WO2010150859A1 - マクロ多孔性グラファイト電極材とその製造方法、及びリチウムイオン二次電池 - Google Patents
マクロ多孔性グラファイト電極材とその製造方法、及びリチウムイオン二次電池 Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Definitions
- the present invention mainly relates to a macroporous graphite electrode material used for a negative electrode active material of a lithium ion secondary battery, a manufacturing method thereof, and a lithium ion secondary battery.
- Lithium ion secondary batteries have high energy density and are widely used as power sources for small electronic devices such as mobile phones and laptop computers. In recent years, in order to apply to electric power sources for electric vehicles, further higher output is desired. Graphite (graphite) is used as a main negative electrode material for lithium ion secondary batteries currently in use, but further improvement is necessary to achieve higher output.
- Patent Documents 1 and 2 As a method for artificially obtaining graphite, a method of heat-treating a soft carbon raw material such as pitch at 2500 ° C. or higher is generally used, and energy consumption is large. In recent years, a method of obtaining at a relatively low temperature from a reaction between a catalyst and carbon has also been developed (Patent Documents 1 and 2).
- JP 2008-66503 A WO2006 / 118120 (Japanese Patent Application No. 2007-514951)
- the present invention provides a macroporous graphite electrode material that can be manufactured at a low temperature of 1500 ° C. or less and that can be charged and discharged at high speed, and a method for manufacturing the same. Moreover, the lithium ion secondary battery using the macroporous graphite electrode material is provided.
- the macroporous graphite electrode material of the present invention is graphitized at a heat treatment temperature of 1500 ° C. or less, and is a porous material in which macropores are three-dimensionally connected. It has a structure, and its pore wall is composed of a macroporous body composed of graphitic carbon.
- the ratio of the specific surface area of the micropores to the total specific surface area is 0 or more and 0.74 or less, and the area ratio (D / G area ratio) of the D band and G band in the Raman spectrum is 0 or more and 1.33 or less. is there.
- macropores indicate pores having a diameter of 50 nm or more
- micropores indicate pores having a diameter of 2 nm or less.
- the charge / discharge capacity can be improved and high-speed charge / discharge can be achieved.
- the manufacturing method of the macroporous graphite electrode material of this invention has the following process. First, a step of preparing a mold made of SiO 2 particles, a step of mixing the mold into a carbon source solution, a step of converting the carbon source into a resin to form a composite of a carbon precursor resin and a mold, and removing the mold And a step of forming the macroporous carbon and a step of supporting the catalyst on the macroporous carbon. And it has the process of graphitizing by heat-processing the macroporous carbon which carry
- the carbon precursor resin refers to a state in which a carbon source is polymerized into a polymer solid.
- the manufacturing method of the macroporous graphite electrode material of this invention has the following process. First, a step of preparing a mold made of SiO 2 particles, a step of preparing a carbon source solution to which a catalyst has been added, a step of mixing the template into the carbon source solution, a carbon source resinized, and a carbon precursor resin Forming a template complex. Then, the carbon precursor resin / template complex is graphitized by heat treatment at a heat treatment temperature of 900 ° C. or more and 1500 ° C. or less to form a graphite / template complex, and the graphite / template complex is converted into a mold. And removing the catalyst.
- graphitization can be performed at a somewhat low heat treatment temperature of 900 ° C. or more and 1500 ° C. or less due to the effect of the catalyst, so that energy during production can be reduced. Further, the charge / discharge capacity is improved, and a macroporous graphite electrode material capable of high-speed charge / discharge is obtained.
- the lithium ion secondary battery of the present invention is composed of a positive electrode member, a negative electrode member, and a non-aqueous electrolyte.
- the positive electrode member includes a lithium transition metal composite compound capable of reversibly occluding and releasing lithium ions as a positive electrode active material.
- the negative electrode member is made of the macroporous graphite electrode material of the present invention described above, and has a negative electrode active material that absorbs and releases lithium ions at a lower potential than the positive electrode active material.
- the non-aqueous electrolyte is configured such that a lithium salt is dissolved in a non-aqueous solvent solution.
- a macroporous graphite electrode material and a lithium ion secondary battery capable of reducing energy during production and capable of high-speed charge / discharge.
- a to H are process diagrams showing a method (part 1) for producing a macroporous graphite electrode material according to a first embodiment of the present invention.
- a to E are process diagrams showing a method (part 2) for producing a macroporous graphite electrode material according to the first embodiment of the present invention.
- 2 is an X-ray diffraction (XRD) pattern of Sample 1, Sample 2, and Sample 3.
- FIG. It is an X-ray diffraction pattern of Sample 1, Sample 4, and Sample 5.
- It is an X-ray diffraction pattern of Sample 14 and Sample 17.
- 3 is an X-ray diffraction pattern of Samples 7 to 13.
- a macroporous carbon obtained by removing a mold after heat-treating a composite of a carbon resin and a mold made of SiO 2 particles having an average particle diameter of 450 nm at 400 ° C. It is a TEM photograph of.
- a and B are a TEM photograph of Sample 6 produced by graphitization at a heat treatment temperature of 1000 ° C., and a TEM photograph in which a part (pore wall portion) of Sample 6 is enlarged.
- A, B TEM photograph of sample 12 produced by graphitization at a heat treatment temperature of 1400 ° C.
- FIG. 3 is a diagram showing a charge / discharge curve of Sample 2 produced according to Example 1.
- FIG. 4 is a diagram showing a charge / discharge curve of Sample 3 produced in Example 1.
- FIG. 3 is a diagram showing a charge / discharge curve of Sample 4 produced according to Example 1.
- FIG. 5 is a diagram showing a charge / discharge curve of Sample 5 produced according to Example 1.
- FIG. 3 is a diagram showing a charge / discharge curve of Sample 6 produced according to Example 1.
- FIG. 3 is a diagram showing a charge / discharge curve of a sample 7 produced according to Example 1. It is the figure which showed the charging / discharging curve of the sample 17 produced by the comparative example. It is the figure which showed the charging / discharging curve of the sample 4, the sample 14, the sample 15, the sample 16, and the sample 18 in the current density of 37.2 mA / g. It is the figure which showed the charging / discharging curve of the sample 10, the sample 12, the sample 13, the sample 19, and the sample 20 in the current density of 37.2 mA / g. The rate characteristics of Sample 4, Sample 6, Sample 7, Sample 14, Sample 15, and artificial graphite are shown.
- the rate characteristics of Sample 4, Sample 6, Sample 7, Sample 14, Sample 15, and artificial graphite are shown.
- the rate characteristics (discharge capacity up to 3 V) of Sample 11, Sample 12, Sample 13, Sample 20, and artificial graphite are shown.
- the rate characteristics (discharge capacity up to 0.5 V) of Sample 11, Sample 12, Sample 13, Sample 20, and artificial graphite are shown.
- the rate characteristics (discharge capacity up to 3 V) of Sample 3, Sample 4, Sample 5, and Sample 20 are shown.
- the rate characteristics (discharge capacity up to 0.5 V) of Sample 3, Sample 4, Sample 5, and Sample 20 are shown. It is the figure which showed the cycle characteristic in the current density of the sample 11 37.2mA / g. It is a schematic block diagram of the lithium ion secondary battery which concerns on the 2nd Embodiment of this invention.
- the macroporous graphite electrode material of this embodiment example has a porous structure in which macropores are three-dimensionally connected, and the pore walls are composed of a macroporous body composed of graphitic carbon.
- the total specific surface area is larger than 69 m 2 g ⁇ 1
- the ratio of the specific surface area of the micropores to the total specific surface area is 0 or more and 0.74 or less
- the area ratio between the D band and G band of the Raman spectrum ( D / G area ratio) is 0 or more and 1.33 or less.
- the micropore indicates a pore having a diameter of 2 nm or less.
- the ratio of the specific surface area of the micropores to the total specific surface area decreases.
- the D / G area ratio also indicates the progress of graphitization. For this reason, when the D / G area ratio is larger than 1.33, graphitization is not sufficient, good conductivity cannot be obtained, and charge / discharge capacity at a low potential cannot be obtained. Thereby, it is preferable that D / G area ratio is 0 or more and 1.33 or less.
- SiO 2 silicon oxide
- SiO 2 opal 1 A SiO 2 particle aggregate (hereinafter, SiO 2 opal 1) composed of SiO 2 particles is obtained.
- This SiO 2 opal 1 serves as a mold in this embodiment, and is composed of an aggregate of a plurality of SiO 2 particles.
- a mixed solution in which phenol and formaldehyde are mixed at a molar ratio of 1: 0.85 is prepared, and a small amount of hydrochloric acid is added to the mixed solution to prepare a carbon source solution.
- the dried SiO 2 opal 1 is immersed in the carbon source solution 2 for 12 hours. Thereafter, the SiO 2 opal 1 immersed in the carbon source solution 2 is filtered, and heat treatment is performed at 128 ° C. for 12 hours to remove moisture and the like, and the carbon source is converted into a resin. As shown in FIG. A composite 3 of SiO 2 particles 1 is prepared.
- the phenol resin corresponds to the carbon precursor resin of the present invention.
- the composite 3 of the phenol resin and the SiO 2 opal 1 is heat-treated at 400 ° C. for 5 hours in an argon atmosphere, whereby the phenol resin is carbonized. As shown in FIG. 1D, the carbon and the SiO 2 opal 1 The complex 4 is obtained.
- the SiO 2 opal 1 is removed by wet etching using an HF (hydrogen fluoride) aqueous solution.
- HF hydrogen fluoride
- the macroporous carbon 5 is immersed in a methanol solution of nickel nitrate (II) for 1 hour.
- the concentration of nickel nitrate is preferably 3 mmol or more and 15 mmol or less with respect to 1 g of macroporous carbon.
- the macroporous carbon is dried at about 100 ° C. to adjust the macroporous carbon 5 carrying nickel nitrate 7 as shown in FIG. 1F. This nickel nitrate 7 is used as a catalyst and is removed in a later step.
- the macroporous carbon 5 carrying nickel nitrate 7 is heat-treated in an argon atmosphere for 3 hours to graphitize the macroporous carbon 5, thereby obtaining graphitized porous carbon 8 as shown in FIG. 1G.
- the heat treatment temperature Tc at this time is 900 ° C. ⁇ Tc ⁇ 1500 ° C.
- the macroporous carbon 5 is graphitized at a heat treatment temperature of 900 ° C. ⁇ Tc ⁇ 1500 ° C.
- the nickel nitrate 7 which is a catalyst supported on the graphitized porous carbon 8 is eluted with, for example, 10% hydrochloric acid.
- the macroporous graphite electrode material 9 having a porous structure in which the macropores are three-dimensionally connected and having a pore wall made of graphitic carbon is completed.
- the pores 6 are formed using a mold (SiO 2 opal 1) made of SiO 2 particles, but the macroporous graphite electrode material 9 finally obtained depending on the size of the particles used for the mold.
- the diameter of the pores 6 can be controlled, and the specific surface area is thereby controlled.
- the particle size referred to here is the size of one SiO 2 particle. That is, the template per pore is SiO 2 particles, and the template of the entire porous structure is SiO 2 opal.
- the specific surface area can be optimally adjusted by adjusting the average particle diameter of the SiO 2 particles constituting the SiO 2 opal 1 between 100 nm and 450 nm.
- the phenol resin is carbonized, but this carbonization step may be omitted.
- the carbonization step is omitted, the carbonization and the graphitization proceed simultaneously or sequentially in the next heat treatment step.
- the heat treatment temperature for graphitization can be set to 900 ° C. ⁇ Tc ⁇ 1500 ° C. due to the effect of the catalyst.
- a colloidal solution containing silicon oxide (SiO 2 ) having an average particle size of 100 nm or more and 450 nm or less is centrifuged, and then dried under reduced pressure, whereby SiO 2 serving as a template made of SiO 2 particles is obtained as shown in FIG. 2A.
- SiO 2 silicon oxide
- a mixed solution in which phenol and formaldehyde are mixed at a molar ratio of 1: 0.85 is prepared, a small amount of hydrochloric acid is added to this mixed solution, and nickel nitrate as a catalyst is added to a predetermined concentration.
- a carbon source solution containing a catalyst is prepared. The concentration of nickel nitrate is set so that the nickel nitrate becomes 3 mmol / g-C or more and 15 mmol / g-C when the carbon source is baked in the subsequent step.
- the dried SiO 2 opal 10 is immersed in the carbon source solution 11 for 12 hours. Thereafter, the SiO 2 opal 10 immersed in the carbon source solution 11 is filtered, and heat treatment is performed at 128 ° C. for 12 hours to remove moisture and the like, and the carbon source is converted into a resin. As shown in FIG. A composite 12 of SiO 2 opal 10 and nickel nitrate is produced.
- the composite 12 of phenol resin, SiO 2 opal 10 and nickel nitrate is heat-treated in an argon atmosphere for 3 hours, and the phenol resin is graphitized simultaneously with carbonization, thereby graphitizing as shown in FIG. 2D.
- a composite 13 of carbon, SiO 2 opal 10 and nickel nitrate is obtained.
- the heat treatment temperature Tc at this time is 900 ° C. ⁇ Tc ⁇ 1500 ° C.
- the phenol resin is carbonized and graphitized at the heat treatment temperature of 900 ° C. ⁇ Tc ⁇ 1500 ° C.
- the SiO 2 opal 10 is removed by wet etching using an HF aqueous solution, and Ni is removed. As a result, the pores 15 are formed in the portion where the SiO 2 opal 10 as the mold is removed, and the macroporous graphite electrode material 14 is completed.
- pores 15 with template (SiO 2 opal 10) made of SiO 2 particles, macroporous finally obtained by the size of the particles used in the mold of graphite electrode materials 14
- the diameter of the pores 15 can be controlled, and the specific surface area is thereby controlled.
- the specific surface area can be optimally adjusted by adjusting the SiO 2 opal 10 serving as a mold between 100 nm and 450 nm.
- the total specific surface area, the ratio of the specific surface area of the micropores to the total specific surface area, and the D / G area ratio are suitably formed.
- a porous graphite electrode material is obtained. Further, in the above manufacturing method (part 2), since the catalyst is mixed in advance with the carbon source, the number of steps can be reduced as compared with the manufacturing method (part 1).
- Part 1 and Part 2 phenol / formaldehyde is used as the carbon source.
- resorcinol / formaldehyde, furfuryl alcohol, polyimide, pitch, and the like can be used.
- nickel nitrate is used as the catalyst.
- nickel, iron, cobalt metal salts (nitrate, acetate, chloride) and complexes (Acelacetone) Complex etc.) can be applied.
- the heat treatment temperature necessary for graphitization can be set to a relatively low temperature of 900 ° C. ⁇ Tc ⁇ 1500 due to the effect of the catalyst.
- Example 1 the sample used as a macroporous graphite electrode material was produced using the manufacturing method (the 1) mentioned above.
- a colloidal solution containing silicon oxide (SiO 2 ) having an average particle diameter of 190 nm was centrifuged, and then dried under reduced pressure, thereby producing a SiO 2 opal as a template made of SiO 2 particles.
- a mixed solution in which phenol and formaldehyde were mixed at a molar ratio of 1: 0.85 was prepared, and a small amount of hydrochloric acid was added to this mixed solution to prepare a carbon source solution.
- the dried SiO 2 opal was immersed in a carbon source for 12 hours. Thereafter, the SiO 2 opal immersed in the carbon source solution was filtered, and heat treatment was performed at 128 ° C. for 12 hours to remove moisture and the like, thereby converting the carbon source into a resin, thereby producing a composite of a phenol resin and SiO 2 particles.
- the composite of phenol resin and SiO 2 opal was heat-treated at 400 ° C. for 5 hours in an argon atmosphere to obtain a composite of carbon and SiO 2 opal.
- the SiO 2 opal was removed by wet etching using an HF aqueous solution to obtain macroporous carbon.
- the macroporous carbon was immersed in a methanol solution of nickel (II) nitrate for 1 hour.
- the concentration of nickel nitrate was 3 mmol with respect to 1 g of macroporous carbon.
- the macroporous carbon was dried at 100 ° C. to prepare a macroporous carbon carrying nickel nitrate.
- porous carbon carrying nickel nitrate was heat-treated in an argon atmosphere at a heat treatment temperature of 900 ° C. for 3 hours to graphitize the macroporous carbon, thereby obtaining macroporous graphite.
- Example 2 the concentration of nickel nitrate was 9 mmol with respect to 1 g of macroporous carbon, and the heat treatment temperature in graphitization was 900 ° C., thereby obtaining Sample 2.
- Example 3 the concentration of nickel nitrate was set to 15 mmol with respect to 1 g of macroporous carbon, and the heat treatment temperature in graphitization was set to 900 ° C. to obtain Sample 3.
- Sample 4 was obtained by setting the heat treatment temperature in graphitization to 1000 ° C.
- Sample 5 was obtained by setting the heat treatment temperature in graphitization to 1500 ° C.
- SiO 2 particles constituting the SiO 2 opal as a template using the SiO 2 particles having an average particle diameter of 450 nm, by the heat treatment temperature in graphitization and 1000 ° C., the sample 6 Obtained.
- Example 1 SiO 2 opal composed of SiO 2 particles with an average particle diameter of 450 nm was used as a template, the concentration of nickel nitrate was 15 mmol with respect to 1 g of macroporous carbon, and the heat treatment temperature in graphitization was 1000 Sample 7 was obtained by adjusting the temperature to 0 ° C.
- Sample 8 was obtained by using SiO 2 particles having an average particle diameter of 450 nm as particles constituting the template and setting the concentration of nickel nitrate to 15 mmol with respect to 1 g of macroporous carbon.
- Example 1 SiO 2 particles having an average particle diameter of 450 nm were used as the particles constituting the template, the concentration of nickel nitrate was 15 mmol with respect to 1 g of macroporous carbon, and the heat treatment temperature in graphitization was 1100 ° C. A sample 9 was obtained.
- Example 1 SiO 2 particles having an average particle diameter of 450 nm were used as particles constituting the template, the concentration of nickel nitrate was 15 mmol with respect to 1 g of macroporous carbon, and the heat treatment temperature in graphitization was 1200 ° C. Thus, Sample 10 was obtained.
- Example 1 SiO 2 particles having an average particle diameter of 450 nm were used as the particles constituting the template, the concentration of nickel nitrate was 15 mmol with respect to 1 g of macroporous carbon, and the heat treatment temperature in graphitization was 1300 ° C. Thus, a sample 11 was obtained.
- Example 1 SiO 2 particles having an average particle diameter of 450 nm were used as particles constituting the template, the concentration of nickel nitrate was 15 mmol with respect to 1 g of macroporous carbon, and the heat treatment temperature in graphitization was 1400 ° C. Thus, a sample 12 was obtained.
- Example 1 SiO 2 particles having an average particle diameter of 450 nm were used as particles constituting the template, the concentration of nickel nitrate was 15 mmol with respect to 1 g of macroporous carbon, and the heat treatment temperature in graphitization was 1500 ° C. Thus, a sample 14 was obtained.
- Example 2 a sample to be a macroporous graphite electrode material was produced using the above-described production method (part 2).
- a colloidal solution containing silicon oxide (SiO 2 ) having an average particle diameter of 190 nm was centrifuged, and then dried under reduced pressure, thereby producing a SiO 2 opal made of SiO 2 particles as a template.
- the dried SiO 2 opal was immersed in the carbon source solution containing the catalyst for 12 hours. Thereafter, the SiO 2 opal immersed in the carbon source solution containing the catalyst is filtered, and heat treatment is performed at 128 ° C. for 12 hours to remove moisture and the like, and the carbon source is converted into a resin, and phenol resin, SiO 2 opal, and nickel nitrate are removed. A composite was prepared.
- the composite of phenol resin, SiO 2 opal and nickel nitrate was heat-treated at 900 ° C. for 3 hours in an argon atmosphere, and the phenol resin was graphitized at the same time as carbonization to obtain graphitized porous carbon.
- Comparative example In the comparative example, first, SiO 2 opal composed of SiO 2 particles having an average particle diameter of 190 nm formed in the same manner as in Example 1 was introduced into a carbon source solution composed of pitch and quinoline, and the carbon source solution and the SiO 2 opal were combined. The composite was heat-treated at 1000 ° C. for 5 hours under an argon atmosphere to carbonize the pitch. As a result, a composite of carbon and SiO 2 opal was formed. Next, SiO 2 opal was removed from the composite of carbon and SiO 2 opal by wet etching using an HF aqueous solution to obtain macroporous carbon.
- sample 15 was obtained by heat-treating the macroporous carbon in an argon atmosphere at 2500 ° C. for 0.5 hours to graphitize the macroporous carbon. That is, the comparative example is an example in which macroporous carbon is graphitized without supporting a catalyst.
- sample 16 (macroporous carbon) was obtained without performing a heat treatment at 2500 ° C.
- the temperature was 1000 ° C., and a sample 19 was obtained without performing heat treatment at 2500 ° C.
- Sample 20 was obtained using SiO 2 opal composed of SiO 2 particles having an average particle diameter of 450 nm as a template.
- FIG. 3 shows X-ray diffraction (XRD) patterns of Sample 1, Sample 2, and Sample 3.
- FIG. 4 shows X-ray diffraction patterns of Sample 1, Sample 4, and Sample 5.
- FIG. 5 shows X-ray diffraction patterns of Sample 14 and Sample 17.
- FIG. 6 shows X-ray diffraction patterns of Sample 6, Sample 7, Sample 8, and Sample 19.
- FIG. 7 shows X-ray diffraction patterns of Samples 7 to 13.
- FIG. 8 shows X-ray diffraction patterns on the high angle side of Sample 7, Sample 11, Sample 12, and Sample 13.
- Each of the X-ray diffraction patterns in FIGS. 3 to 6 is obtained by analyzing the crystal structure by the Bragg-Brentano method after irradiating CuK ⁇ rays, and the horizontal axis is the angle formed by the incident X-rays of the CuK ⁇ rays and the diffraction X-rays The vertical axis represents the diffracted X-ray intensity (arbitrary scale).
- Example 1 the catalyst amount dependency in Example 1 can be observed.
- Sample 1, Sample 2, and Sample 3 all have clear peaks in the graphite phase, but Sample 1 with less catalyst has a broader peak due to the amorphous phase than Sample 2 and Sample 3. It can be said that the graphite phase and the amorphous phase coexist. Thereby, when the heat processing temperature in graphitization is as low as 900 degreeC, it turns out that it can graphitize by increasing a catalyst amount only by the desired amount.
- the sample 14 in Example 2 in which the catalyst was mixed with the carbon source in advance also shows a broad peak derived from the graphite phase. This shows that graphitization is possible at a heat treatment temperature as low as about 900 ° C. even when a catalyst is mixed with a carbon source in advance.
- the sample 18 in the comparative example in which the catalyst was not used and the heat treatment temperature was 1000 ° C. a broad peak showing an amorphous phase was seen, but no graphite phase was seen. This shows that when no catalyst is used, graphitization does not proceed at a heat treatment temperature of about 1000 ° C.
- SiO 2 opal composed of SiO 2 particles having an average particle diameter of 450 nm is used as a template, and all of Sample 7 to Sample 13 having a heat treatment temperature for graphitization of 900 ° C. to 1500 ° C. Phase peaks were seen. Further, as shown in FIG. 8, when the X-ray diffraction peak on the high angle side is seen, in the sample 12 graphitized at the heat treatment temperature of 1400 ° C., higher-order peaks such as (004) plane and (103) plane are observed. It was observed more strongly, and it was found that especially graphitization was progressing.
- Example 1 According to the TEM photograph of FIG. 9, in Example 1, the SiO 2 opal that is the template is removed, so that the SiO 2 opal is formed with a diameter approximately equal to 190 nm, which is the average particle diameter of the SiO 2 particles. It can be confirmed that a porous structure is formed by the fine pores.
- the macropores are three-dimensional due to the macropores formed with a diameter of about 130 nm to 180 nm. It can be confirmed that the connected porous structure is formed. Further, from FIG. 10B, it can be confirmed that the graphite phase is generated on the pore wall of the macropore formed in the sample 4.
- the macropore indicates a pore having a diameter of 50 nm or more.
- FIG. 11 shows a template after heat-treating a composite of a phenol resin and SiO 2 opal composed of SiO 2 particles having an average particle diameter of 450 nm at 400 ° C. in the preparation of Sample 6 using Example 1. It is a TEM photograph of a sample obtained by removing SiO 2 opal. 12A is a TEM photograph of Sample 6 produced by graphitization at a heat treatment temperature of 1000 ° C., and FIG. 12B is an enlarged TEM photograph of a part (pore wall part) of FIG. 12A.
- the SiO 2 opal as a template was removed, and the sample was formed with a diameter similar to 450 nm that was the average particle diameter of the SiO 2 particles. It can be confirmed that a porous structure is formed by the pores.
- the macropores are three-dimensionally connected by the macropores formed with a diameter of about 300 to 380 nm. It can be confirmed that a porous structure is formed. Moreover, it can confirm that the graphite phase has produced
- FIG. 13A is a TEM photograph of Sample 12 produced by graphitizing at a heat treatment temperature of 1400 ° C. using SiO 2 particles having an average particle diameter of 450 nm as a template
- FIG. 13B is a part of FIG. It is the TEM photograph which expanded the hole wall part).
- the diameter of the macropores formed after graphitization is 90 to 130 nm (not shown).
- the shrinkage rate of the pores when using the catalyst as in Example 1 is smaller than the shrinkage rate of the pores when no catalyst is used as in the comparative example.
- FIG. 14 shows Raman spectra of Sample 4 and Sample 18.
- FIG. 15 shows Raman spectra of Sample 2 and Sample 3.
- FIG. 16 shows Raman spectra of Sample 6, Sample 7, Sample 8, and Sample 19. 14 to 16, the horizontal axis represents the Raman shift (cm ⁇ 1 ), and the vertical axis represents the Raman scattering intensity (arbitrary scale).
- the intensity of the G band is large, and the intensity of the D band is smaller than the intensity of the G band.
- Sample 6, Sample 7, and Sample 8 are graphitized and the influence of the amorphous phase is small.
- the sample 19 produced in the comparative example has a smaller G band intensity than the sample 6, sample 7, and sample 8, and a larger D band intensity. Thereby, it turns out that the influence of an amorphous phase is large.
- D obtained by Raman spectrum Table 1 shows the measurement results of the area ratio of the band to the G band (D / G area ratio) and the hexagonal carbon network interlayer distance (d (002)).
- a micropore is a pore having a diameter of 2 nm or less.
- the total specific surface area and the specific surface area of the micropores were determined from the nitrogen adsorption isotherm measured at 77K using the BET method (BET: Brunauer-Emmett-Teller).
- the D / G area ratio was measured by the Raman spectrum shown in FIGS.
- the hexagonal carbon network interlayer distance (d (002)) was calculated from the angle of the diffraction peak (peak between 20 and 30 degrees at 2 ⁇ ) corresponding to the interlayer of the graphite phase of the X-ray diffraction pattern by the Bragg equation.
- the ratio of the specific surface area of the micropores to the total specific surface areas of Samples 1 to 8 and Sample 14 prepared in Example 1 and Example 2 is 0 or more and 0.74 or less.
- the value is smaller than that of the sample manufactured at a heat treatment temperature of 1000 ° C. or lower. Since the proportion of micropores decreases as graphitization proceeds, it can be seen that graphitization proceeds favorably in Samples 1 to 8.
- the specific surface area of the micropores is not shown, but as can be seen from the X-ray diffraction patterns of FIGS. 3 to 8, when a template made of particles having an average particle diameter of 450 nm is used. In this case, graphitization proceeds even when a template made of 190 nm particles is used, so that the ratio of the specific surface area of the micropores sufficiently satisfies 0 or more and 0.74 or less.
- the area ratio (D / G area ratio) between the D band and the G band of the Raman spectrum indicating the graphite phase is , 0 or more and 1.33 or less. Further, as described above, the progress of graphitization can be seen also by the D / G area ratio. However, in all of samples 1 to 14, the area ratio is 0 or more and 1.33 or less, and graphitization is not caused. It turns out that it is made well.
- the charge / discharge characteristics of the samples prepared in Examples 1 and 2 and the comparative example were measured using a tripolar cell composed of a working electrode, a reference electrode, a counter electrode, and a non-aqueous electrolyte.
- the working electrode was prepared by mixing each sample with a binder composed of polytetrafluoroethylene (PTFE) at a ratio of 10 wt% and pressing the mixture onto a nickel mesh.
- the reference electrode and the counter electrode were produced by pressure bonding metallic lithium to a nickel mesh.
- nonaqueous electrolytic solution a solution obtained by dissolving 1 mol of electrolyte LiPF 6 in a mixed solvent (1: 1 v / v) of ethylene carbonate (EC) and dimethyl carbonate (DMC) was used.
- FIG. 17 is a diagram showing a charge / discharge curve of Sample 2 manufactured according to Example 1.
- FIG. 18 is a diagram showing a charge / discharge curve of Sample 3 produced in Example 1.
- FIG. 19 is a diagram showing a charge / discharge curve of Sample 4 produced in Example 1.
- FIG. 20 is a diagram showing a charge / discharge curve of Sample 5 produced in Example 1.
- FIG. 21 is a diagram showing a charge / discharge curve of Sample 6 produced in Example 1.
- FIG. 22 is a diagram showing a charge / discharge curve of Sample 7 produced in Example 1.
- FIG. FIG. 23 is a diagram showing a charge / discharge curve of the sample 17 produced according to the comparative example.
- FIG. 18 is a diagram showing a charge / discharge curve of Sample 3 produced in Example 1.
- FIG. 19 is a diagram showing a charge / discharge curve of Sample 4 produced in Example 1.
- FIG. 20 is a diagram showing a charge / discharge curve of Sample 5 produced in Example 1.
- FIG. 21 is a
- FIG. 24 shows charge / discharge curves of Sample 4, Sample 14, Sample 15, Sample 16, and Sample 18 at a current density of 37.2 mA / g.
- FIG. 25 is a diagram showing charge / discharge curves of Sample 10, Sample 12, Sample 13, Sample 19, and Sample 20 at a current density of 37.2 mA / g. 17 to 25, the horizontal axis represents the charge / discharge capacity per unit time, and the vertical axis represents the discharge potential [Vvs. Li / Li + ]. Further, the curve in which the potential increases in the direction in which the capacity increases is the discharge curve, and vice versa.
- the heat treatment temperature is preferably 900 ° C. or higher and 1500 ° C. or lower. Further, a heat treatment temperature of about 1000 ° C. is more suitable.
- the catalyst amount is preferably 3 mmol / g-C or more and 15 mmol / g-C or less.
- the charge / discharge characteristics of the sample 6 and the sample 7 manufactured in Example 1 are compared using FIG. 21 and FIG.
- FIG. 21 and FIG. 22 are compared, when SiO 2 opal composed of SiO 2 particles having an average particle diameter of 450 nm is used as a template, it is 15 mmol / g more than that of sample 6 using a 3 mmol / g—C catalyst.
- Sample 7 using the -C catalyst has a larger flat portion at a low potential in the discharge curve and a larger capacity. This is because the D / G area ratio is smaller in the sample 7 than in the sample 6, and the graphitization is more advanced.
- Example 24 the samples manufactured in Example 1, Example 2, and Comparative Example are compared.
- SiO 2 particles having an average particle diameter of 190 nm are used as template particles
- Sample 16 and Sample 18 prepared at a heat treatment temperature of 1000 ° C. without using a catalyst are around 0.2 V to 0.3 V of the discharge curve. There is no flat part, and the potential changes greatly with discharge.
- a flat portion of 0.3 V or less due to insertion / desorption of lithium ions into / from the graphite phase was observed.
- the battery When used as a negative electrode material of a lithium ion secondary battery, it is preferable that the battery can be discharged at a constant low potential in order to ensure a high electromotive force. For this reason, when the sample 4 and the sample 14 which have a flat part of 0.3 V or less of a discharge curve are used as a negative electrode material of a lithium ion secondary battery, a lithium ion secondary battery excellent in charge / discharge characteristics is obtained. However, the non-graphitized samples 16 and 18 are not suitable for the negative electrode material of the lithium ion secondary battery.
- the sample 4 prepared using a catalyst at a lower heat treatment temperature (1000 ° C.) than the sample 15 produced from the pitch at a higher heat treatment temperature (2500 ° C.). It can be seen that the charge / discharge capacity is larger.
- FIG. 26 and FIG. 27 show the rate characteristics of Sample 4, Sample 6, Sample 7, Sample 14, Sample 15, and artificial graphite.
- the horizontal axis of FIG. 26 is current density [mAg ⁇ 1 ], and the vertical axis is discharge capacity [mAhg ⁇ 1 ] up to 1V.
- the horizontal axis represents the current density
- the vertical axis represents the capacity retention ratio at 1 V, and is a value normalized with the capacity of the current density 37.21 mAg ⁇ 1 as 1.
- Sample 4 in Examples 1 and 2 have a higher discharge capacity than Sample 15 in the comparative example. Further, the capacity at a current density of 37.21 mAg-1 is higher than the capacity of the sample 15 of 74 mAhg- 1 .
- Sample 15 has a small capacity value in [Table 1] although the ratio of the specific surface area of the micropores and the D / G area ratio have the same values as in Example 1 and Example 2. I understand. This is presumably because the total specific surface area is as small as 174 m 2 g ⁇ 1 .
- Sample 4 in Examples 1 and 2 have a higher capacity retention rate than Sample 15 and Graphite in Comparative Example, and an excellent discharge rate. And high-speed charge / discharge characteristics.
- FIGS. 28 and 29 show rate characteristics of Sample 11, Sample 12, Sample 13, Sample 20, and artificial graphite.
- the horizontal axis of FIG. 28 is current density [mAg ⁇ 1 ], and the vertical axis is discharge capacity [mAhg ⁇ 1 ] up to 3V.
- the horizontal axis represents current density, and the vertical axis represents discharge capacity up to 0.5V.
- Samples 12 and 13 graphitized at a heat treatment temperature of 1400 ° C. are 0 to 3 V and 0 to 0.5 V. In any of these ranges, a high capacity is maintained up to a high current density.
- artificial graphite has a capacity that rapidly decreases as the current density increases, but is superior to the sample 20 in high-speed charge / discharge characteristics.
- FIGS. 30 and 31 show rate characteristics of Sample 3, Sample 4, Sample 5, and Sample 20.
- FIG. The horizontal axis in FIG. 30 is current density [mAg ⁇ 1 ], and the vertical axis is discharge capacity [mAhg ⁇ 1 ] up to 3V. Further, the horizontal axis of FIG. 31 is the current density, and the vertical axis is the discharge capacity up to 0.5V.
- the sample having a larger pore size is more graphitized. Yes. That is, when the pore size is small, the graphitization is insufficient, and thus the discharge capacity at a low potential is considered to be small.
- FIG. 32 is a diagram showing cycle characteristics of the sample 11 produced in the example.
- the horizontal axis represents the number of cycles (measured number)
- the vertical axis represents the discharge capacity [mAhg ⁇ 1 ] at a current density [37.2 mA / g].
- the discharge capacity is stably maintained in the measurement up to 75 times.
- the macroporous graphite electrode material of this embodiment example has a higher charge / discharge capacity at a higher current density than that of the conventional graphite electrode material, and has high-speed charge / discharge characteristics. It turns out that it is also excellent.
- FIG. 33 shows a schematic configuration diagram of a lithium ion secondary battery according to the second embodiment of the present invention.
- the lithium ion secondary battery 20 of this embodiment is an example in which the composite nanoporous electrode material of the first embodiment is used as the positive electrode active material.
- the lithium ion secondary battery 20 of the present embodiment includes a cylindrical casing 26 made of nickel, a roll body 30 accommodated in the casing 26, and a non-aqueous electrolyte that is also accommodated in the casing 26. It consists of and.
- a positive terminal 27 is formed on the upper bottom of the housing 26. Further, although not shown, a negative electrode terminal is formed on the bottom bottom of the housing 26.
- the roll body 30 has a configuration in which a laminated body in which a belt-like positive electrode member 22, a separator 21, and a negative electrode member 23 are sequentially laminated is wound in a roll shape.
- the positive electrode member 22 is, for example, a metal foil made of aluminum and a positive electrode active material made of a lithium transition metal composite compound capable of reversibly occluding and releasing lithium ions, and a mixture made of a conductive agent and a binder. It is configured.
- the negative electrode member 23 has a configuration in which, for example, a negative electrode active material made of the macroporous graphite electrode material of the first embodiment, a conductive agent, and a mixture made of a binder are pressure-bonded to a metal foil made of copper.
- the separator 21 can use the material used conventionally, for example, is comprised by polymer films, such as a polypropylene.
- the positive electrode member 22 and the negative electrode member 23 are electrically separated by the separator 21.
- nonaqueous electrolytic solution a conventionally used material can be used, and a mixed solution in which lithium hexafluorophosphate (LiPF 6 ) or the like is dissolved as a lithium salt in an organic solvent such as ethylene carbonate (EC). Is used.
- LiPF 6 lithium hexafluorophosphate
- EC ethylene carbonate
- the non-aqueous electrolyte is impregnated in the housing.
- the positive electrode member 22 is connected to a positive electrode current collecting tab 25 formed on the upper bottom portion in the casing 26 by a lead wiring 24, and the positive electrode current collecting tab 25 is a positive electrode formed on the upper bottom portion of the casing 26.
- the terminal 27 is electrically connected.
- the negative electrode member 23 is connected to a negative electrode current collecting tab 28 formed in the lower bottom portion of the housing 26 by a lead wire 29, and the negative electrode current collecting tab 28 is a negative electrode formed in the lower bottom portion of the housing 26. It is electrically connected to the terminal.
- the above-described macroporous graphite electrode material of the present invention is used as the negative electrode active material, a high-performance lithium ion having a high charge / discharge capacity and capable of high-speed charge / discharge.
- the secondary battery 20 is obtained.
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Abstract
Description
ここで、カーボン前駆体樹脂とは、カーボン源が重合しポリマー固体になった状態をいう。
以下に、本発明の第1の実施形態に係るマクロ多孔性グラファイト電極材とその製造方法を、図1A~図1Hを参照しながら説明する。
まず、本実施形態例のマクロ多孔性グラファイト電極材の構成とその特性について説明する。本実施形態例のマクロ多孔性グラファイト電極材は、マクロ細孔が3次元的に連結した多孔構造を有し、その細孔壁がグラファイト性カーボンから構成されるマクロ多孔体で構成される。そして、その全比表面積が69m2g-1よりも大きく、全比表面積に対するミクロ孔の比表面積の割合が0以上0.74以下で、かつ、ラマンスペクトルのDバンドとGバンドの面積比(D/G面積比)が0以上1.33以下とされている。
ここで、ミクロ孔とは、直径2nm以下の細孔を示す。
次に、図1A~図1Hを用いて、本実施形態例のマクロ多孔性グラファイト電極材の製造方法について説明する。
ここで、フェノール樹脂とは、本発明のカーボン前駆体樹脂に相当するものである。
次に、図2A~図2Eを用いて、本実施形態例のマクロ多孔性グラファイト電極材の製造方法の他の例について説明する。
また、上述の製造方法(その1、その2)では、触媒として硝酸ニッケルを用いる例としたが、その他、ニッケルや鉄、コバルトの金属塩(硝酸塩、酢酸塩、塩化物)や錯体(アセルアセトン錯体など)等を適用することができる。本実施形態例では、触媒の効果により、グラファイト化に必要な熱処理温度を900℃≦Tc≦1500と、比較的低い温度とすることができる。
実施例1では、上述した製造方法(その1)を用いてマクロ多孔性グラファイト電極材となる試料を作製した。
一方、フェノールとホルムアルデヒドをモル比で1:0.85となるように混合した混合溶液を作製し、この混合溶液に塩酸を少量加えることにより、カーボン源溶液を準備した。
実施例2では、上述した製造方法(その2)を用いてマクロ多孔性グラファイト電極材となる試料を作製した。
比較例では、まず、実施例1と同様にして形成した平均粒子径190nmのSiO2粒子からなるSiO2オパールを、ピッチとキノリンからなるカーボン源溶液に導入し、カーボン源溶液とSiO2オパールの複合体をアルゴン雰囲気下において、1000℃で5時間加熱処理し、ピッチをカーボン化した。これにより、カーボンとSiO2オパールの複合体が形成された。次に、HF水溶液を用いたウエットエッチングにより、カーボンとSiO2オパールの複合体からSiO2オパールを除去し、マクロ多孔カーボンを得た。次に、マクロ多孔カーボンをアルゴン雰囲気中において2500℃で0.5時間加熱処理しマクロ多孔カーボンをグラファイト化することにより、試料15を得た。
すなわち、比較例は触媒を担持させずにマクロ多孔カーボンをグラファイト化した例である。
図3は、試料1、試料2、試料3のX線回折(XRD:X-Ray Diffraction)パターンである。また、図4は、試料1、試料4、試料5のX線回折パターンである。また、図5は、試料14、試料17のX線回折パターンである。また、図6は、試料6、試料7、試料8、試料19のX線回折パターンである。また、図7は、試料7~試料13のX線回折パターンである。また、図8は、試料7、試料11、試料12、試料13の高角度側のX線回折パターンである。
全比表面積及びミクロ孔の比表面積は、77Kで測定した窒素吸着等温線からBET法(BET:Brunauer-Emmett-Teller)を用いて求めた。
D/G面積比は、図14~図16に示すラマンスペクトルにより測定した。
六角炭素網層間距離(d(002))は、X線回折パターンのグラファイト相の層間に対応する回折ピーク(2θで20~30度の間のピーク)の角度からBragg式より算出した。
図17~図25の横軸は単位時間あたりの充放電容量であり、縦軸は、放電電位[Vvs.Li/Li+]である。また、容量が増加する方向において電位が増加する方の曲線が放電曲線、その逆は充電曲線である。
図17、図18、図23の充放電曲線を比較すると、比較例で作製した試料17に比較して、実施例1で作製した試料2及び試料3では、放電曲線の0.3V以下の容量が増大しており、グラファイト相へのリチウムイオンの挿入・脱離の寄与が認められる。また、試料2と試料3では、図3のX線回折パターンにより、どちらもグラファイト相の明瞭なピークが確認できたが、充放電特性では、試料3よりも試料2のほうがレート特性に優れていることがわかる。これにより、触媒の適量は、15mmol/g-C以下にあると考えられる。また、X線回折パターンの結果より、グラファイト化における熱処理温度が900℃の場合には、触媒量が3mmol/g-Cであるとアモルファス相のピークも大きくなることがわかっている。このため、触媒量は、3mmol/g-C以上15mmol/g-C以下であることが好ましい。
したがって、本発明では、鋳型となるSiO2粒子の平均粒子径の上限は、450nmであると考えられる。
図33に、本発明の第2の実施形態に係るリチウムイオン二次電池の概略構成図を示す。本実施形態例のリチウムイオン二次電池20は、正極活物質に第1の実施形態の複合ナノ多孔電極材を用いた例である。
筐体26上底部には、正極端子27が形成されている。また、筐体26下底部には、図示しないが、負極端子が形成されている。
ロール体30では、正極部材22と、負極部材23とが、セパレータ21により電気的に分離されている。
Claims (12)
- 1500℃以下の熱処理温度でグラファイト化されたマクロ多孔性グラファイト電極材であって、
マクロ細孔が3次元的に連結した多孔構造を有し、その細孔壁がグラファイト性カーボンから構成されるマクロ多孔体であり、全比表面積に対するミクロ孔の比表面積の割合が、0以上0.74以下であり、ラマンスペクトルにおけるDバンドとGバンドの面積比(D/G面積比)が0以上1.33以下である
マクロ多孔性グラファイト電極材。 - さらに、前記全比表面積が69m2g-1よりも大きい
請求項1記載のマクロ多孔性グラファイト電極材。 - 37.2mA/gの電流密度における0~1V(vsLi/Li+)の範囲の放電容量が74mAh/gよりも大きい値を有する
請求項2記載のマクロ多孔性グラファイト電極材。 - SiO2粒子からなる鋳型を準備する工程と、
前記鋳型をカーボン源溶液に混入する工程と、
前記カーボン源溶液から溶媒等を除去し、カーボン源を樹脂化し、カーボン前駆体樹脂と鋳型の複合体を形成する工程と、
前記鋳型を除去し、マクロ多孔カーボンを形成する工程と、
前記マクロ多孔カーボンに触媒を担持する工程と、
前記触媒を担持したマクロ多孔カーボンを900℃以上1500℃以下の熱処理温度で加熱処理することによりグラファイト化し、マクロ多孔グラファイトを形成する工程と、
を有するマクロ多孔性グラファイト電極材の製造方法。 - 前記触媒は、前記マクロ多孔カーボン1グラムに対し、3mmol以上15mmol以下で添加する
請求項4記載のマクロ多孔性グラファイト電極材の製造方法。 - 前記鋳型を構成する粒子の平均粒子径は、100nm以上450nm以下である
請求項5記載のマクロ多孔性グラファイト電極材の製造方法。 - SiO2粒子からなる鋳型を準備する工程と、
触媒を添加したカーボン源を準備する工程と、
前記鋳型を前記カーボン源溶液に混入する工程と、
前記カーボン源溶液から溶媒等を除去し、カーボン源を樹脂化し、カーボン前駆体樹脂と鋳型の複合体を形成する工程と、
前記カーボン前駆体樹脂と鋳型の複合体を900℃以上1500℃以下の熱処理温度で加熱処理することによりグラファイト化し、グラファイトと鋳型の複合体を形成する工程と、
前記グラファイトと鋳型の複合体から前記鋳型と触媒を除去する工程と、
を有するマクロ多孔性グラファイト電極材の製造方法。 - 前記触媒は、前記カーボン前駆体樹脂をカーボン化したあとのカーボン1gに対して3mmol以上15mmol以下となるように添加する
請求項7記載のマクロ多孔性グラファイト電極材の製造方法。 - 前記SiO2粒子の平均粒子径は、100nm以上450nm以下である
請求項7記載のマクロ多孔性グラファイト電極材の製造方法。 - リチウムイオンを可逆的に吸蔵・放出可能なリチウム遷移金属複合化合物を正極活物質として有する正極部材と、
1500℃以下の熱処理温度でグラファイト化された負極部材であって、マクロ細孔が3次元的に連結した多孔構造を有し、その細孔壁がグラファイト性カーボンから構成されるマクロ多孔体であり、全比表面積に対するミクロ孔の比表面積の割合が、0以上0.74以下であり、ラマンスペクトルにおけるDバンドとGバンドの面積比(D/G面積比)が0以上1.33以下であり、前記正極活物質よりも低い電位でリチウムイオンを吸蔵・放出する負極活物質からなる負極部材と、
非水溶媒液中にリチウム塩が溶解された非水電解液と、
を有して構成されるリチウムイオン二次電池。 - さらに、前記全比表面積は、前記全比表面積が69m2g-1よりも大きい
請求項10記載のリチウムイオン二次電池。 - 37.2mA/gの電流密度における0~1V(vsLi/Li+)の範囲の放電容量が74mAh/gよりも大きい値を有する
請求項11記載のリチウムイオン二次電池。
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US (1) | US20120094173A1 (ja) |
JP (1) | JP5669070B2 (ja) |
KR (1) | KR20120111934A (ja) |
CN (1) | CN102804464B (ja) |
WO (1) | WO2010150859A1 (ja) |
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US20130130115A1 (en) * | 2011-11-22 | 2013-05-23 | Samsung Electronics Co., Ltd. | Composite negative active material, method of preparing the same, and lithium secondary battery including the same |
JP2014012629A (ja) * | 2012-06-18 | 2014-01-23 | Toyota Motor Engineering & Manufacturing North America Inc | 高表面積炭素オパールとそこから得られる逆オパール |
WO2014141769A1 (ja) * | 2013-03-13 | 2014-09-18 | ソニー株式会社 | リチウム-硫黄二次電池及び電極材料 |
US9212062B2 (en) | 2011-07-27 | 2015-12-15 | Heraeus Quarzglas Gmbh & Co. Kg | Porous carbon product and method for producing an electrode for a rechargeable lithium battery |
US20160064154A1 (en) * | 2011-08-31 | 2016-03-03 | Semiconductor Energy Laboratory Co., Ltd. | Negative electrode of power storage device and power storage device |
WO2016080300A1 (ja) * | 2014-11-18 | 2016-05-26 | 国立大学法人 長崎大学 | 二次電池 |
JP2016526755A (ja) * | 2013-06-12 | 2016-09-05 | ヘレーウス クヴァルツグラース ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフトHeraeus Quarzglas GmbH & Co. KG | 二次電池用のリチウムイオンセル |
JP2017199656A (ja) * | 2011-09-28 | 2017-11-02 | ジョンソン、マッセイ、フュエル、セルズ、リミテッドJohnson Matthey Fuel Cells Limited | カーボン担持触媒 |
JP2018012626A (ja) * | 2016-07-21 | 2018-01-25 | 新日鉄住金化学株式会社 | 多孔質炭素材料、固体高分子形燃料電池用触媒および固体高分子形燃料電池ならびに多孔質炭素材料の製造方法 |
JP2019175550A (ja) * | 2018-03-26 | 2019-10-10 | リンテック株式会社 | 負極シートの製造方法 |
JP2021061089A (ja) * | 2019-10-02 | 2021-04-15 | 株式会社クラレ | 蓄電デバイス用炭素質材料の製造方法および蓄電デバイス用炭素質材料 |
US11171335B2 (en) | 2015-09-09 | 2021-11-09 | Nec Corporation | Fast chargeable carbon anode material with inner channels |
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WO2012119666A1 (en) * | 2011-03-04 | 2012-09-13 | Heraeus Quarzglas Gmbh & Co. Kg | Porous carbon product and use thereof |
US9212062B2 (en) | 2011-07-27 | 2015-12-15 | Heraeus Quarzglas Gmbh & Co. Kg | Porous carbon product and method for producing an electrode for a rechargeable lithium battery |
US20160064154A1 (en) * | 2011-08-31 | 2016-03-03 | Semiconductor Energy Laboratory Co., Ltd. | Negative electrode of power storage device and power storage device |
US10998141B2 (en) | 2011-08-31 | 2021-05-04 | Semiconductor Energy Laboratory Co., Ltd. | Negative electrode of power storage device and power storage device |
US10614967B2 (en) * | 2011-08-31 | 2020-04-07 | Semiconductor Energy Laboratory Co., Ltd. | Negative electrode of power storage device and power storage device |
JP2017199656A (ja) * | 2011-09-28 | 2017-11-02 | ジョンソン、マッセイ、フュエル、セルズ、リミテッドJohnson Matthey Fuel Cells Limited | カーボン担持触媒 |
US20130130115A1 (en) * | 2011-11-22 | 2013-05-23 | Samsung Electronics Co., Ltd. | Composite negative active material, method of preparing the same, and lithium secondary battery including the same |
CN103137953A (zh) * | 2011-11-22 | 2013-06-05 | 三星电子株式会社 | 复合负极活性材料、其制备方法和包括其的锂二次电池 |
JP2013110112A (ja) * | 2011-11-22 | 2013-06-06 | Samsung Electronics Co Ltd | 複合負極活物質、その製造方法及びそれを含むリチウム二次電池 |
US10099965B2 (en) | 2012-06-18 | 2018-10-16 | Toyota Motor Engineering & Manufacturing North America, Inc. | Methods for forming carbon opal templates and their use in forming inverse opals |
JP2014012629A (ja) * | 2012-06-18 | 2014-01-23 | Toyota Motor Engineering & Manufacturing North America Inc | 高表面積炭素オパールとそこから得られる逆オパール |
WO2014141769A1 (ja) * | 2013-03-13 | 2014-09-18 | ソニー株式会社 | リチウム-硫黄二次電池及び電極材料 |
JP2016526755A (ja) * | 2013-06-12 | 2016-09-05 | ヘレーウス クヴァルツグラース ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフトHeraeus Quarzglas GmbH & Co. KG | 二次電池用のリチウムイオンセル |
US10879537B2 (en) | 2013-06-12 | 2020-12-29 | Heraeus Quarzglas Gmbh & Co. Kg | Lithium ion cell for a secondary battery |
WO2016080300A1 (ja) * | 2014-11-18 | 2016-05-26 | 国立大学法人 長崎大学 | 二次電池 |
US11171335B2 (en) | 2015-09-09 | 2021-11-09 | Nec Corporation | Fast chargeable carbon anode material with inner channels |
JP2018012626A (ja) * | 2016-07-21 | 2018-01-25 | 新日鉄住金化学株式会社 | 多孔質炭素材料、固体高分子形燃料電池用触媒および固体高分子形燃料電池ならびに多孔質炭素材料の製造方法 |
JP2019175550A (ja) * | 2018-03-26 | 2019-10-10 | リンテック株式会社 | 負極シートの製造方法 |
JP7203505B2 (ja) | 2018-03-26 | 2023-01-13 | リンテック株式会社 | 負極シートの製造方法 |
JP2021061089A (ja) * | 2019-10-02 | 2021-04-15 | 株式会社クラレ | 蓄電デバイス用炭素質材料の製造方法および蓄電デバイス用炭素質材料 |
JP7414233B2 (ja) | 2019-10-02 | 2024-01-16 | 株式会社クラレ | 蓄電デバイス用炭素質材料の製造方法および蓄電デバイス用炭素質材料 |
Also Published As
Publication number | Publication date |
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US20120094173A1 (en) | 2012-04-19 |
CN102804464B (zh) | 2015-04-08 |
JPWO2010150859A1 (ja) | 2012-12-10 |
KR20120111934A (ko) | 2012-10-11 |
JP5669070B2 (ja) | 2015-02-12 |
CN102804464A (zh) | 2012-11-28 |
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