JP6065390B2 - Composite of silicon or silicon oxide and carbon nanohorn aggregate for electrode material of lithium ion secondary battery and silicon or silicon oxide and carbon nanohorn aggregate for electrode material of lithium ion secondary battery and lithium ion secondary battery A method for producing a complex with a body. - Google Patents

Description

  The present invention relates to a composite of silicon or silicon oxide and carbon nanohorn, an electrode material, a lithium ion secondary battery, and a method for manufacturing a composite of silicon or silicon oxide and carbon nanohorn.

  In recent years, lithium-ion secondary batteries that are lightweight and have a large charge capacity have been widely used as secondary batteries used in electric devices and electric vehicles. With the improvement in performance of electric devices and electric vehicles, further increase in capacity and excellent rate characteristics are required for lithium ion secondary batteries used in these devices. For this reason, as the negative electrode material, use of a silicon-based material having a large capacity per unit weight from a conventional carbon-based material (graphite carbon, hard carbon, etc.) has been studied.

  However, a large volume change occurs in a silicon-based negative electrode material when a charge / discharge cycle is repeated. For this reason, there are problems that the active material is miniaturized, cracks are generated on the electrode surface, the active material and the electrode are peeled off, and the charge / discharge cycle characteristics deteriorate. In order to solve such problems, the following proposals have been made.

  For example, Patent Document 1 describes a negative electrode active material that is composed of an oxide containing silicon and a carbonaceous material, and in which the oxide is embedded in the carbonaceous material.

  Patent Document 2 describes a negative electrode material provided with an electron conductive material layer on the surface of silicon oxide particles.

  In Patent Document 3, the surface of silicon particles is at least partially covered with a silicon carbide layer, there is a diffraction line derived from silicon in X-ray diffraction, and the amount of free carbon is 5 mass% or less. There is described a silicon composite for non-aqueous electrolyte secondary batteries, characterized in that it exists.

  Patent Document 4 discloses a negative electrode active material capable of inserting and desorbing lithium ions, which is made of silicon, an alloy containing silicon, or silicon oxide (SiOx (1 ≦ x <2)), and carbon nanohorn. And a negative electrode material for a lithium secondary battery, characterized by having an average particle diameter of 2 nm to 10 μm.

JP 2000-243396 A JP 2002-42806 Patent No. 4450192 JP 2010-118330 A

  However, even if any material described in the above-mentioned patent document is used, the relaxation of the volume change of silicon accompanying charge / discharge is insufficient.

An object of the present invention is to provide a composite of silicon or a silicon oxide and a carbon nanohorn aggregate in which volume change associated with insertion / extraction of lithium ions is mitigated , and a method for producing the same.

The composite of silicon or silicon oxide and carbon nanohorn aggregate for electrode material of a lithium ion secondary battery according to the present invention comprises a carbon nanohorn aggregate having pores and silicon or silicon oxide (SiOx (0 < and x ≦ 2)), includes at least a, the silicon or silicon oxide mosquitoes over carbon nanohorn is encapsulated in a complex with the carbon nanohorn aggregates aggregated spherically.

In addition, the method for producing a composite of silicon or silicon oxide and carbon nanohorn aggregates according to the present invention, in a liquid phase atmosphere, mixes silicon or silicon oxide precursors with carbon nanohorn aggregates having pores, Alternatively, the carbon nanohorn encapsulating the silicon or silicon oxide precursor by heating in a vacuum or an inert atmosphere and adsorbing the silicon or silicon oxide precursor inside the carbon nanohorn aggregate having the opening. A step of forming an aggregate, and heating the carbon nanohorn aggregate including the silicon or silicon oxide precursor at 100 ° C. or higher and 1800 ° C. or lower in a vacuum, an inert atmosphere, or a hydrogen atmosphere, A step of changing a silicon oxide precursor to silicon or silicon oxide Characterized in that it contains.

ADVANTAGE OF THE INVENTION According to this invention, the composite_body | complex of the silicon | silicone or silicon oxide with which the volume change accompanying the insertion / detachment | desorption of lithium ion was relieve | moderated, and a carbon nanohorn aggregate | assembly is provided.

It is the schematic which shows the composite_body | complex of the silicon | silicone or silicon oxide which concerns on the 1st Embodiment of this invention, and carbon nanohorn. It is a scanning transmission electron microscope (STEM) image of the carbon nanohorn aggregate | assembly which concerns on the 1st Embodiment of this invention. It is a scanning electron microscope (SEM) image of the carbon nanohorn aggregate | assembly which concerns on the 1st Embodiment of this invention. It is the schematic which shows the mechanism by which silicon or silicon oxide inserts and desorbs lithium ions in the composite of silicon or silicon oxide and carbon nanohorn according to the first embodiment of the present invention. It is the schematic which shows the mechanism of the charging / discharging on the electrode of the composite of the silicon | silicone or silicon oxide which concerns on the 2nd Embodiment of this invention, and a carbon nanohorn. It is the schematic which shows the manufacturing method of the composite_body | complex of the silicon | silicone or silicon oxide which concerns on the 3rd Embodiment of this invention, and carbon nanohorn. 2 is a scanning transmission electron microscope (STEM) image of a composite of silicon or silicon oxide and carbon nanohorn according to Example 1. FIG. It is a figure which shows the result of having analyzed the composite_body | complex of the silicon | silicone or silicon oxide which concerns on Example 1, and carbon nanohorn by energy dispersive X-ray analysis (EDX).

(First embodiment)
Hereinafter, with reference to FIG. 1 to FIG. 4, a composite of silicon or silicon oxide and a carbon nanohorn aggregate according to the first embodiment of the present invention will be described.

FIG. 1 is a schematic view showing a composite of silicon or silicon oxide and carbon nanohorn according to the first embodiment of the present invention. A composite 10 of silicon or silicon oxide and a carbon nanohorn aggregate in the present embodiment includes a carbon nanohorn aggregate 21 having an opening 211, and silicon or silicon oxide 31 included in the carbon nanohorn aggregate 21. including.

  The carbon nanohorn aggregate 21 has a shape in which a plurality of carbon nanohorns 212 are aggregated in a spherical shape. This schematic diagram represents the silicon or silicon oxide 31 that is transmitted through the carbon nanohorn aggregate 21 and included in the carbon nanohorn aggregate 21.

  FIG. 2 is a scanning transmission electron microscope (STEM) image of the carbon nanohorn aggregate according to the first embodiment of the present invention, and FIG. 3 is a scanning electron microscope of the carbon nanohorn aggregate according to the first embodiment of the present invention. (SEM) image. 2 and 3 is a carbon nanohorn aggregate.

  Each carbon nanohorn 212 constituting the carbon nanohorn aggregate 21 has a tube shape and is closed at one end, but has an opening 211 at one end as will be described later. Sometimes it is. The diameter of the carbon nanohorn 212 is not limited, but preferably 2-5 nm.

  The carbon nanohorn 212 is provided with a plurality of apertures 211. As shown in FIG. 1, the opening 211 may be present at the one end portion of the carbon nanohorn 212 or may be present at the side surface of the tube-shaped carbon nanohorn 212. The diameter of the opening 211 is not particularly limited, but preferably 5 nm or less.

  The carbon nanohorn aggregate 21 is an aggregate in which a plurality of carbon nanohorns 212 are aggregated in a spherical shape. The carbon nanohorn 212 is formed so that the one end portion where the carbon nanohorn 212 is closed or provided with the opening 211 is located outside the carbon nanohorn assembly 21 than the other end portion. The one end portion is not limited to the one facing the outer direction, but includes one that is bent or one that faces the inner side.

  The diameter of the carbon nanohorn aggregate 21 is not limited, but a carbon nanohorn aggregate 21 of preferably 30 nm to 200 nm can be used. Since the carbon nanohorn aggregate 21 has the opening 211, the internal space can be used, the specific surface area can be remarkably improved, and the capacity can be increased.

  When silicon or silicon oxide 31 is described as SiOx, it can be used up to 0 ≦ x ≦ 2, but can preferably be used in the range of 0 ≦ x ≦ 1.5. If x is larger than 1.5, the amount of silicon particles is reduced and the cycle characteristics are good, but a large charge / discharge capacity cannot be obtained. The diameter of silicon or silicon oxide 31 is preferably 0.3 nm or more and 30 nm or less. This is because silicon or silicon oxide 31 having such a diameter can be included in the central portion of the carbon nanohorn aggregate 21.

  Further, the silicon or silicon oxide 31 is included in the carbon nanohorn aggregate 21 having the opening 211. Here, the inclusion means a state where silicon or silicon oxide 31 is fixed inside the carbon nanohorn aggregate 21 or a state surrounded by the carbon nanohorn aggregate 21.

FIG. 4 shows a mechanism for inserting and desorbing lithium ions into silicon or silicon oxide 31 included in the composite 10 of silicon or silicon oxide and a carbon nanohorn aggregate having such a configuration. FIG. 4A shows a composite 10 of silicon or silicon oxide and a carbon nanohorn aggregate according to the first embodiment before occlusion of lithium ions.

As shown in FIG. 4B, when lithium ions are inserted into silicon or silicon oxide 31, silicon or silicon oxide 31 becomes a lithium compound 32 and expands. At this time, since the carbon nanohorn 212 is a one-dimensional structure, the lithium compound 32, as shown in FIG. 4 (b), to expand within the range surrounded by the carbon nanohorn 212, silicon or silicon oxide and the carbon nanohorn aggregate composite 10 itself volume and does not change. That is, the carbon nanohorn aggregate 21 serves as a template for expanding silicon or silicon oxide 31 (hereinafter referred to as a template effect).

  And as shown in FIG.4 (c), in the case of detachment | desorption of lithium ion, carbon nanohorn and the lithium compound 32 return to the shape before lithium ion insertion.

  With the above mechanism, the carbon nanohorn aggregate 21 exhibits a template effect that can reduce deterioration due to volume change of silicon or silicon oxide 31, and therefore, it is possible to alleviate the volume change of silicon accompanying lithium ion insertion / extraction. .

  (Second Embodiment) An electrode material of a lithium ion secondary battery including a composite of silicon or silicon oxide and carbon nanohorn according to a second embodiment of the present invention and a lithium ion secondary battery using the same will be described. To do. The constituent elements in the present embodiment are the same as the constituent elements of the first embodiment and the numbers shown in FIGS.

The lithium ion secondary battery according to the second embodiment includes a negative electrode obtained by applying a negative electrode material including a composite 10 of silicon or silicon oxide and a carbon nanohorn aggregate according to the first embodiment to a negative electrode current collector. And a positive electrode obtained by applying a positive electrode material to a positive electrode current collector, a separator, and an electrolyte.

The lithium ion secondary battery according to the second embodiment includes a negative electrode obtained by applying a negative electrode material including a composite 10 of silicon or silicon oxide and a carbon nanohorn aggregate according to the first embodiment to a negative electrode current collector. And a positive electrode obtained by applying a positive electrode material to a positive electrode current collector, a separator, and an electrolyte.

  A known lithium-containing transition metal oxide can be used as the positive electrode material. Specifically, LiCoO2, LiNiO2, LiMn2O4, LiFePO4, LiFeSiO4, LiFeBO3, Li3V2 (PO4) 3, Li2FeP2O7, and the like can be given.

  As the electrolyte, for example, a non-aqueous solution containing a lithium salt such as LiPF6, LiClO4, LiBF4, LiAlO4, LiAlCl4, LiSbF6, LiSCN, LiCl, LiCF3SO3 is used, and one or a mixture of two or more types may be used. I can do it.

As the nonaqueous solvent for the electrolyte, one or two or more of propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and the like are used in combination.
In the lithium ion secondary battery having the above-described configuration, the carbon nanohorn aggregate 21 exhibits a template effect that can reduce deterioration due to volume change of silicon or silicon oxide 31. Since the volume change of silicon or silicon oxide accompanying lithium ion insertion / extraction can be relaxed, cracks can be generated on the negative electrode surface, and the active material and electrodes can be prevented from peeling off. The effect that the charge / discharge cycle characteristics are reduced can be achieved.

  Furthermore, since the carbon nanohorn aggregate 21 having the apertures 211 has a low resistance, there is an effect that there is little loss due to charge / discharge resistance. FIG. 5 is a schematic view showing the movement of electrons in the negative electrode of the lithium ion secondary battery according to the second embodiment. FIG. 5 (a) shows a state before or after charging, and FIG. Show. In addition, this schematic diagram expresses silicon or silicon oxide 31 and lithium compound 32 that are transmitted through the carbon nanohorn aggregate 21 and included in the carbon nanohorn aggregate 21.

Since the carbon nanohorn aggregate 21 has a low resistance, there is little loss due to resistance with the negative electrode current collector 51. In addition, as represented by an arrow indicating the movement trajectory of the electrons 41 at the time of charging in FIG. 5B, the electrons at the time of insertion / extraction of lithium ions are negative electrode current collectors 51 via carbon nanohorns. Therefore, there is little loss due to resistance. Since the composite 10 of silicon or silicon oxide and carbon nanohorn aggregates according to the first embodiment of the present invention has little loss due to resistance, it does not impair the high ion storage capability of silicon and has a high capacity lithium. An ion secondary battery can be realized. In addition, since there is little loss due to resistance, rate characteristics (C rate: discharge to a predetermined voltage in 1 hour is assumed to be 1C) and a lithium ion secondary battery capable of rapid charge / discharge are realized. Can do.

As described above, the volume change of the silicon or silicon oxide 31 can be achieved by using the composite 10 of the silicon or silicon oxide and the carbon nanohorn aggregate according to the first embodiment as the electrode material of the lithium ion secondary battery. Can be provided, and a lithium ion secondary battery having excellent cycle characteristics can be provided. At the same time, since high conductivity can be imparted, it is possible to provide an electrode material for a lithium ion secondary battery that has high capacity, excellent rate characteristics, and can be rapidly charged and discharged, and a lithium ion secondary battery using the same. .

  In addition, since the diameter of the carbon nanohorn aggregate 21 containing silicon or silicon oxide 31 is 30 nm or more and 200 nm or less, when mixed with another active material, it is possible to enter the gap between them. The composite 10 of silicon or silicon oxide and carbon nanohorn of the present application can be used not only as a negative electrode active material but also as a conductive auxiliary material that can be charged and discharged, and the resistance of the electrode can be reduced without a conductive material. is there.

(Third Embodiment) With reference to FIG. 6, a method for producing a composite of silicon or silicon oxide and a carbon nanohorn aggregate according to a third embodiment of the present invention will be described. The constituent elements in this embodiment and the numbers described in FIG. 6 are the same as the constituent elements in the first and second embodiments and the numbers shown in FIGS. This schematic diagram represents the silicon or silicon oxide 31 and the silicon or silicon oxide precursor 33 contained in the carbon nanohorn aggregate 21 through the carbon nanohorn aggregate 21.

  First, as shown in FIG. 6A, a carbon nanohorn aggregate 21 having a shape in which a plurality of carbon nanohorns 212 are aggregated in a spherical shape is prepared. Next, as shown in FIG. 6B, the carbon nanohorn aggregate 21 is oxidized to preferentially oxidize the five-membered ring and the seven-membered ring of the carbon nanohorn 212, thereby providing the opening 211. . Thereby, the carbon nanohorn aggregate 21 having the opening 211 is obtained.

  The fine pores in the carbon nanohorn can be controlled in size depending on various oxidation conditions. In oxidation by heat treatment in an oxygen atmosphere, the diameter of the opening 211 can be controlled by changing the oxidation treatment temperature, and the opening 211 having a diameter of 0.3 to 5 nm can be provided at 350 to 550 ° C. Further, as disclosed in Japanese Patent Application Laid-Open No. 2003-95624, the opening 211 can be provided by treatment with acid or the like. In the case of a nitric acid solution, it is possible to provide an opening 211 of 1 nm at 110 ° C. for 15 minutes, and in the case of hydrogen peroxide, an opening 211 of 1 nm can be provided at 100 ° C. for 2 hours.

  Next, silicon or silicon oxide precursor 33 is prepared, and carbon nanohorn aggregate 21 having silicon or silicon oxide precursor 33 and opening 211 is mixed in a liquid phase atmosphere. As shown in FIG. 6C, the silicon or silicon oxide precursor 33 is adsorbed inside the energetically stable carbon nanohorn aggregate 21. At this time, the silicon or silicon oxide precursor 33 is also preferentially adsorbed in the gap between the carbon nanohorn 212 and the carbon nanohorn 212.

  Adsorption of the silicon precursor to the apertured carbon nanohorn aggregate 21 can be performed by a conventional loading method such as a concentration-drying method or an impregnation method after mixing both in a liquid phase. At this time, any dispersion solvent such as an aqueous solvent or an organic solvent solvent can be used, but hexane, methanol, ethanol, acetonitrile, benzene, toluene and the like are more preferable. In the gas phase, the silicon or silicon oxide precursor 33 is adsorbed inside the carbon nanohorn aggregate 21 by heating in a vacuum or an inert gas atmosphere.

  Thereafter, as shown in FIG. 6 (d), the inclusion is reduced in an inert atmosphere in the region of 100 ° C. or higher and 1800 ° C. or lower in a hydrogen atmosphere at a high temperature (hereinafter referred to as “heat treatment”). As a result, the silicon or silicon oxide precursor 33 is changed to silicon or silicon oxide 31 and deposited inside the carbon nanohorn aggregate 21.

  The heat treatment can be performed in a vacuum, an inert gas, hydrogen, or a combination thereof. In this case, the temperature of the heat treatment is preferably performed in the range of 100 ° C. to 1800 ° C. This is because if the temperature is lower than 100 ° C., crystallization of the silicon or silicon oxide precursor 33 does not proceed, and if the temperature is higher than 1800 ° C., the carbon nanohorn 212 starts to fuse. More preferably, it can be performed in the range of 100 to 1200 ° C. This is because when the temperature reaches around 1200 ° C., the aperture 211 of the carbon nanohorn 212 shrinks.

  Through the above steps, the composite 10 of silicon or silicon oxide and carbon nanohorn of the present invention is completed.

  The details of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Example 1]
1. Production of composite of silicon or silicon oxide and carbon nanohorn aggregate (1-1) Preparation of carbon nanohorn aggregate CO ₂ laser under conditions of laser power density (30 kW / cm ² ) and target rotation speed (2 rpm) Carbon nanohorn aggregates were synthesized by an ablation method. The synthesis atmosphere was room temperature and Ar. As a result of observing the obtained sample with an electron microscope, it was found that carbon nanohorns having a diameter of 2 nm or more and 5 nm or less aggregated to form an aggregate of about 30 nm or more and 200 nm or less.

(1-2) Opening treatment of carbon nanohorn aggregates Subsequently, the carbon nanohorn aggregates were subjected to opening treatment. The temperature was raised to 550 ° C. at 1 ° C./min in dry air, and then allowed to cool naturally. At this time, the gas flow rate was 200 ml / min.

(1-3) Mixing of silicon precursors Next, tetraethoxysilane ((C2H5O) 4Si) (100 ml) and carbon nanohorn aggregates (100 mg) having pores obtained in (1-2) were added in 30 ml of ethanol solution. And stirred at room temperature for about 12 hours. Then, after filtering once using a filter, it vacuum-dried for 24 hours and evaporated and removed the solvent etc. which were contained.

(1-4) The carbon nanohorn aggregate containing the silicon or silicon oxide precursor obtained in the heat treatment (1-3) is placed in a mixed gas atmosphere of hydrogen and Ar (hydrogen: Ar = 50 ml: 200 ml). Then, it was heated at 650 ° C. for 1 hour, and the silicon or silicon oxide precursor was changed to silicon or silicon oxide and deposited inside the carbon nanohorn aggregate.

(1-5) a complex of an aggregate of silicon or silicon oxide and carbon nanohorn obtained in the complex or more steps of the silicon or silicon oxide and the carbon nanohorn aggregate in Example 1 (hereinafter SiOx-CNHox FIG. 7 shows a scanning transmission electron microscope (STEM) image. Here, FIG. 8 shows the result of analyzing the region of the solid line in the figure by energy dispersive X-ray analysis (EDX). Since the apertured carbon nanohorn aggregate is spherical, the center of the carbon peak is largely detected. Moreover, since the peaks of Si and O also increased toward the center, it was found that silicon oxide was taken into the open nanohorn. Further, it was found that Si and O exist adjacent to each other because the peak shapes are similar.

2. Production of lithium ion secondary battery (2-1) Production of negative electrode material 5 wt% of SiOx-CNHox produced by the above production method, 15 wt% of polyimide to 75 wt% of negative electrode material of SiO, and further N-methyl-2-pyrrolidinone Were mixed well and a paste was prepared. Here, SiO used was a material whose surface was coated with carbon after heat treatment at 1000 ° C. in Ar.

(2-2) Preparation of Negative Electrode The paste obtained in (2-1) was applied to a copper foil for a current collector with a thickness of 50 μm. Then, after drying at 120 degreeC for 1 hour, the electrode was pressure-molded with the roller press. Further, this electrode was fired at 350 ° C. for 1 hour in a nitrogen atmosphere, punched out to 2 cm ² and used as a negative electrode.

(2-3) Preparation of counter electrode Li foil was used as a counter electrode.

(2-4) Preparation of Electrolytic Solution As an electrolytic solution, LiPF6 was mixed at a volume ratio of 3: 7 with 3: 7 ethylene carbonate and diethyl carbonate.

(2-5) Preparation of Separator A 30 μm polyethylene porous film was used as the separator.

(2-6) Production of Lithium Ion Secondary Battery A lithium ion secondary battery cell for evaluation was produced using the negative electrode, counter electrode, electrolytic solution, and separator prepared or prepared by the above production method.

[Comparative Example 1]
A lithium ion secondary battery cell for evaluation was produced in the same manner as in Example 1 except that only SiO was used without including SiOx-CNHox as the paste.

(Experiment 1)
The following experiment was conducted using the lithium ion secondary battery cells for evaluation prepared by the methods of Example 1 and Comparative Example 1 obtained as described above.

  The lithium ion secondary battery cells of Example 1 and Comparative Example 1 obtained by the above manufacturing method are set in a charge / discharge tester, and the voltage reaches 0.02 V at a constant current of charge density of 0.5 mA / cm2. Charging was performed, and charging was performed by reducing the current in a state of 0.02V. The charging was terminated when the current value reached 60 μA / cm 2. Then, it was performed at a constant current with a current density of 0.5 mA / cm 2 and finished when the cell voltage reached 2.0V. This process was repeated 50 cycles, and cycle characteristics were obtained.

  Moreover, the lithium ion secondary battery cell of Example 1 obtained by said manufacturing method and the comparative example 1 was set to a charging / discharging test machine, and 1C (1C: electric current value which can fully charge / discharge a battery in 1 hour) A value (rate characteristic) of discharge capacity (mAh) /0.2C discharge capacity (mAh) × 100 was determined.

(Result 1)
The above experimental results are shown in Table 1.

  The initial charge capacities of Example 1 and Comparative Example 1 were 2300 mA / g and 2200 mA / g, respectively, and the initial discharge capacities were 1600 mA / g and 1400 mA / g, respectively. The initial charge and discharge efficiencies were about 70% and 65%, respectively, and Example 1 to which SiOx-CNHox was added showed better battery characteristics than Comparative Example 1 that was not added. This is considered to be the result of the increase in capacity due to silicon inside the carbon nanohorn.

  Further, the capacity retention ratios after 50 cycles were 85% in the case of Example 1 and 75% in the case of Comparative Example 1, respectively. This is thought to be due to the fact that SiOx-CNHox itself is less deteriorated and the size of SiOx-CNHox is 50-200 nm, so that the effect of volume expansion and contraction is mitigated by filling the gap between SiO. .

  Moreover, as a result of comparing the rate characteristics, it was found that Example 1 to which SiOx-CNHox was added was improved by 5% compared to Comparative Example 1 to which SiO was added. These results are thought to be due to the fact that carbon nanohorns are good conductors, so that the resistance between active materials has decreased and the diffusion resistance of Li ions has decreased.

[Example 2]
A lithium ion secondary battery cell for evaluation was produced in the same manner as in Example 1 except that a paste was prepared by mixing 5 wt% SiOx-CNHox with graphite.

[Comparative Example 2]
A lithium ion secondary battery cell for evaluation was prepared in the same manner as in Example 1 except that 5 wt% of carbon nanohorn was mixed with graphite to prepare a paste.

[Comparative Example 3]
A lithium ion secondary battery cell for evaluation was produced in the same manner as in Example 1 except that 5 wt% acetylene black was mixed with graphite to produce a paste.

[Comparative Example 4]
A lithium ion secondary battery cell for evaluation was produced in the same manner as in Example 1 except that 5 wt% ketjen black was mixed with graphite to produce a paste.

[Comparative Example 5]
A lithium ion secondary battery cell for evaluation was produced in the same manner as in Example 1 except that 5 wt% of carbon nanotubes were mixed with graphite to produce a paste.

[Comparative Example 6]
A lithium ion secondary battery cell for evaluation was produced in the same manner as in Example 1 except that 5 wt% carbon fiber was mixed with graphite to produce a paste.

(Experiment 2)
Experiments similar to Experiment 1 were performed using the evaluation lithium ion secondary battery cells prepared by the methods of Example 2 and Comparative Examples 2 to 6 obtained as described above.

(Result 2)
It was found that the initial charge capacity of Example 2 increased by 5% with respect to any of Comparative Examples 1-6. Moreover, it turned out that the structure of Comparative Examples 2-6 does not have big influence on a capacity | capacitance.
Further, the capacity retention ratio after 50 cycles showed a high capacity retention ratio of 95% in the case of Example 2. This is considered to be because carbon nanohorns not only have high conductivity but also high dispersibility, and thus acted to fill gaps between graphite particles.

DESCRIPTION OF SYMBOLS 10 Composite of silicon or silicon oxide and carbon nanohorn aggregate 21 Carbon nanohorn aggregate 211 Opening 212 Carbon nanohorn 31 Silicon or silicon oxide 32 Lithium compound 33 Silicon or silicon oxide precursor 41 Electron 51 Current collector

Claims (9)

An assembly of carbon nanohorns having pores;
Silicon or silicon oxide and (SiOx (0 <x ≦ 2 )), includes at least a, the silicon or silicon oxide mosquitoes over carbon nanohorn is encapsulated in a complex with the carbon nanohorn aggregates aggregated spherically lithium A composite of silicon or silicon oxide and an assembly of carbon nanohorns for an electrode material of an ion secondary battery. The diameter of the silicon or silicon oxide is 0.3nm or 30nm or less, silicon or silicon oxide and a complex of the carbon nanohorn aggregate of electrode material of a lithium ion secondary battery according to claim 1. Furthermore, silicon, silicon oxide (SiOx (0 <x ≦ 2)), carbon, silicon coated with carbon, or silicon oxide (SiOx (0 <x ≦ 2)) is included. 3. A composite of silicon or silicon oxide for an electrode material of a lithium ion secondary battery according to 2 and a carbon nanohorn aggregate . The lithium ion secondary battery according to claim 3, wherein the carbon includes at least one of graphite, hard carbon, soft carbon, acetylene black, ketjen black, carbon fiber, carbon nanotube, carbon nanohorn, and graphene sheet. A composite of silicon or silicon oxide and carbon nanohorn aggregate for the electrode material. An electrode having a composite comprising carbon nanohorn aggregates having carbon nanospheres aggregated in a spherical shape and having pores and silicon or silicon oxide (SiOx (0 <x ≦ 2)) included in the carbon nanohorn aggregates;
A separator;
And a lithium ion secondary battery.   The lithium ion secondary battery according to claim 5, wherein a diameter of the silicon or silicon oxide is 0.3 nm or more and 30 nm or less. The electrode further includes any one of silicon, silicon oxide (SiOx (0 <x ≦ 2)), carbon, silicon covered with carbon, or silicon oxide (SiOx (0 <x ≦ 2)). The lithium ion secondary battery according to claim 5 or 6.   The lithium ion secondary battery according to claim 7, wherein the carbon includes at least one of graphite, hard carbon, soft carbon, acetylene black, ketjen black, carbon fiber, carbon nanotube, carbon nanohorn, and graphene sheet. . A step of mixing a carbon nanohorn aggregate having an opening and a silicon or silicon oxide precursor under a liquid phase atmosphere;
Heating the mixed carbon nanohorn aggregate and the silicon or silicon oxide precursor in a vacuum or an inert gas atmosphere to encapsulate the silicon or silicon oxide precursor in the carbon nanohorn aggregate; and
Heating the carbon nanohorn aggregate containing the silicon or silicon oxide precursor at 100 ° C. or higher and 1800 ° C. or lower in an inert or hydrogen atmosphere in a vacuum, for an electrode material of a lithium ion secondary battery A method for producing a composite of silicon or silicon oxide and a carbon nanohorn aggregate .

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