preferably 1 minute 30 seconds or longer, and further preferably 2 minutes or longer. Moreover, it is usually 3 hours or less, preferably 2.5 hours or less, more preferably 2 hours or less. If the pulverization time is too short, the particle size control tends to be difficult, and if the pulverization time is too long, the productivity tends to decrease.
As the classification treatment condition of the classification treatment step, the opening is usually 53 μm or less, preferably 45 μm or less, more preferably 38 μm or less so as to have the above particle diameter.

  There are no particular restrictions on the equipment used for classification, but for example, when dry sieving: rotary sieving, oscillating sieving, rotating sieving, vibrating sieving, etc. can be used. : Gravity classifier, inertial classifier, centrifugal classifier (classifier, cyclone, etc.) can be used. For wet sieving: mechanical wet classifier, hydraulic classifier, settling classifier, A centrifugal wet classifier or the like can be used.

Among the above-described methods (i) to (iii), by encapsulating silicon element in the spheroidized graphite, electrode plate swelling and particle destruction can be suppressed, and the reaction between the electrolyte and silicon element The method (ii) is more preferable from the viewpoint of suppressing the property.
[Composite carbon particles (B)]
The composite carbon particles (B) in the present invention will be described below.

The composite carbon particles (B) of the present invention are composite particles containing graphite particles, carbonaceous particles, and carbonaceous materials. By containing the carbonaceous particles, a uniform and continuous fine flow path is generated on the surface of the composite carbon particles (B), and the lithium ions can move smoothly even at low temperatures. It is possible to improve the input / output characteristics of the battery at a low temperature. As used herein, “graphite particles, carbonaceous particles and carbonaceous material-containing composite particles” means that carbonaceous particles and BR carbonaceous materials exemplified below are attached to, adhered to, and combined with graphite particles. More specifically, it represents a state of adhering in the pores of the graphite particles, a state of being bound to the entire or part of the surface of the graphite particles, and a composite state.

(Characteristics of composite carbon particles (B))
The composite carbon particles (B) of the present invention preferably have the following characteristics.
(A) X-ray parameters of composite carbon particles (B) The interplanar spacing (d ₀₀₂ ) of the composite carbon particles (B) according to the X-ray wide angle diffraction method is usually 0.337 nm or less, preferably 0.336 nm or less. It is. If the d002 value is too large, it indicates that the crystallinity is low, and the initial irreversible capacity may increase when a non-aqueous secondary battery is used. On the other hand, since the theoretical value of the interplanar spacing of the 002 plane of graphite is 0.3354 nm, the d value is usually 0.3354 nm or more.

  The crystallite size (Lc) of the composite carbon particles (B) is usually in the range of 30 nm or more, preferably 50 nm or more, more preferably 100 nm or more. Below this range, the crystallinity decreases and the discharge capacity of the battery tends to decrease. The lower limit of Lc is the theoretical value of graphite.

(B) Volume-based average particle diameter (d50) of composite carbon particles (B)
The average particle diameter d50 of the composite carbon particles (B) is usually 50 μm or less, preferably 40 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less, usually 5 μm or more, preferably 7 μm or more, more preferably 10 μm or more. It is. If the average particle diameter d50 is too small, the specific surface area becomes large, so that the decomposition of the electrolytic solution increases and the initial efficiency of the non-aqueous secondary battery tends to decrease. If the average particle diameter d50 is too large, the rapid charge / discharge characteristics are reduced. It tends to cause a decline.

(C) Aspect ratio of composite carbon particles (B) The aspect ratio of the composite carbon particles (B) is usually 1 or more, preferably 1.5 or more, more preferably 1.6 or more, still more preferably 1.7 or more, Usually, it is 4 or less, preferably 3 or less, more preferably 2.5 or less, and still more preferably 2 or less.
If the aspect ratio is too large, the particles tend to be aligned in the direction parallel to the current collector when used as an electrode, so that there are not enough continuous voids in the thickness direction of the electrode, and lithium ion mobility in the thickness direction. However, the rapid charge / discharge characteristics of the non-aqueous secondary battery tend to be reduced.

(D) BET specific surface area (SA) of composite carbon particles (B)
The specific surface area according to the BET method of the composite carbon particles (B) is usually 0.5 m ² / g or more, preferably 1 m ² / g or more, more preferably 2 m ² / g or more, and further preferably 3 m ² / g or more. Moreover, it is 15 m < ² > / g or less normally, Preferably it is 12 m < ² > / g or less, More preferably, it is 10 m < ² > / g or less, More preferably, it is 8 m < ² > / g or less, Most preferably, it is 6 m < ² > / g or less. If the specific surface area is too large, the reactivity between the portion exposed to the electrolyte and the electrolyte when used as the negative electrode active material is increased, which tends to cause a decrease in initial efficiency and an increase in the amount of gas generated, making it difficult to obtain a preferable battery. Tend. When the specific surface area is too small, there are few sites where lithium ions enter and exit, and the high-speed charge / discharge characteristics and output characteristics tend to be inferior.

(E) Tap density of composite carbon particles (B) The tap density of the composite carbon particles (B) is preferably 0.8 g / cm ³ or more, and 0.9 g / c.
m ³ or more is more preferable, and 0.95 g / cm ³ or more is still more preferable. Moreover, 1.8 g / cm ³ or less is usually preferable and 1.5 g / cm ³ or less is preferable, and 1.3 g / cm ³ or less is more preferable.

That the tap density is 0.8 g / cm ³ or more is one of the indexes indicating that the composite carbon particles (B) are spherical. That the tap density is smaller than 0.8 g / cm ³ is one of the indicators that the graphite particles as the raw material of the composite carbon particles (B) are not sufficiently spherical particles. If the tap density is less than 0.8 g / cm ³ , sufficient continuous voids are not ensured in the electrode, and the mobility of lithium ions in the electrolyte held in the voids is reduced. The rapid charge / discharge characteristics tend to decrease.

(F) Circularity of the composite carbon particles (B) The circularity of the composite carbon particles (B) is usually 0.88 or more, more preferably 0.9 or more, and further preferably 0.92 or more. Further, the circularity is usually 1 or less, preferably 0.99 or less, more preferably 0.97 or less. If the circularity is too small, the high current density charge / discharge characteristics of the non-aqueous secondary battery tend to deteriorate.

(G) Raman R value of composite carbon particle (B) The Raman R value (as defined above) of composite carbon particle (B) is usually 1 or less, preferably 0.8 or less, more preferably 0.6. In the following, it is more preferably 0.5 or less, usually 0.05 or more, preferably 0.1 or more, more preferably 0.2 or more, and further preferably 0.25 or more. If the Raman R value is less than this range, the crystallinity of the particle surface becomes too high, the number of Li insertion sites decreases, and the rapid charge / discharge characteristics of the nonaqueous secondary battery tend to be reduced. On the other hand, if it exceeds this range, the crystallinity of the particle surface will be disturbed, the reactivity with the electrolyte will increase, and the charge / discharge efficiency will tend to decrease and the gas generation will increase.

<Method for producing composite carbon particle (B)>
(Raw material for composite carbon particles (B))
The composite carbon particles (B) described above are not particularly limited as long as they are composite carbon particles containing at least graphite particles, carbonaceous particles, and carbonaceous materials. For example, graphite particles, carbonaceous particles, and carbonaceous materials are used. It can manufacture using the organic compound used.

Graphite particles As the graphite particles used as raw materials for the composite carbon particles (B) of the present invention (hereinafter sometimes referred to as graphite particles (C)), as described in the above-mentioned section of the Si composite carbon particles (A) Either natural graphite or artificial graphite may be used, but it is preferable to use spheroidized natural graphite for reasons such as easy control of the electrode plate structure.

  The graphite particles (graphite particles (C)) used as raw materials for the composite carbon particles (B) in the present invention preferably satisfy any one or more of the following physical properties. In the present invention, one type of graphite particles (C) exhibiting such physical properties may be used alone, or two or more types may be used in combination in any combination.

(A) Volume-based average particle diameter d50 of graphite particles (C)
The average particle diameter d50 of the graphite particles (C) is usually 50 μm or less, preferably 40 μm or less, more preferably 30 μm or less, still more preferably 25 μm or less, usually 1 μm or more, preferably 4 μm or more, more preferably 10 μm or more. It is. If the average particle diameter d50 is too small, the specific surface area increases, so that the decomposition of the electrolyte increases, and the initial efficiency tends to decrease. If the average particle diameter d50 is too large, the rapid charge / discharge characteristics tend to decrease. .

(B) Aspect ratio of the graphite particles (C) The aspect ratio of the graphite particles (C) is usually 1 or more, preferably 1.5 or more, more preferably 1.6 or more, still more preferably 1.7 or more, Usually, it is 4 or less, preferably 3 or less, more preferably 2.5 or less, and still more preferably 2 or less.
If the aspect ratio is too large, the particles tend to be aligned in the direction parallel to the current collector when used as an electrode, so that there are not enough continuous voids in the thickness direction of the electrode, and lithium ion mobility in the thickness direction. Tends to decrease, leading to a decrease in rapid charge / discharge characteristics.

(C) Graphite particles (C) BET specific surface area (SA)
The specific surface area of the graphite particles (C) by the BET method is usually 0.5 m ² / g or more, preferably 1 m ² / g or more, more preferably 2 m ² / g or more, and further preferably 3 m ² / g or more. Moreover, it is 15 m < ² > / g or less normally, Preferably it is 10 m < ² > / g or less, More preferably, it is 8 m < ² > / g or less, More preferably, it is 7 m < ² > / g or less, Especially preferably, it is 6.5 m < ² > / g or less. If the specific surface area is too large, the reactivity between the portion exposed to the electrolyte and the electrolyte when used as the negative electrode active material is increased, which tends to cause a decrease in initial efficiency and an increase in the amount of gas generated, making it difficult to obtain a preferable battery. Tend. When the specific surface area is too small, there are few sites where lithium ions enter and exit, and the high-speed charge / discharge characteristics and output characteristics tend to be inferior.

(D) Graphite Particle (C) Tap Density The tap density of the graphite particles (C) is preferably 0.8 g / cm ³ or more, more preferably 0.9 g / cm ³ or more, and 0.95 g / cm ³ or more. Is more preferable. Moreover, 1.8 g / cm ³ or less is usually preferable and 1.5 g / cm ³ or less is preferable, and 1.3 g / cm ³ or less is more preferable.
That the tap density is 0.8 g / cm ³ or more is one of the indexes indicating that the graphite particles (C) are spherical. If the tap density is less than 0.8 g / cm ³ , sufficient continuous voids are not secured in the electrode, and the mobility of lithium ions in the electrolyte held in the voids is reduced, resulting in reduced rapid charge / discharge characteristics. Tend to.

(E) Graphite Particle (C) Circularity The circularity of the graphite particles (C) is usually 0.88 or more, more preferably 0.9 or more, and still more preferably 0.92 or more. Further, the circularity is usually 1 or less, preferably 0.99 or less, more preferably 0.97 or less. If the circularity is too small, the high current density charge / discharge characteristics of the non-aqueous secondary battery tend to deteriorate.

(F) Graphite particles (C) Raman R value The Raman R value of the graphite particles (C) is usually 1 or less, preferably 0.8 or less, more preferably 0.6 or less, and even more preferably 0.5 or less. Yes, usually 0.05 or more, preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more. When the Raman R value is less than this range, the crystallinity of the particle surface becomes too high, the number of Li insertion sites decreases, and rapid charge / discharge characteristics tend to be deteriorated. On the other hand, if it exceeds this range, the crystallinity of the particle surface will be disturbed, the reactivity with the electrolyte will increase, and the charge / discharge efficiency will tend to decrease and the gas generation will increase.
The graphite particles in the composite carbon particles (B) preferably have properties similar to the physical properties of the graphite particles (C).

Carbonaceous particles The material constituting the composite carbon particles of the present invention, the type of carbonaceous particles is not particularly limited, but coal fine powder, vapor phase carbon powder, carbon black, ketjen black, carbon nanofiber, etc. It is done. Among these, carbon black is particularly preferable. Carbon black has the advantage that the input / output characteristics are improved even at low temperatures, and at the same time, it can be obtained inexpensively and easily.

The shape is not particularly limited, and may be any of granular, spherical, chain-like, needle-like, fibrous, plate-like, and scale-like shapes.
The carbonaceous particles in the present invention preferably satisfy any one or more of the following physical properties. In the present invention, one kind of carbonaceous particles exhibiting such physical properties may be used alone, or two or more kinds may be used in any combination.

(A) Primary particle size of carbonaceous particles The primary particle size of the carbonaceous particles in the present invention is usually 3 nm or more, preferably 10 nm or more, more preferably 15 nm or more, still more preferably 20 nm or more, usually It is 500 nm or less, preferably 300 nm or less, more preferably 200 nm or less, still more preferably 100 nm or less, and particularly preferably 70 nm or less. The primary particle diameter of the carbonaceous particles can be measured by observation with an electron microscope such as SEM or a laser diffraction particle size distribution analyzer.
When the primary particle size is too large, the specific surface area becomes small, and the input / output characteristics at low temperatures tend to deteriorate. Also, if the primary particle size is too small, the specific surface area becomes large and the capacity tends to decrease.

(B) BET specific surface area (SA) of carbonaceous particles
BET specific surface area of the carbonaceous particles is usually ^{1 m} 2 / g or more, preferably ^{10 m} 2 / g or more, more preferably ^{30 m} 2 / g or more, more preferably ^{50 m} 2 / g or more, particularly preferably ^70m 2 / g or more, usually in the range of 1000 m ² / g or less, preferably 500 m ² / g or less, more preferably 200 m ² / g or less, still more preferably 150 m ² / g or less. If the specific surface area is too large, the reactivity between the portion exposed to the electrolyte and the electrolyte when used as the negative electrode active material is increased, which tends to cause a decrease in initial efficiency and an increase in the amount of gas generated, making it difficult to obtain a preferable battery. Tend. When the specific surface area is too small, there are few sites where lithium ions enter and exit, and the high-speed charge / discharge characteristics and output characteristics tend to be inferior.

(C) Bulk density of carbonaceous particles The bulk density of carbonaceous particles is usually 0.01 g / cm ³ or more, preferably 0.1 g / cm ³ or more, more preferably 0.15 g / cm ³ or more, and Preferably it is 0.17 g / cm ³ or more, usually 1 g / cm ³ or less, preferably 0.8 g / cm ³ or less, more preferably 0.6 g / cm ³ or less.

When the bulk density is too large, the low-temperature input / output characteristics tend to deteriorate. Moreover, when the bulk density is too small, the battery capacity tends to decrease.
The bulk density was measured by using a powder density measuring device to drop the raw carbon material into a cylindrical tap cell having a diameter of 1.6 cm and a volume capacity of 20 cm ³ through a sieve having an opening of 300 μm, and filling the cell to the full. It can be measured by determining the density from the volume at that time and the weight of the sample.

(D) Tap density of carbonaceous particles The tap density of carbonaceous particles is usually 0.1 g / cm ³ or more, preferably 0.15 g / cm ³ or more, more preferably 0.2 g / cm ³ or more. It is 2 g / cm ³ or less, preferably 1 g / cm ³ or less, more preferably 0.8 g / cm ³ or less. If the tap density is too high, the low-temperature input / output characteristics tend to be reduced, and if it is too low, the battery capacity tends to be reduced.

(E) DBP oil absorption amount of carbonaceous particles The DBP oil absorption amount of carbonaceous particles is usually 10 ml / 100 g or more, preferably 50 ml / 100 g or more, more preferably 60 ml / 100 g or more, usually 1000 ml / 100 g or less, preferably 500 ml / The amount is 100 g or less, more preferably 200 ml / 100 g or less, still more preferably 150 ml / 100 g or less.
When the DBP oil absorption is too large, the capacity tends to decrease, and when it is too small, the low temperature input / output characteristics tend to decrease.

Organic compound that becomes carbonaceous material The organic compound that becomes the carbonaceous material used as the raw material of the composite carbon particle (B) of the present invention is the organic compound that becomes the carbonaceous material described in the above-mentioned section of Si composite carbon particles (A). Any of these may be used.

(Production method)
The composite carbon particles (B) of the present invention are not particularly limited as long as the composite carbon particles (B) are composite particles of graphite particles, carbonaceous particles, and carbonaceous materials. For example, the following viewpoints (1) and (2) It is preferable to adopt a manufacturing method that takes into account.
(1) A mixed powder obtained by mixing graphite particles (C) and carbonaceous particles is prepared, and an organic compound that becomes a carbonaceous material is mixed therewith and heat-treated in an inert gas.
By adopting such a production method, a multilayer structure in which carbonaceous particles and carbonaceous materials cover a part or the entire surface of the composite carbon particles (B), which is a preferred form of the composite carbon particles (B) of the present invention. There exists an advantage which becomes easy to produce a carbon material.

(2) As a device for mixing the graphite particles (C) and the carbonaceous particles, not only the mixing and stirring mechanism for mixing and stirring the graphite particles (C) and the carbonaceous particles, but also the graphite particles (C) and the carbonaceous particles Adopting a device equipped with a crushing mechanism for crushing particles, a so-called crushing mixer, and mixing.
By mixing the graphite particles (C) and the carbonaceous particles using such a crushing mixer, the aggregates of the graphite particles (C) and the carbonaceous particles can be crushed and mixed uniformly. it can. By sufficiently crushing the graphite particles (C) and the aggregates of the carbonaceous particles and mixing them uniformly before compositing, the aggregation of the carbonaceous particles generated in the subsequent steps can be suppressed. it can. For example, a carbon material in which many aggregates of carbonaceous particles remain has a tendency that the ratio between the total pore volume and the Raman R value measured by a microscopic Raman spectroscopic device tends to increase, and the storage characteristics tend to deteriorate.

As a manufacturing method in consideration of the above viewpoints (1) and (2), a manufacturing method including the following steps (a) to (c) can be given.
Step (a): Step of mixing and stirring the graphite particles (C) and carbonaceous particles while pulverizing Step (b): Step of mixing an organic compound that becomes a carbonaceous material into the powder obtained in step (a) Step (c): a step of heat-treating the mixture obtained in step (b) at a temperature of 2600 ° C. or lower in an inert gas. In addition, graphitic particles (C), carbonaceous particles, and organic compounds that become carbonaceous materials are each One type may be used alone, or two or more types may be used in combination.

<Process (a)>
The method of mixing and stirring the graphite particles (C) and the carbonaceous particles while pulverizing them can be performed by a conventional method. An example is shown below.
(1) Mixing ratio of graphite particles (C) and carbonaceous particles The mixing ratio of graphite particles (C) and carbonaceous particles should be appropriately selected based on the composition of the target composite particles. The carbonaceous particles are usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and usually 20% by mass or less with respect to the graphite particles (C). Preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less. Within the above range, there are advantages that the input / output characteristics are enhanced even at low temperatures while satisfying various characteristics required for the lithium ion secondary battery such as the charge / discharge efficiency and discharge capacity of the battery.

(2) Mixing device When a crushing mixer is used as a device for mixing the graphite particles (C) and the carbonaceous particles, the specific device is not particularly limited, and a commercially available one may be appropriately adopted. For example, a rocking mixer, a Roedige mixer, a Henschel mixer, and the like can be given. Moreover, although the crushing and mixing conditions are not particularly limited, the rotation speed of the crushing blade (chopper) is usually 100 rpm or more, preferably 1000 rpm or more, more preferably 2000 rpm or more, and usually 100,000 rpm or less, preferably 30000 rpm or less, preferably Is 10,000 rpm or less. Furthermore, the crushing and mixing time is usually 30 seconds or longer, preferably 1 minute or longer, more preferably 10 minutes or longer, and is usually 24 hours or shorter, preferably 3 hours or shorter, more preferably 1 hour or shorter. Within the above range, aggregation of the graphite particles (C) and the carbonaceous particles can be effectively prevented.

<Step (b)>
Mixing of the powder obtained in the step (a) and the organic compound to be a carbonaceous material can be performed by a conventional method. An example is shown below.
(1) Mixing temperature The mixing temperature is equal to or higher than the softening point of the organic compound that becomes the carbonaceous material. It is usually 5 ° C. or higher, preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 180 ° C. or lower, more preferably 150 ° C. or lower. When mixed at a temperature lower than the softening point, the fluidity of the organic compound that becomes the carbonaceous material is deteriorated and not only cannot be mixed uniformly, but also tends to cause liquid leakage during the pressure treatment. On the other hand, when the temperature is too high, it becomes difficult to uniformly mix or combine, and there is a tendency for productivity to be lacking because it is necessary to extend the heating time until it becomes liquid or to handle it at a high temperature.

(2) Mixing ratio of powder obtained in step (a) and organic compound that becomes carbonaceous material The mixing ratio of powder obtained in step (a) and organic compound that becomes carbonaceous material is the target composite particle The organic compound to be a carbonaceous material is usually 0.01% by mass or more, preferably 0.1% by mass or more, based on the graphite particles (C). More preferably, it is 0.5 mass% or more, More preferably, it is 1 mass% or more, Usually 60 mass% or less, Preferably it is 30 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 10 mass% % Or less, and particularly preferably 5% by mass or less. Within the above range, there is an advantage that the charge / discharge efficiency of the battery, the discharge capacity, and the input / output characteristics at a low temperature are improved.

Moreover, when mixing with the powder obtained at the process (a), the organic compound used as a carbonaceous material may be diluted with an organic solvent. The reason for diluting is that by diluting with an organic solvent, the viscosity of the organic compound to be mixed is lowered, and the raw material carbon material can be coated more efficiently and uniformly.
Organic solvents include pentane, hexane, isohexane, heptane, octane, isooctane, decane, dimethylbutane, cyclohexane, methylcyclohexane and other hydrocarbons; ethyl ether, isopropyl ether, diisoamyl ether, methylphenyl ether, amylphenyl ether Ethers such as ethyl benzyl ether; ketones such as acetone, methyl acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone; methyl formate, ethyl formate, isobutyl formate, methyl acetate, isoamyl acetate, methoxybutyl acetate, cyclohexyl acetate, methyl butyrate, Esters such as ethyl butyrate, butyl benzoate, isoamyl benzoate; benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylben Aromatic hydrocarbons such as but not limited to benzene, amylbenzene, diamylbenzene, triamylbenzene, tetraamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, tetralin, cyclohexylbenzene, etc. .

Moreover, what mixed these 2 or more types may be used. Among these, benzene, toluene, and xylene are organic solvents having a relatively high boiling point and a low viscosity, and are particularly preferable in that the concentration change due to volatilization hardly occurs and the viscosity of the carbonaceous material precursor can be lowered.
The dilution ratio with the organic solvent is such that the organic compound that becomes a carbonaceous material is usually 5% by mass or more, preferably 25% by mass or more, more preferably 40% by mass or more, and still more preferably mass, with respect to the mass of the organic solvent. It is 50% or more, usually 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less. If the dilution ratio is too large, the concentration of the organic compound that becomes a carbonaceous material tends to decrease, and the raw carbon material tends not to be efficiently coated. If the dilution ratio is too small, the concentration of the organic compound that becomes a carbonaceous material is not sufficiently lowered, and the raw material carbon material tends not to be efficiently coated.

Mixing is usually carried out under normal pressure, but if desired, it can also be carried out under reduced pressure or under pressure. Mixing can be carried out either batchwise or continuously. In any case, mixing efficiency can be improved by using a combination of an apparatus suitable for rough mixing and an apparatus suitable for fine mixing.
The viscosity of the mixture or diluted mixture obtained in this step is usually 100 cP or less, preferably 70 cP or less, more preferably 50 cP or less. Moreover, it is 1 cP or more, preferably 10 cP or more. If the viscosity is too high, deterioration during cycling tends to occur, and cycle characteristics tend to deteriorate.

(3) Mixing device As a batch mixing device, a mixer with a structure in which two frame molds rotate and revolve; a single high-speed, high-shear mixer, such as a dissolver and a high-viscosity butterfly mixer A device with a structure in which the blade stirs and disperses in the tank; a so-called kneader-type device in which a stirring blade such as a sigma type rotates along the side surface of the semi-cylindrical mixing tank; the stirring blade has three axes A so-called bead mill type apparatus having a rotating disk and a dispersion medium in a container is used.

  It also has a container with a paddle that is rotated by a shaft, and the inner wall surface of the container is formed substantially along the outermost line of rotation of the paddle, preferably in a long twin cylinder shape, and the paddle has side surfaces facing each other. A device having a structure in which many pairs are arranged in the axial direction of the shaft so as to be slidably engaged (for example, KRC reactor manufactured by Kurimoto Iron Works, SC processor, TEM manufactured by Toshiba Machine Celmac, TEX-K manufactured by Nippon Steel Works) Furthermore, it has a container in which a single inner shaft and a plurality of pavement or sawtooth paddles fixed to the shaft are arranged in different phases, and the inner wall surface is the outermost line of rotation of the paddle (External heat type) apparatus having a structure preferably formed in a cylindrical shape (e.g., a Redige mixer manufactured by Redige Co., Ltd., a flow share mixer manufactured by Taiyo Koki Co., Ltd., Tsukishima Machine Co., Ltd.) Of DT dryers, etc.) can also be used. In order to perform mixing in a continuous manner, a pipeline mixer, a continuous bead mill, or the like may be used.

  Further, the mixing conditions are not particularly limited, but the rotational speed of the rotor blade is usually 5 rpm or more, preferably 10 rpm or more, more preferably 50 rpm or more, further preferably 100 rpm, particularly preferably 150 rpm, and usually 100000 rpm or less, preferably Is 10,000 rpm or less, more preferably 1000 rpm or less, still more preferably 500 rpm or less, and particularly preferably 200 rpm or less. Furthermore, the mixing time is usually 30 seconds or longer, preferably 1 minute or longer, more preferably 10 minutes or longer, and is usually 24 hours or shorter, preferably 3 hours or shorter, more preferably 1 hour or shorter. Within the above range, the graphite particles (C) can be uniformly coated with an organic compound that becomes a carbonaceous material.

<Step (c)>
(1) Firing temperature The calcining temperature varies depending on the organic compound used as the carbonaceous material used for the preparation of the mixture, but when carbonizing, it is usually heated to 600 ° C or higher, preferably 700 ° C or higher, more preferably 800 ° C or higher. In general, it is preferable to stop at 1500 ° C. or less, preferably 1400 ° C. or less, more preferably 1200 ° C. or less.

When graphitizing, it is usually heated to 2500 ° C. or higher, preferably 2700 ° C. or higher, more preferably 2900 ° C. or higher. The upper limit of the heating temperature is usually 3500 ° C. or lower, preferably 3200 ° C. or lower, more preferably 3100 ° C. or lower, even if the carbide of the organic compound is usually high.
In the firing treatment conditions, the heat history temperature condition, the temperature rise rate, the cooling rate, the heat treatment time, etc. are appropriately set. Further, after heat treatment in a relatively low temperature region, the temperature can be raised to a predetermined temperature. In addition, the reactor used for this process may be a batch type or a continuous type, and may be one or more.

(2) Furnace used for firing The furnace used for firing is not particularly limited as long as the above requirements are satisfied. A heat treatment tank), a Tamman furnace, an Atchison furnace, a high-frequency induction heating furnace, or the like can be used, and a direct resistance heating, an indirect resistance heating, a direct combustion heating, a radiant heat heating or the like can also be used as a heating method. During the heat treatment, stirring may be performed as necessary.

<Other processes>
You may grind | pulverize separately about the composite particle obtained by the above-mentioned manufacturing method.
Examples of the coarse pulverizer used in the pulverization process include a jaw crusher, an impact crusher, and a cone crusher. Examples of the intermediate pulverizer include a roll crusher and a hammer mill. Examples of the fine pulverizer include a ball mill and vibration. Examples thereof include a mill, a pin mill, a stirring mill, and a jet mill.

Among these, a ball mill, a vibration mill and the like are preferable from the viewpoint of processing speed because of a short grinding time.
The grinding speed is appropriately set depending on the type and size of the apparatus. For example, in the case of a ball mill, it is usually 50 rpm or more, preferably 100 rpm or more, more preferably 150 rpm or more, and further preferably 200 rpm or more. Moreover, it is 2500 rpm or less normally, Preferably it is 2300 rpm or less, More preferably, it is 2000 rpm or less. If the speed is too high, control of the particle size tends to be difficult, and if the speed is too low, the processing speed tends to be slow.

The grinding time is usually 30 seconds or longer, preferably 1 minute or longer, more preferably 1 minute 30 seconds or longer, and still more preferably 2 minutes or longer. Moreover, it is usually 3 hours or less, preferably 2.5 hours or less, more preferably 2 hours or less. If the pulverization time is too short, the particle size control tends to be difficult, and if the pulverization time is too long, the productivity tends to decrease.
In the case of a vibration mill, the grinding speed is usually 50 rpm or more, preferably 100 rpm or more, more preferably 150 rpm or more, and still more preferably 200 rpm or more. Moreover, it is 2500 rpm or less normally, Preferably it is 2300 rpm or less, More preferably, it is 2000 rpm or less. If the speed is too high, control of the particle size tends to be difficult, and if the speed is too low, the processing speed tends to be slow.

The grinding time is usually 30 seconds or longer, preferably 1 minute or longer, more preferably 1 minute 30 seconds or longer, and further preferably 2 minutes or longer. Moreover, it is usually 3 hours or less, preferably 2.5 hours or less, more preferably 2 hours or less. If the pulverization time is too short, the particle size control tends to be difficult, and if the pulverization time is too long, the productivity tends to decrease.
Further, the composite particles obtained by the above-described production method may be subjected to a particle size classification treatment.

As classification treatment conditions, the opening is usually 53 μm or less, preferably 45 μm or less, more preferably 38 μm or less.
There are no particular restrictions on the equipment used for classification, but for example, when dry sieving: rotary sieving, oscillating sieving, rotating sieving, vibrating sieving, etc. can be used. : Gravity classifier, inertial classifier, centrifugal classifier (classifier, cyclone, etc.) can be used. For wet sieving: mechanical wet classifier, hydraulic classifier, settling classifier, A centrifugal wet classifier or the like can be used.

(Content of carbonaceous material)
The content of the carbonaceous material in the composite carbon particles (B) of the present invention is usually 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 0.1% by mass or more, based on the graphite particles in the composite carbon particles (B). Preferably it is 0.3% or more, particularly preferably 0.7% by weight or more, and the content is usually 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, still more preferably. It is 7 mass% or less, Most preferably, it is 5 mass% or less.

If the content is too high, the carbon material will be damaged and material destruction will occur when rolling at a sufficient pressure to achieve a high capacity in a non-aqueous secondary battery. There is a tendency to increase capacity and decrease initial efficiency.
On the other hand, if the content is too small, the effect of coating tends to be difficult to obtain. That is, the side reaction with the electrolytic solution in the battery cannot be sufficiently suppressed, and the charge / discharge irreversible capacity during the initial cycle tends to increase and the initial efficiency tends to decrease.

The content of the carbonaceous material is determined by the mass of the graphite particles and the mass of the carbonaceous particles contained in the composite carbon particles (B), the amount of the organic compound that becomes the carbonaceous material, and the micro method based on JIS K 2270. It can be calculated by the following formula (4) based on the measured residual carbon ratio.
Formula (4)
Carbonaceous material content (% by mass)
= (Mass of organic compound to be carbonaceous material × residual carbon ratio × 100) / {sample (composite carbon particle (B)
) Total mass of graphitic particles (C) and carbonaceous particles contained in) + (mass of organic compound to be carbonaceous material × residual carbon ratio)}

(Content of carbonaceous particles)
The content of the carbonaceous particles in the composite carbon particles (B) of the present invention indicates the content of the carbonaceous particles relative to the graphite particles in the composite carbon particles (B). 01% by mass or more, preferably 0.1% by mass or more, more preferably 0.3% or more, particularly preferably 0.7% by mass or more, and the content is usually 20% by mass or less, preferably 15%. It is not more than mass%, more preferably not more than 10 mass%, still more preferably not more than 7 mass%, particularly preferably not more than 5 mass%.

When there is too much content, the reactivity with electrolyte solution will increase and there exists a tendency for the cycling characteristics of a battery to fall.
On the other hand, if the content is too small, the effect of coating tends to be difficult to obtain. That is, the side reaction with the electrolytic solution in the battery cannot be sufficiently suppressed, and the charge / discharge irreversible capacity during the initial cycle tends to increase and the initial efficiency tends to decrease.
The content of the carbonaceous particles is the amount added when the carbonaceous particles are mixed.

[Carbon material for negative electrode of non-aqueous secondary battery]
The carbon material for a non-aqueous secondary battery negative electrode of the present invention is not particularly limited as long as it contains the Si composite carbon particles (A) and the composite graphite particles (B) described above, but has the following characteristics. preferable.
The various characteristics of the carbon material of the present invention include Si composite carbon particles (A) and amorphous composite graphite particles (B) constituting the carbon material, natural graphite particles (D) when present, and other properties described later. It can be roughly predicted by weighted averaging the values of the corresponding properties of the material.

(A) X-ray parameter of carbon material for negative electrode of non-aqueous secondary battery The interplanar spacing (d ₀₀₂ ) of the 002 surface according to the X-ray wide angle diffraction method of the carbon material for negative electrode of the non-aqueous secondary battery of the present invention is usually 0. It is 337 nm or less, preferably 0.336 nm or less. An excessively high d ₀₀₂ value indicates that the graphite crystallinity is low, and the initial irreversible capacity may increase when a non-aqueous secondary battery is used. On the other hand, since the theoretical value of the surface spacing of the 002 plane of graphite is 0.3356 nm, the d value is usually 0.3356 nm or more.
In addition, the crystallite size (Lc) of the carbon material for a nonaqueous secondary battery negative electrode of the present invention is usually in the range of 30 nm or more, preferably 50 nm or more, more preferably 100 nm or more. Below this range, the crystallinity decreases and the discharge capacity of the battery tends to decrease. The lower limit of Lc is the theoretical value of graphite.

(B) Volume-based average particle diameter (d50) of carbon material for negative electrode of non-aqueous secondary battery
The average particle diameter d50 of the carbon material for a non-aqueous secondary battery negative electrode of the present invention is usually 50 μm or less, preferably 40 μm or less, more preferably 30 μm or less, still more preferably 25 μm or less, particularly preferably 22 μm or less. It is 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, further preferably 15 μm, and particularly preferably 18 μm or more. If the average particle diameter d50 is too small, the specific surface area becomes large, so that the decomposition of the electrolytic solution increases and the initial efficiency of the non-aqueous secondary battery tends to decrease. If the average particle diameter d50 is too large, the rapid charge / discharge characteristics are reduced. It tends to cause a decline.

(C) Aspect ratio of carbon material for non-aqueous secondary battery negative electrode The aspect ratio of the carbon material for non-aqueous secondary battery negative electrode of the present invention is usually 1 or more, preferably 1.3 or more, more preferably 1.4 or more. More preferably, it is 1.5 or more, usually 4 or less, preferably 3 or less, more preferably 2.5 or less, and still more preferably 2 or less.
If the aspect ratio is too large, the particles tend to be aligned in the direction parallel to the current collector when used as an electrode, so that there are not enough continuous voids in the thickness direction of the electrode, and lithium ion mobility in the thickness direction. However, the rapid charge / discharge characteristics of the non-aqueous secondary battery tend to be reduced.

(D) BET specific surface area (SA) of carbon material for negative electrode of non-aqueous secondary battery
The specific surface area by the BET method of the carbon material for a nonaqueous secondary battery negative electrode of the present invention is usually 0.5 m ² / g or more, preferably 1 m ² / g or more, more preferably 3 m ² / g or more, and further preferably 5 m ^2. / G or more, particularly preferably 8 m ² / g. Moreover, it is 30 m < ² > / g or less normally, Preferably it is 20 m < ² > / g or less, More preferably, it is 18 m < ² > / g or less, More preferably, it is 16 m < ² > / g or less, Most preferably, it is 14 m < ² > / g or less. If the specific surface area is too large, the reactivity between the portion exposed to the electrolyte and the electrolyte when used as the negative electrode active material is increased, which tends to cause a decrease in initial efficiency and an increase in the amount of gas generated, making it difficult to obtain a preferable battery. Tend. When the specific surface area is too small, there are few sites where lithium ions enter and exit, and the high-speed charge / discharge characteristics and output characteristics of the nonaqueous secondary battery tend to be inferior.

(E) Circularity of carbon material for negative electrode of nonaqueous secondary battery The circularity of the carbon material for negative electrode of the nonaqueous secondary battery of the present invention is usually 0.85 or more, preferably 0.88 or more, more preferably 0.8. 89 or more, more preferably 0.90 or more. Further, the circularity is as follows: · BR> C is usually 1 or less, preferably 0.99 or less, more preferably 0.98 or less, and still more preferably 0.97 or less. If the circularity is too small, particles tend to be aligned in parallel with the current collector when used as an electrode, so that there is not enough continuous void in the thickness direction of the electrode, and lithium ion mobility in the thickness direction Tends to decrease, leading to a decrease in rapid charge / discharge characteristics. If the circularity is too large, there is a tendency that the effect of suppressing the conduction path breakage is reduced and the cycle characteristics of the nonaqueous secondary battery are lowered.

(F) Raman R value of carbon material for nonaqueous secondary battery negative electrode The Raman R value (as defined above) of the carbon material for nonaqueous secondary battery negative electrode of the present invention is usually 1 or less, preferably 0. 8 or less, more preferably 0.6 or less, still more preferably 0.5 or less, usually 0.05 or more, preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.25 or more. is there. If the Raman R value is less than this range, the crystallinity of the particle surface becomes too high, the number of Li insertion sites decreases, and the rapid charge / discharge characteristics of the nonaqueous secondary battery tend to be reduced. On the other hand, if it exceeds this range, the crystallinity of the particle surface is disturbed, the reactivity with the electrolytic solution is increased, and the charge / discharge efficiency of the nonaqueous secondary battery tends to decrease and the gas generation tends to increase.

(G) Tap density of carbon material for non-aqueous secondary battery negative electrode The carbon material for non-aqueous secondary battery negative electrode of the present invention has a tap density of usually 0.6 g / cm ³ or more, preferably 0.7 g / cm ³ or more. , more preferably 0.8 g / cm ³ or more, more preferably 0.9 g / cm ³ or more, and particularly preferably 1.1 g / cm ³ or more, whereas, usually 1.8 g / cm ³ or less, preferably 1 .5g / cm ³ or less, more preferably 1.3 g / cm ³ or less, further preferably 1.2 g / cm ³ or less.
If the tap density is smaller than the above range, sufficient continuous voids are not secured in the electrode, and the mobility of lithium ions in the electrolyte held in the voids is reduced, so that the rapid charge / discharge characteristics of the non-aqueous secondary battery Tends to decrease.

<Mass ratio of Si composite carbon particles (A) and composite carbon particles (B)>
In the carbon material for a non-aqueous secondary battery negative electrode of the present invention, the mass ratio of the composite carbon particles (B) to the total amount of the Si composite carbon particles (A) and the composite carbon particles (B) is not particularly limited, but is 0 mass. %, Preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, particularly preferably 30% by mass or more, and usually 90% by mass or less, preferably 80% by mass or less, More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less, Most preferably, it is 50 mass% or less.

When the ratio of the Si composite carbon particles (A) to the total amount of the Si composite carbon particles (A) and the composite carbon particles (B) is too large, the initial efficiency of the non-aqueous secondary battery is decreased and the electrode plate strength is decreased. There is. Moreover, when there is too little ratio of composite carbon particle (A), there exists a tendency which causes the fall of a capacity | capacitance.
In obtaining the carbon material of the present invention, the mixing method is not particularly limited as long as these Si composite carbon particles (A) and composite carbon particles (B) are uniformly mixed. As a mixing device, a mixer with a structure in which two frame molds rotate and revolve; a single blade, such as a dissolver that is a high-speed high-shear mixer and a butterfly mixer for high viscosity, is stirred and dispersed in a tank. A so-called kneader-type device having a structure in which a stirring blade such as a sigma type rotates along the side surface of a semi-cylindrical mixing tank; a trimix type device with three stirring blades; A so-called bead mill type apparatus having a rotating disk and a dispersion medium is used.

It also has a container with a paddle that is rotated by a shaft, and the inner wall surface of the container is formed substantially along the outermost line of rotation of the paddle, preferably in a long twin cylinder shape, and the paddle has side surfaces facing each other. A device having a structure in which many pairs are arranged in the axial direction of the shaft so as to be slidably engaged (for example, KRC reactor manufactured by Kurimoto Iron Works, SC processor, TEM manufactured by Toshiba Machine Celmac, TEX-K manufactured by Nippon Steel Works) Furthermore, it has a container in which a single inner shaft and a plurality of pavement or sawtooth paddles fixed to the shaft are arranged in different phases, and the inner wall surface is the outermost line of rotation of the paddle (External heat type) apparatus having a structure preferably formed in a cylindrical shape (e.g., a Redige mixer manufactured by Redige Co., Ltd., a flow share mixer manufactured by Taiyo Koki Co., Ltd., Tsukishima Machine Co., Ltd.) Of DT dryers, etc.) can also be used. In order to perform mixing in a continuous manner, a pipeline mixer, a continuous bead mill, or the like may be used.

<Mixing with other materials>
The carbon material for a non-aqueous secondary battery negative electrode of the present invention is suitably used as a negative electrode material for a non-aqueous secondary battery by using Si composite carbon particles (A) and composite carbon particles (B) in any composition and combination. Although it can be used, it may be used as a negative electrode material for non-aqueous secondary batteries, preferably non-aqueous secondary batteries, by mixing with one or more other materials not corresponding to the above-mentioned materials. .

When other carbon materials are mixed, the mixing amount of the other materials with respect to the total amount of the carbon material for the nonaqueous secondary battery negative electrode is usually 10% by mass or more, preferably 20% by mass or more, and usually 90% by mass or less, preferably Is 70% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and particularly preferably 30% by mass or less.
When the mixing ratio of other carbon materials is less than the above range, the added effect tends to hardly appear. On the other hand, when the above range is exceeded, the characteristics of the carbon material for a non-aqueous secondary battery negative electrode of the present invention tend to hardly appear.

As other materials not corresponding to the present invention, for example, materials selected from natural graphite, artificial graphite, amorphous carbon-coated graphite, amorphous carbon, metal particles, and metal compounds can be used. Any one of these materials may be used alone, or two or more of these materials may be used in any combination and composition.
As the natural graphite, for example, highly purified scaly graphite particles or scaly graphite can be used.

Examples of the artificial graphite include particles obtained by graphitizing a carbon material. For example, particles obtained by firing and graphitizing a single graphite precursor particle while it is powdered can be used.
As the amorphous carbon-coated graphite, for example, natural graphite or artificial graphite coated with an amorphous carbon precursor and fired particles, or natural graphite or artificial graphite coated with amorphous carbon by CVD are used. be able to.
As the amorphous carbon, for example, particles obtained by firing a bulk mesophase, or particles obtained by firing an infusible carbonizable pitch or the like can be used.

  Examples of the metal particles include Fe, Co, Sb, Bi, Pb, Ni, Ag, Si, Sn, As, Sb, Al, Zr, Cr, P, S, V, Mn, Nb, Mo, Cu, A metal selected from the group consisting of Zn, Ge, In, Ti or the like or a compound thereof is preferable. Further, an alloy composed of two or more kinds of metals may be used, and the metal particles may be alloy particles formed of two or more kinds of metal elements. Among these, a metal selected from the group consisting of Si, Sn, As, Sb, Al, Zn, and W or a compound thereof is preferable.

Examples of the metal compound include metal oxides, metal nitrides, and metal carbides. Moreover, you may use the alloy which consists of 2 or more types of metals.
Among these, Si compounds are preferable. As the Si compound, the same compound as the Si compound in the Si composite carbon particles (A) can be used.
There are no particular restrictions on the device used for mixing the essential components of the non-aqueous secondary battery negative electrode carbon material with other materials. For example, in the case of a rotary mixer: a cylindrical mixer, a twin cylindrical mixer, Double cone type mixer, regular cubic type mixer, saddle type mixer, fixed type mixer: spiral type mixer, ribbon type mixer, Muller type mixer, Helical Flight type mixer, Pug
A mill type mixer, a fluidized type mixer, or the like can be used.

[Negative electrode for non-aqueous secondary battery]
The present invention also relates to a negative electrode for a non-aqueous secondary battery formed using the carbon material for a non-aqueous secondary battery negative electrode of the present invention, and a specific example thereof includes a negative electrode for a lithium ion secondary battery. .
The method for producing the negative electrode for nonaqueous secondary battery and the selection of materials other than the carbon material for nonaqueous secondary battery negative electrode of the present invention constituting the negative electrode for nonaqueous secondary battery are not particularly limited.

The negative electrode for a non-aqueous secondary battery of the present invention includes a current collector and an active material layer formed on the current collector, and the active material layer is a carbon material for a non-aqueous secondary battery negative electrode of the present invention. It contains. The active material layer preferably further contains a binder.
The binder is not particularly limited, but a binder having an olefinically unsaturated bond in the molecule is preferable. Specific examples include styrene-butadiene rubber, styrene / isoprene / styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, and ethylene / propylene / diene copolymer.

By using such a binder having an olefinically unsaturated bond in the molecule, the swellability of the active material layer with respect to the electrolytic solution can be reduced. Of these, styrene-butadiene rubber is preferred because of its availability.
By using such a binder having an olefinically unsaturated bond in the molecule and the carbon material for a nonaqueous secondary battery negative electrode of the present invention in combination, the mechanical strength of the negative electrode plate can be increased. When the mechanical strength of the negative electrode plate is high, deterioration of the negative electrode due to charging / discharging of the nonaqueous secondary battery is suppressed, and the cycle life can be extended.

The binder having an olefinically unsaturated bond in the molecule preferably has a large molecular weight and / or a large proportion of unsaturated bonds.
As the molecular weight of the binder, the weight average molecular weight can usually be 10,000 or more, and can usually be 1,000,000 or less. If it is this range, both mechanical strength and flexibility can be controlled to a favorable range. The weight average molecular weight is preferably 50,000 or more, and preferably 300,000 or less.

As the ratio of olefinically unsaturated bonds in the binder molecule, the number of moles of olefinically unsaturated bonds per 1 g of the total binder can be usually 2.5 × 10 ⁻⁷ mol or more, and usually 5 × It can be 10 <^-6> mol or less. If it is this range, the intensity | strength improvement effect will be acquired sufficiently and flexibility will also be favorable. The number of moles is preferably 8 × 10 ⁻⁷ mol or more, and preferably 1 × 10 ⁻⁶ mol or less.

Moreover, about the binder which has an olefinically unsaturated bond in a molecule | numerator, the unsaturation degree can be normally 15% or more and 90% or less. The degree of unsaturation is preferably 20% or more, more preferably 40% or more, and preferably 80% or less. In the present specification, the degree of unsaturation represents the ratio (%) of the double bond to the repeating unit of the polymer.
As the binder, a binder having no olefinically unsaturated bond in the molecule can also be used. By using a binder having an olefinically unsaturated bond in the molecule and a binder having no olefinically unsaturated bond in the molecule, improvement in coating property can be expected.

When the binder having an olefinically unsaturated bond in the molecule is 100% by mass, the mixing ratio of the binder having no olefinically unsaturated bond in the molecule is to suppress the strength of the active material layer from being lowered. Usually, it can be 150 mass% or less, Preferably it is 120 mass% or less.
Examples of the binder having no olefinically unsaturated bond in the molecule include thickening polysaccharides such as methylcellulose, carboxymethylcellulose, starch, carrageenan, pullulan, guar gum, xanthan gum (xanthan gum);
Polyethers such as polyethylene oxide and polypropylene oxide;
Vinyl alcohols such as polyvinyl alcohol and polyvinyl butyral;
Polyacids such as polyacrylic acid and polymethacrylic acid or metal salts thereof;
Fluorine-containing polymers such as polyvinylidene fluoride;
Examples thereof include alkane polymers such as polyethylene and polypropylene, and copolymers thereof.

In order to improve the electroconductivity of a negative electrode, you may make the active material layer in the negative electrode for non-aqueous secondary batteries of this invention contain a conductive support agent. The conductive aid is not particularly limited, and examples thereof include carbon black such as acetylene black, ketjen black, and furnace black, fine powder made of Cu, Ni having an average particle size of 1 μm or less, or an alloy thereof.
It is preferable that the addition amount of a conductive support agent is 10 mass parts or less with respect to 100 mass parts of carbon materials for non-aqueous secondary battery negative electrodes of this invention.

The negative electrode for a non-aqueous secondary battery of the present invention is a slurry obtained by dispersing the carbon material for a non-aqueous secondary battery negative electrode of the present invention and optionally a binder and / or a conductive additive in a dispersion medium. It can be formed by coating and drying. As the dispersion medium, an organic solvent such as alcohol or water can be used.
It does not specifically limit as a collector which apply | coats a slurry, A well-known thing can be used. Specific examples include metal thin films such as rolled copper foil, electrolytic copper foil, and stainless steel foil.

The thickness of the current collector can usually be 4 μm or more, and can usually be 30 μm or less. The thickness is preferably 6 μm or more, and preferably 20 μm or less.
The thickness of the active material layer obtained by applying and drying the slurry is usually 5 μm or more from the viewpoint of practicality as a negative electrode and sufficient lithium ion occlusion / release function for high-density current values. In addition, it can usually be 200 μm or less. Preferably it is 20 micrometers or more, More preferably, it is 30 micrometers or more, Preferably it is 100 micrometers or less, More preferably, it is 75 micrometers or less.

You may adjust the thickness of an active material layer so that it may become the thickness of the said range by pressing after application | coating of a slurry and drying.
Although the density of the carbon material for the non-aqueous secondary battery negative electrode in the active material layer varies depending on the application, for example, in an application in which input / output characteristics such as an in-vehicle application and a power tool application are emphasized, usually 1.1 g / cm ³ or more, 1.65 g / cm ³ or less. Within this range, it is possible to avoid an increase in contact resistance between particles due to the density being too low, and it is also possible to suppress a decrease in rate characteristics due to the density being too high.

The density is preferably 1.2 g / cm ³ or more, more preferably 1.25 g / cm ³ or more.
In applications in which capacity is important, such as portable device applications such as mobile phones and personal computers, it is usually 1.45 g / cm ³ or more, and usually 1.9 g / cm ³ or less.

If it is this range, the capacity | capacitance fall of the battery per unit volume by a density being too low can be avoided, On the other hand, the fall of the rate characteristic by a density being too high can also be suppressed.
Density is preferably 1.55 g / cm ³ or more, more preferably 1.65 g / cm ³ or more, and particularly preferably 1.7 g / cm ³ or more.

[Non-aqueous secondary battery]
The basic configuration of the nonaqueous secondary battery according to the present invention can be the same as, for example, a known lithium ion secondary battery, and usually includes a positive electrode and a negative electrode capable of inserting and extracting lithium ions, and an electrolyte. The negative electrode is a negative electrode for a non-aqueous secondary battery according to the present invention described above.

<Positive electrode>
The positive electrode can include a current collector and an active material layer formed on the current collector. The active material layer preferably contains a binder in addition to the positive electrode active material.
Examples of the positive electrode active material include metal chalcogen compounds that can occlude and release alkali metal cations such as lithium ions during charge and discharge. Of these, metal chalcogen compounds capable of inserting and extracting lithium ions are preferred.
Examples of metal chalcogen compounds include transition metal oxides such as vanadium oxide, molybdenum oxide, manganese oxide, chromium oxide, titanium oxide, and tungsten oxide;
Transition metal sulfides such as vanadium sulfide, molybdenum sulfide, titanium sulfide, CuS;
Phosphorus-sulfur compounds of transition metals such as NiPS ₃ and FePS ₃ ;
Selenium compounds of transition metals such as VSe ₂ and NbSe ₃ ;
Complex oxides of transition metals such as Fe _0.25 V _0.75 S ₂ , Na _0.1 CrS ₂ ;
Examples thereof include composite sulfides of transition metals such as LiCoS ₂ and LiNiS ₂ .

Among them, from the viewpoint of occlusion / release of lithium ions, V ₂ O ₅ , V ₅ O ₁₃ , VO ₂ , Cr ₂ O ₅ , MnO ₂ , TiO ₂ , MoV ₂ O ₈ , LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , TiS ₂ , V ₂ S ₅ , Cr _0.25 V _0.75 S ₂ , Cr _0.5 V _0.5 S _{2 and the} like are preferable, and LiCoO ₂ , LiNiO ₂ , LiMn ₂ O _4, and their transitions A lithium transition metal composite oxide in which a part of the metal is substituted with another metal is particularly preferable.

These positive electrode active materials may be used alone or in combination.
The binder for positive electrodes is not specifically limited, A well-known thing can be selected arbitrarily and can be used. Examples include inorganic compounds such as silicate and water glass, and resins having no unsaturated bond such as Teflon (registered trademark) and polyvinylidene fluoride. Among them, a resin having no unsaturated bond is preferable because it is difficult to decompose during the oxidation reaction.

The weight average molecular weight of the binder can usually be 10,000 or more, and can usually be 3 million or less. The weight average molecular weight is preferably 100,000 or more, and preferably 1,000,000 or less.
The positive electrode active material layer may contain a conductive additive in order to improve the conductivity of the positive electrode. The conductive auxiliary agent is not particularly limited, and examples thereof include carbon powders such as acetylene black, carbon black, and graphite, and various metal fibers, powders, and foils.

  In the present invention, in the same manner as the above-described negative electrode manufacturing method, the positive electrode is dispersed in a dispersion medium with an active material and, optionally, a binder and / or a conductive auxiliary agent, and this is applied to the surface of the current collector. Can be formed. The current collector of the positive electrode is not particularly limited, and examples thereof include aluminum, nickel, stainless steel (SUS), and the like.

<Electrolyte>
The electrolyte (sometimes referred to as “electrolyte”) is not particularly limited, and a non-aqueous electrolyte obtained by dissolving a lithium salt as an electrolyte in a non-aqueous solvent, or an organic polymer compound or the like is added to the non-aqueous electrolyte. By doing so, a gel-like, rubber-like, or solid sheet-like shape can be mentioned.
The non-aqueous solvent used for the non-aqueous electrolyte is not particularly limited, and a known non-aqueous solvent can be used.

Examples thereof include chain carbonates such as diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate;
Cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate;
Chain ethers such as 1,2-dimethoxyethane;
Cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, 1,3-dioxolane;
Chain esters such as methyl formate, methyl acetate and methyl propionate;
and cyclic esters such as γ-butyrolactone and γ-valerolactone.

A non-aqueous solvent may be individual or may use 2 or more types together. In the case of a mixed solvent, a combination of a mixed solvent containing a cyclic carbonate and a chain carbonate is preferable from the balance of conductivity and viscosity, and the cyclic carbonate is preferably ethylene carbonate.
The lithium salt used in the non-aqueous electrolyte is not particularly limited, and a known lithium salt can be used. For example, halides such as LiCl and LiBr;
Perhalogenates such as LiClO ₄ , LiBrO ₄ , LiClO ₄ ;
Inorganic lithium salts such as inorganic fluoride salts such as LiPF ₆ , LiBF ₄ , LiAsF ₆ ;
Perfluoroalkanesulfonates such as LiCF ₃ SO ₃ , LiC ₄ F ₉ SO ₃ ;
Fluorine-containing organic lithium salts such as perfluoroalkanesulfonic acid imide salts such as Li trifluoromethanesulfonylimide ((CF ₃ SO ₂ ) ₂ NLi) can be used. Among these, LiClO ₄ , LiPF ₆ , and LiBF ₄ are preferable.

A lithium salt may be used independently or may use 2 or more types together. The concentration of the lithium salt in the nonaqueous electrolytic solution can be in the range of 0.5 mol / L to 2.0 mol / L.
When the organic polymer compound is included in the non-aqueous electrolyte solution described above and used in the form of a gel, rubber, or solid sheet, specific examples of the organic polymer compound include polyethylene oxide, polypropylene oxide, and the like. Polyether polymer compounds;
A crosslinked polymer of a polyether polymer compound;
Vinyl alcohol polymer compounds such as polyvinyl alcohol and polyvinyl butyral; insolubilized vinyl alcohol polymer compounds;
Polyepichlorohydrin;
Polyphosphazene;
Polysiloxane;
Vinyl polymer compounds such as polyvinylpyrrolidone, polyvinylidene carbonate, and polyacrylonitrile;
Examples thereof include polymer copolymers such as poly (ω-methoxyoligooxyethylene methacrylate), poly (ω-methoxyoligooxyethylene methacrylate-co-methyl methacrylate) and poly (hexafluoropropylene-vinylidene fluoride).

The non-aqueous electrolyte solution described above may further contain a film forming agent.
Specific examples of the film forming agent include carbonate compounds such as vinylene carbonate, vinyl ethyl carbonate, and methyl phenyl carbonate;
Alkene sulfides such as ethylene sulfide and propylene sulfide;
Sultone compounds such as 1,3-propane sultone and 1,4-butane sultone;
Examples of the acid anhydride include maleic acid anhydride and succinic acid anhydride.

Further, an overcharge inhibitor such as diphenyl ether or cyclohexylbenzene may be added to the non-aqueous electrolyte.
When using the above-mentioned various additives, the total content of the additives is the total amount of the non-aqueous electrolyte so as not to adversely affect other battery characteristics such as an increase in initial irreversible capacity, low temperature characteristics, and deterioration in rate characteristics. In general, it can be 10% by mass or less, in particular, 8% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

Further, as the electrolyte, a polymer solid electrolyte which is a conductor of an alkali metal cation such as lithium ion can be used.
Examples of the polymer solid electrolyte include those obtained by dissolving a Li salt in the aforementioned polyether polymer compound, and polymers in which the terminal hydroxyl group of the polyether is substituted with an alkoxide.

<Others>
In order to prevent a short circuit between the electrodes, a porous separator such as a porous membrane or a nonwoven fabric can usually be interposed between the positive electrode and the negative electrode, and the non-aqueous electrolyte is impregnated into the porous separator. It is convenient to use it. As a material for the separator, polyolefin such as polyethylene and polypropylene, polyethersulfone, and the like are used, and polyolefin is preferable.

The form of the non-aqueous secondary battery is not particularly limited, for example, a cylinder type in which a sheet electrode and a separator are spiraled;
Examples include an inside-out structure cylinder type in which a pellet electrode and a separator are combined; a coin type in which a pellet electrode and a separator are stacked, and the like.
Further, by storing batteries of these forms in an optional outer case, the battery can be used in an arbitrary shape and size such as a coin shape, a cylindrical shape, and a square shape.

The procedure for assembling the non-aqueous secondary battery is not particularly limited, and can be assembled by an appropriate procedure according to the structure of the battery. For example, a negative electrode can be placed on an outer case, an electrolyte and a separator can be provided thereon, and a positive electrode can be placed so as to face the negative electrode, and can be caulked together with a gasket and a sealing plate to form a battery.
By using the carbon material for a non-aqueous secondary battery negative electrode of the present invention, it is possible to provide a non-aqueous secondary battery having excellent stability, high output, high capacity, small irreversible capacity, and excellent cycle retention. it can.

EXAMPLES Next, specific embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the measuring method of each physical property is as follows.
<Measuring method of average particle diameter d50>
The measuring method of the average particle diameter d50 is as follows. A commercially available laser diffraction / scattering particle size is prepared by suspending 0.01 g of a sample in 10 mL of a 0.2 mass% aqueous solution of polyoxyethylene sorbitan monolaurate (for example, Tween 20 (registered trademark)) as a surfactant. The sample was introduced into a distribution measuring device “LA-920 manufactured by HORIBA” and irradiated with 28 kHz ultrasonic waves at an output of 60 W for 1 minute, and then the volume-based median diameter in the measuring device was measured. Defined.

<Measurement method of BET specific surface area (SA)>
The BET specific surface area (SA) was measured by a BET 1-point method by a nitrogen gas adsorption flow method using a specific surface area measuring device “AMS8000” manufactured by Okura Riken. Specifically, 0.4 g of a sample is filled in a cell, heated to 350 ° C., pretreated, cooled to liquid nitrogen temperature, and saturated adsorption of 30% nitrogen and 70% He gas is performed. The amount of gas desorbed by heating to room temperature was measured. From the obtained results, the specific surface area was calculated by a normal BET method.

<Raman R value>
The sample to be measured was filled by naturally dropping into the measurement cell, and measurement was performed while rotating the measurement cell in a plane perpendicular to the laser beam while irradiating the measurement cell with an argon ion laser beam. The measurement conditions of the Raman spectrum are shown below.
Raman spectrometer: "Raman spectrometer" manufactured by JASCO
Argon ion laser light wavelength: 514.5 nm
Laser power on sample: 25 mW
Resolution: 4cm ^-1
Measurement range: 1100 cm ^{−1 to} 1730 cm ⁻¹
Peak intensity measurement, peak half-width measurement: background processing, smoothing processing (convolution 5 points by simple average)
The obtained Raman spectrum, the intensity _{I A} of the peak _{P A} in the vicinity of 1580 cm ^-1, and measuring the intensity _{I B} of a peak _{P B} in the vicinity of 1360 cm ^-1, the intensity ratio R _{(R =} I B / _{I A} ) And calculated as the Raman R value.

<Tap density>
The method for measuring the tap density is as follows. Using a powder density measuring device, a sample was dropped into a cylindrical tap cell having a diameter of 1.6 cm and a volume capacity of 20 cm ³ through a sieve having an opening of 300 μm, and the cell was fully filled. The density obtained from the volume and the mass of the sample was defined as the tap density.

<DBP oil absorption>
The DBP oil absorption amount is defined by measured values when 40 g of measurement material is added, the dropping speed is 4 ml / min, the rotation speed is 125 rpm, and the set torque is 500 N · m, in accordance with JIS K6217. For the measurement, an absorption measuring device (S-500) from Asahi Research Institute was used.

<Si content of composite carbon particles>
The Si content of the composite carbon particles was determined as follows. The composite carbon particles were completely melted with an alkali, then dissolved and fixed in water, measured with an inductively coupled plasma emission spectrometer (HORIBA, Ltd. ULTIMA2C), and the amount of Si was calculated from a calibration curve. Thereafter, the Si content of the composite carbon particles was calculated by dividing the Si amount by the weight of the composite carbon particles.

<Observation of cross-sectional structure of composite carbon particles>
The cross-sectional structure of the composite carbon particles was measured as follows. The electrode plate prepared in <Preparation of Electrode Sheet> described later was processed with a cross section polisher (JEOL IB-09020CP) to obtain an electrode plate cross section. While observing the obtained electrode plate cross section with SEM (Hitachi High-Tech SU-70), mapping of graphite and Si was performed using EDX. The SEM acquisition conditions were an acceleration voltage of 3 kV and a magnification of 2000 times, and an image in a range where one particle could be acquired at a resolution of 256 dpi was obtained.

<Initial discharge capacity, initial efficiency>
Using a non-aqueous secondary battery (2016 coin type battery) produced by the method described later, the capacity during battery charging / discharging was measured by the following measurement method.
Charge to 5 mV with respect to the lithium counter electrode at a current density of 0.05 C (the current value for discharging the rated capacity with a 1 hour rate discharge capacity in 1 hour is assumed to be 1 C), and the current at a constant voltage of 5 mV. After charging until the density is 0.005 C, after doping lithium in the negative electrode,
The battery was discharged to 1.5 V with respect to the lithium counter electrode at a current density of 0.1 C. The discharge capacity (mAh / g) at this time is taken as the discharge capacity (mAh / g) of the tested carbon material, and the difference between the charge capacity (mAh / g) and the discharge capacity (mAh / g) is the irreversible capacity (mAh / g). It was. Moreover, the discharge capacity (mAh / g) of the first cycle obtained here was divided by the charge capacity (mAh / g), and the value obtained by multiplying by 100 was defined as the initial efficiency (%).

<Input / output resistance>
The battery is charged for 150 minutes at a constant current of 0.2C in a 25 ° C environment, and then stored in a constant temperature bath at 25 ° C for 3 hours or more, and then for 10 seconds at 0.25C, 1.00C, 3.00C, and 4.50C, respectively. The battery was discharged and charged, and the voltage at 10 seconds was measured.
The slope of the current-voltage line obtained by measurement was defined as the input / output resistance (Ω).

<Cycle characteristics>
The cycle characteristics were measured by the following measuring method using a laminate type non-aqueous secondary battery manufactured by the following non-aqueous secondary battery manufacturing method.
For non-aqueous secondary batteries that have not undergone a charge / discharge cycle, voltage range 4.1 V to 3.0 V at 25 ° C., current cycle 0.2 C, 3 cycles, voltage range 4.2 V to 3.0 V, current value Initial charge / discharge was performed for 2 cycles at 0.2 C (constant voltage charging was further performed for 2.5 hours at 4.2 V during charging).
Further, after charging and discharging for 10 cycles at 60 ° C. in a voltage range of 4.2 V to 3.0 V and a current value of 2.0 C, a value obtained by dividing the discharge capacity at the 10th cycle by the discharge capacity at the 1st cycle is discharged. The capacity maintenance rate (cycle maintenance rate) was calculated.

<Production of electrode sheet>
Using the carbon material (negative electrode material) of the example or the comparative example, an electrode plate having an active material layer with an active material layer density of 1.6 ± 0.03 g / cm ³ was produced. Specifically, negative electrode material 20.00 ± 0.02 g
20.00 ± 0.02 g (0.200 g in terms of solid content) of a 1% by mass carboxymethylcellulose sodium salt aqueous solution and 0.75 ± 0.05 g of a styrene / butadiene rubber aqueous dispersion having a weight average molecular weight of 270,000 ( 0.3 g in terms of solid content) was added, stirred for 5 minutes with a Keyence hybrid mixer, and defoamed for 30 seconds to obtain a slurry.

This slurry was applied to a width of 5 cm using a doctor blade so that the negative electrode material was 12.0 ± 0.3 mg / cm ² on a 18 μm-thick copper foil as a current collector, and air-dried at room temperature. Went. Further, after drying at 110 ° C. for 30 minutes, roll pressing was performed using a roller having a diameter of 20 cm to adjust the density of the active material layer to be 1.60 ± 0.03 g / cm ³ to obtain an electrode sheet.

<Preparation of non-aqueous secondary battery (2016 coin type battery)>
The electrode sheet produced by the above method was punched into a disk shape with a diameter of 12.5 mm, and a lithium metal foil was punched into a disk shape with a diameter of 14 mm as a counter electrode. Between both electrodes, a mixed solvent of ethylene carbonate and ethyl methyl carbonate (volume ratio = 3: 7) and LiPF ₆ of 1 mol /
A separator (made of a porous polyethylene film) impregnated with an electrolytic solution dissolved so as to be L was placed, and 2016 coin-type batteries were produced.

<Creation of non-aqueous secondary battery (laminate cell)>
Lithium nickel manganese cobaltate (LiNi _1/3 Mn _1/3 Co _1/3 O ₂ ) is used as the positive electrode active material, and this is mixed with a conductive agent and polyvinylidene fluoride (PVdF) as a binder to form a slurry. did. The obtained slurry was applied to an aluminum foil having a thickness of 15 μm, dried, and rolled with a press, and the positive electrode active material layer had a width of 30 mm, a length of 40 mm, and an uncoated portion for current collection. A positive electrode was cut out into a shape. The density of the positive electrode active material layer was 2.6 g / cm ³ .

As the negative electrode, an electrode sheet produced by the above-described method was cut out into a shape having a width of 32 mm as a size of the negative electrode active material layer, a length of 42 mm, and an uncoated portion as a current collector tab welded portion. . At this time, the density of the negative electrode active material layer was 1.35 g / cm ³ .
The positive electrode and the negative electrode were arranged so that the active material surfaces face each other, and a porous polyethylene sheet separator was sandwiched between the electrodes. At this time, the positive electrode active material surface was faced so as not to deviate from the negative electrode active material surface.

  A laminate sheet (total thickness) obtained by laminating a polypropylene film, an aluminum foil having a thickness of 0.04 mm, and a nylon film in this order by welding current collecting tabs to uncoated portions of each of the positive electrode and the negative electrode. 0.1 mm) was used to sandwich the polypropylene film on the inner surface side, and the region without electrodes was heat sealed except for one side for injecting the electrolyte solution.

Then, the non-aqueous electrolyte solution (ethylene carbonate (EC) / dimethyl carbonate (DMC) / ethyl methyl carbonate (EMC) = 3/3/4 (volume ratio)) was added to the active material layer at a concentration of 1.2 mol / L. 200 μL of lithium phosphate (LiPF ₆ ) dissolved therein was injected, sufficiently infiltrated into the electrode, and sealed to prepare a laminate cell. The rated capacity of this battery is 20 mAh.

Initial conditioning was performed under the following conditions in a 25 ° C. environment.
1 cycle: Charged for 1 hour at 0.2C, then discharged to 3V at 0.2C. 2 cycles: Charged to 4.1V at 0.2C, then discharged to 3V at 0.2C. 3 cycles: 4.2V cccv at 0.5C. 0 after charging (current amount 0.05C cut condition)
. Discharge to 3V at 2C 4 cycles: 4.2V cccv charge at 0.5C (current amount 0.05C cut condition)
("Ccvv charge" means charging after a certain amount of charge at a constant current until a termination condition is reached at a constant voltage.)

(Creation of graphite particles)
Table 1 below shows the physical properties of the graphite particles used in the examples and comparative examples.
Si composite carbon particles (A), composite carbon particles (B), composite carbon particles (X), natural graphite particles (D1), and natural graphite particles (D2) were prepared as follows.

・ Si composite carbon particles (A)
Single-crystal Si having a d50 of 30 μm was pulverized together with NMP (N-methyl-2-pyrrolidone) to a d50 of 0.17 μm with a bead mill (Ashizawa Finetech) to prepare Si slurry (I). After adding 650 g of NMP to 4050 g of this Si slurry (I) (solid content 9.8%), 90 g of polyacrylonitrile was added and dissolved uniformly. Next, 3000 g of scaly natural graphite (d50: 8 μm) was added and mixed to obtain slurry (II) in which polyacrylonitrile, Si, and graphite were uniformly dispersed. The slurry (II) was appropriately dried under reduced pressure for 3 hours at 150 ° C., which is lower than the thermal decomposition temperature of polyacrylonitrile, so that the polyacrylonitrile is not denatured. In addition, the decomposition temperature of polyacrylonitrile was 270 degree | times from DSC analysis. The obtained lump was crushed with a hammer mill (MF10 manufactured by IKA) at a rotation speed of 6000 rpm, and then charged into a hybridization system (manufactured by Nara Machinery Co., Ltd.). A spheroidizing treatment was performed by circulating or staying in the apparatus, and Si composite graphite particles (E) enclosing Si particles were obtained.

Coal tar pitch was mixed with Si composite graphite particles (E) so that the coverage after firing was 7.5%, and kneaded and dispersed by a biaxial kneader.
The obtained dispersion was introduced into a firing furnace and fired at 1100 ° C. for 1 hour in a nitrogen atmosphere. From the firing yield, it was confirmed that the amount of amorphous carbon added was 7.5% by mass in the obtained carbonaceous particles (B). The fired lump is crushed using the mill described above under the condition of 3000 rpm, and then classified with a vibrating screen having an opening of 45 μm to obtain Si composite graphite particles (A) coated with amorphous carbon. (Si content is 8.2% by mass).
In addition, when the cross-sectional structure was observed by the above measurement method, the Si composite carbon particles (A) had a structure in which flaky graphite was folded, and Si compound particles were present in the gaps in the folded structure. It was. Moreover, it was observed that there is a portion where the Si compound particles and the scaly graphite are in contact.

・ Composite carbon particles (B)
The scaly natural graphite having a d50 of 100 μm was spheroidized by a mechanical action for 3 minutes at a rotor peripheral speed of 85 m / sec using a hybridization system NHS-1 manufactured by Nara Machinery Co., Ltd. This sample was processed by classification to obtain spherical graphite particles (C1) having a d50 of 15.7 μm. Carbon black having a primary particle diameter of 24 nm, a BET specific surface area (SA) of 115 m ² / g, and a DBP oil absorption of 110 ml / 100 g is added to the obtained spheroidized graphite particles (C) with respect to the graphite particles. 0% by mass was added and mixed and stirred. The mixed powder and a heavy petroleum oil obtained at the time of naphtha pyrolysis as a carbonaceous material precursor are mixed, subjected to heat treatment at 1300 ° C. in an inert gas, and then the fired product is pulverized and classified to obtain graphite. Composite carbon particles (B) in which carbon black fine particles and amorphous carbon were attached to the surface of the carbonaceous particles were obtained.
From the residual carbon ratio, in the obtained composite carbon particles (B), the mass ratio of spheroidized graphite particles (C) to amorphous carbon (spheroidized graphite particles: amorphous carbon) is 1: 0.03. It was confirmed that there was.

・ Composite carbon particles (X)
The scaly natural graphite having a d50 of 100 μm was spheroidized by a mechanical action for 3 minutes at a rotor peripheral speed of 85 m / sec using a hybridization system NHS-1 manufactured by Nara Machinery Co., Ltd. This sample was processed by classification to obtain spherical graphite particles (C2) having a d50 of 22.7 μm. By mixing the obtained spheroidized graphite particles (C2) and coal tar pitch as an amorphous carbon precursor and subjecting to 1300 ° C. heat treatment in an inert gas, the fired product is crushed and classified, A multilayered carbon material in which spheroidized graphite particles and amorphous carbon were combined was obtained. From the residual carbon ratio, it was confirmed that the mass ratio of spheroidized graphite particles to amorphous carbon (spheroidized graphite particles: amorphous carbon) was 1: 0.03 in the obtained multilayer carbon material. It was done.

・ Natural graphite particles (D1)
Spherical graphite particles (C1) used when producing the composite carbon particles (B) were natural graphite particles (D1).
・ Natural graphite particles (D2)
Spherical graphite particles (C2) used when producing composite carbon particles (X) were natural graphite particles (D2).

・ MCMB
Commercially available mesocarbon microbeads (MCMB) were used.
The various properties of the above various materials are summarized in Table 1 below.

[Example 1]
Si composite carbon particles (A) and composite carbon particles (B) are mixed at Si composite carbon particles (A) / composite carbon particles (B) = 70/30 (mass ratio), and a carbon material for a nonaqueous secondary battery negative electrode It was. With respect to this sample, the initial discharge capacity, the initial efficiency, the input / output resistance, and the discharge capacity retention ratio (cycle retention ratio) were measured by the above measurement methods. The results are shown in Table 2 below.

[Example 2]
Si composite carbon particles (A) and composite carbon particles (B) are mixed at Si composite carbon particles (A) / composite carbon particles (B) = 50/50 (mass ratio), and a carbon material for a nonaqueous secondary battery negative electrode It was. With respect to this sample, the initial discharge capacity, the initial efficiency, the input / output resistance, and the discharge capacity retention ratio (cycle retention ratio) were measured by the above measurement methods. The results are shown in Table 2 below.

[Example 3]
Si composite carbon particles (A) and composite carbon particles (B) are mixed at Si composite carbon particles (A) / composite carbon particles (B) = 30/70 (mass ratio), and a carbon material for a non-aqueous secondary battery negative electrode It was. With respect to this sample, the initial discharge capacity, the initial efficiency, the input / output resistance, and the discharge capacity retention ratio (cycle retention ratio) were measured by the above measurement methods. The results are shown in Table 2 below.

[Comparative Example 1]
Si composite carbon particles (A) were used as a carbon material for a nonaqueous secondary battery negative electrode. With respect to this sample, the initial discharge capacity, the initial efficiency, the input / output resistance, and the discharge capacity retention ratio (cycle retention ratio) were measured by the above measurement methods. The results are shown in Table 2 below.
[Comparative Example 2]
The composite carbon particle (B) was used as a carbon material for a non-aqueous secondary battery negative electrode. With respect to this sample, the initial discharge capacity, the initial efficiency, the input / output resistance, and the discharge capacity retention ratio (cycle retention ratio) were measured by the above measurement methods. The results are shown in Table 2 below.

[Comparative Example 3]
Si composite carbon particles (A) and composite graphite particles (X) are mixed at Si composite carbon particles (A) / composite graphite particles (X) = 70/30 (mass ratio), and a carbon material for a nonaqueous secondary battery negative electrode It was. With respect to this sample, the initial discharge capacity, the initial efficiency, the input / output resistance, and the discharge capacity retention ratio (cycle retention ratio) were measured by the above measurement methods. The results are shown in Table 2 below.

[Comparative Example 4]
Si composite carbon particles (A) and MCMB were mixed at Si composite carbon particles (A) / MCMB = 70/30 (mass ratio) to obtain a carbon material for a nonaqueous secondary battery negative electrode. With respect to this sample, the initial discharge capacity, the initial efficiency, the input / output resistance, and the discharge capacity retention ratio (cycle retention ratio) were measured by the above measurement methods. The results are shown in Table 2 below.

As can be seen from Table 2, the non-aqueous secondary battery negative electrode carbon materials (Examples 1 to 3) containing the Si composite carbon particles (A) and the composite carbon particles (B) are comparative examples 1 that are single materials. Compared with 2, the balance of initial discharge capacity, initial efficiency, input / output resistance, and discharge capacity maintenance ratio is excellent.
Moreover, when Example 1 and Comparative Example 3 and Comparative Example 4 containing the same amount of Si composite carbon particles (A) are compared, it can be seen that the initial discharge capacity, input / output resistance, and discharge capacity retention ratio are high.
This is because the fine irregularities of the carbonaceous particles on the surface of the composite carbon particles (B) ensure a fine flow path of the electrolyte, and improve the input / output characteristics at low temperatures. Furthermore, the composite carbon particles (B This is thought to be due to the increase in the number of contact points between the particles due to the minute irregularities of

  Thus, by using the carbon material for a negative electrode of a non-aqueous secondary battery according to the present invention, a non-aqueous secondary battery balanced at a high level of initial discharge capacity, initial efficiency, input / output resistance, and discharge capacity maintenance ratio is provided. can do.

Claims (6)

A carbon material for a non-aqueous secondary battery negative electrode containing composite carbon particles (A) and composite carbon particles (B),
The composite carbon particles (A) include at least graphite particles and silicon element,
The composite carbon particles (B) comprising at least graphite particles, carbonaceous particles, and a carbonaceous material, the
Carbonaceous particles include coal fine powder, vapor phase carbon powder, carbon black, ketjen black, carbon
Selected from the group of nanofibers, and the carbonaceous material is blacker than graphite particles.
A carbon material for a negative electrode of a non-aqueous secondary battery, wherein the carbon material is an amorphous material having low lead crystallinity . The carbon material for a nonaqueous secondary battery negative electrode according to claim 1, wherein the graphite particles are natural graphite. The carbon material for a non-aqueous secondary battery negative electrode according to claim 1 or 2 , wherein the silicon element is at least one Si compound selected from the group consisting of Si and SiOx (0 <x <2). It said composite carbon particles (A) has a flake graphite are folded structure, more of claims 1 to 3, characterized in that the gap in the folded structure Si compound particles are present The carbon material for a non-aqueous secondary battery negative electrode according to claim 1. It is a negative electrode for non-aqueous secondary batteries provided with a collector and the active material layer formed on the said collector, Comprising: The said active material layer is as described in any one of Claims 1 thru | or 4 . A negative electrode for a non-aqueous secondary battery, comprising a carbon material for a non-aqueous secondary battery negative electrode. A non-aqueous secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein the negative electrode is claim 5.
A non-aqueous secondary battery, which is the negative electrode for a non-aqueous secondary battery described in 1.