WO2016129557A1 - 炭素材料、その製造方法及びその用途 - Google Patents
炭素材料、その製造方法及びその用途 Download PDFInfo
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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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- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
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Definitions
- the present invention relates to a carbon material, a manufacturing method thereof, and an application thereof. More specifically, it has a good electrode filling property, high energy density, and high input / output characteristics as an electrode material for a non-aqueous electrolyte secondary battery, a manufacturing method thereof, charge / discharge cycle characteristics, and high coulomb efficiency.
- the present invention relates to a secondary battery.
- Lithium ion secondary batteries are used in a variety of applications, ranging from small ones such as portable devices to large ones such as battery electric vehicles (BEV) and hybrid electric vehicles (HEV). Appropriate performance is required.
- BEV battery electric vehicles
- HEV hybrid electric vehicles
- lithium-ion secondary batteries having higher energy density are required due to the reduction in size and weight of electrical and electronic devices and the increase in power consumption accompanying diversification of functions.
- secondary batteries with high output and large capacity for applications such as electric tools such as electric drills and hybrid vehicles.
- lead secondary batteries, nickel cadmium secondary batteries, and nickel metal hydride secondary batteries have been mainly used in this field.
- expectations for high-density lithium-ion secondary batteries that are small, light, and high are high.
- carbon materials such as graphite, hard carbon, and soft carbon are used for the negative electrode active material of the lithium ion secondary battery.
- Hard carbon and soft carbon described in Japanese Patent No. 36553105 (US Pat. No. 5,587,255, Patent Document 1) have excellent large current characteristics and relatively good cycle characteristics. What is used is graphite.
- Graphite includes natural graphite and artificial graphite.
- natural graphite is available at a low price, and because of its high degree of graphitization, the discharge capacity and electrode density are high, but the particle shape is scaly, has a large specific surface area, and has a highly reactive graphite edge surface.
- the electrolytic solution is decomposed, the Coulomb efficiency at the first charge / discharge is very low, and gas is generated. Also, the cycle characteristics were not good.
- Japanese Patent No. 3534391 US Pat. No. 6,632,569, Patent Document 2 and the like have proposed a method of coating carbon on the surface of natural graphite processed into a spherical shape.
- Patent Document 4 Japanese Patent No. 3361510
- Patent Document 5 In Japanese Patent Application Laid-Open No. 2003-77534 (Patent Document 5), studies have been made for the purpose of charging and discharging at a high speed with a relatively large gap.
- WO2011 / 049199 discloses artificial graphite having excellent cycle characteristics.
- Japanese Patent No. 4945029 discloses an artificial graphite negative electrode produced by adding boron to raw acicular coke having a flow structure.
- Patent Document 8 discloses a scaly carbon material obtained by applying a surface coating to a carbon material having a specific optical structure.
- WO 2014/058040 discloses a carbon material having a specific optical structure and containing boron.
- Japanese Patent No. 36553105 (US Pat. No. 5,587,255) Japanese Patent No. 3534391 (US Pat. No. 6,632,569) Japanese Patent No. 3126030 Japanese Patent No. 3361510 Japanese Unexamined Patent Publication No. 2003-77534 WO2011 / 049199 (US Pat. No. 8,372,373) Japanese Patent No. 4945029 (U.S. Pat. No. 7,141,229) WO2014 / 003135 WO2014 / 058040 (U.S. Patent Application Publication No. 2015/0263348)
- the negative electrode material described in Patent Document 1 is excellent in characteristics against a large current, but has a low volumetric energy density and a very expensive price, so it is used only for some special large batteries.
- Patent Document 2 The material manufactured by the method described in Patent Document 2 can cope with the high capacity, low current, and medium cycle characteristics required for mobile applications and the like, but the large current and super long cycle of the large battery as described above. It is very difficult to meet requirements such as characteristics.
- the graphitized product described in Patent Document 3 is a well-balanced negative electrode material and excellent in capacity and input / output characteristics. However, since it is a true spherical particle having a high degree of circularity, the contact area between the particles is small, and the resistance is high. There is a disadvantage that input / output characteristics are low.
- fine powder such as natural graphite can be used in addition to fine powder of artificial graphite raw material, and as a negative electrode material for mobile, very excellent performance is exhibited.
- this material can cope with the high capacity, low current, and medium cycle characteristics required by mobile applications and the like, it does not meet the requirements for the large current and ultra-long cycle characteristics of the large battery as described above.
- Patent Document 5 the capacity is not sufficiently maintained during charging and discharging, and is practically insufficient for use in a secondary battery.
- Patent Document 6 there is room for improvement in the diffusion of active material ions because the graphite structure is dense.
- the particle shape is almost spherical, there is a problem that when the electrode is produced, the contact between the particles becomes small and the electric resistance becomes large.
- Patent Document 7 although the capacity and initial charge / discharge efficiency are improved compared to the conventional artificial graphite, the raw coke is pulverized and then carbonized by firing, or graphitization is performed in an argon stream, which is very costly. This is not practical because it involves a manufacturing process.
- the present invention provides the following carbon materials, methods for producing the same, and uses thereof.
- the ratio I110 / I004 of the peak intensity I110 of the (110) plane and the peak intensity I004 of the (004) plane of the graphite crystal obtained from the powder XRD measurement is 0.10 or more and 0.35 or less, and the average circularity is 0.00.
- the total pore volume of pores having a diameter of 80 or more and 0.95 or less, an average interplanar spacing d002 of (002) plane by X-ray diffraction method of 0.337 nm or less, and a diameter of 0.4 ⁇ m or less measured by nitrogen gas adsorption method is 25.
- a non-flaky carbon material of 0.0 ⁇ L / g or more and 40.0 ⁇ L / g or less Regarding the optical structure observed in the cross section of the carbon material, the area is accumulated from the structure having a small area, the area of the optical structure when the accumulated area is 60% of the total optical tissue area is SOP, and the aspect ratio When the number of tissues is counted from the small structures of the above, the aspect ratio in the 60th tissue of the total number of tissues is AROP, and the median diameter in the volume-based cumulative particle size distribution by laser diffraction method is D50, 1.5 ⁇ AROP ⁇ 6.0 and 0.2 ⁇ D50 ⁇ (SOP ⁇ AROP) 1/2 ⁇ 2 ⁇ D50 Carbon material having the relationship [2] The carbon material as described in 1 above, wherein D50 is 1 ⁇ m or more and 30 ⁇ m or less.
- the coke accumulates the area from the small area of the optical structure observed in the cross section, the cumulative area of the total optical tissue area area of the optical tissue when the 60% of the area is at 50 [mu] m 2 or more 5000 .mu.m 2 or less, and an aspect ratio of 60% th tissue in the number of whole tissue counting the number of tissues from a small tissue aspect ratio of 1.
- the manufacturing method of the carbon material using the coke which is 5-6. [6] The method for producing a carbon material as described in 5 above, wherein the step of bringing into contact with oxygen gas is brought into contact with oxygen during heating in the step of graphitizing.
- a method for producing an electrode for a lithium battery comprising a step of applying the electrode paste described in 10 above onto a current collector and drying it, and then compressing the paste with a pressure of 1 to 3 t / cm 2 .
- the carbon material of the present invention When the carbon material of the present invention is used as a carbon material for a battery electrode, a battery electrode having a high capacity, a high energy density, a high coulomb efficiency and a low resistance that can be charged / discharged at high speed while maintaining high cycle characteristics is obtained. be able to. Moreover, the carbon material of the present invention is excellent in economic efficiency and mass productivity, and can be produced by a method with improved safety.
- the polarizing microscope photograph (480 micrometers x 640 micrometers) of the coke of Example 1 is shown.
- the black part is the embedded resin, and the gray part is the optical structure.
- the polarizing microscope photograph (480 micrometers x 640 micrometers) of the carbon material of Example 1 is shown.
- the black part is the embedded resin, and the gray part is the optical structure.
- Carbon material The electrode of a rechargeable battery is required to store more electricity per unit volume.
- Graphite has excellent Coulomb efficiency for the first charge / discharge, but there is an upper limit to the stoichiometric ratio of lithium atoms to carbon atoms during lithium insertion, and it is difficult to further improve the energy density per mass. .
- the active material is coated on a current collector plate and dried, and then pressed to improve the filling property of the negative electrode active material per volume. At this time, if the graphite particles are soft and deformed to some extent with the press, the electrode density can be extremely increased.
- graphite particles are hard when the structure is complicated, it is preferable to use graphite particles having a large structure in order to improve the electrode density.
- the structures observed in the graphite particles include optical anisotropy due to the development of crystals and alignment of the graphite network surface, and the occurrence of crystals that are undeveloped or due to large crystal turbulence such as hard carbon. It has been known for a long time that there is an organization showing isotropic properties. For the observation of these structures, it is possible to measure the size of the crystallite by using X-ray diffraction method. For example, “Latest carbon material experiment technology (analysis / analysis bias) Carbon Society of Japan bias (2001)” , Publishing: Sipec Co., Ltd., pages 1 to 8, etc. ".
- the carbon material in a preferred embodiment of the present invention is a material in which the size and shape of the optical texture are in a specific range, and further has an appropriate degree of graphitization, so that both the crushing characteristics and the battery characteristics as an electrode material are excellent. It becomes.
- the carbon material of the present invention satisfies the following formula. 1.5 ⁇ AROP ⁇ 6.0 and 0.2 ⁇ D50 ⁇ (SOP ⁇ AROP) 1/2 ⁇ 2 ⁇ D50
- the SOP is an accumulation of an area from a small area of the optical structure observed using a polarizing microscope in the cross section of the carbon material molded body, and the accumulated area is 60% of the total optical structure area. It represents the area of the optical structure.
- AROP represents the aspect ratio in the tissue that is 60% of the total number of tissues by counting the number of tissues from the tissues having a small aspect ratio.
- the optical structure in the carbon material hardens while flowing, it often has a band shape, and when the cross section of the carbon material is observed, the shape of the optical structure is generally rectangular, and the area is short of the optical structure. It can be estimated that the diameter is multiplied by the major axis.
- the minor axis is the major axis / aspect ratio. If it is assumed that the optical structure to be subjected to the area SOP and the optical structure to be subjected to the aspect ratio AROP are the same, the major axis in the optical structure is (SOP ⁇ AROP) 1/2 . That is, (SOP ⁇ AROP) 1/2 assumes a long axis of an optical structure having a specific size, and the above formula shows that the optical structure has a certain size or more depending on the ratio of DSOP to D50. It prescribes.
- (SOP ⁇ AROP) 1/2 assuming the major axis of the optical texture is usually smaller than D50, but when (SOP ⁇ AROP) 1/2 and the value of D50 are close, the particles in the carbon material are more It means that it consists of a small number of optical structures, and when (SOP ⁇ AROP) 1/2 is small relative to D50, it means that the particles in the carbon material contain a large number of optical structures.
- the value of (SOP ⁇ AROP) 1/2 is 0.2 ⁇ D50 or more, there are few boundaries of the optical structure, which is convenient for the diffusion of lithium ions, so that charge / discharge can be performed at a high speed. Moreover, the larger the value, the more lithium ions that can be retained.
- the value is preferably 0.25 ⁇ D50 or more, more preferably 0.28 ⁇ D50 or more, and further preferably 0.35 ⁇ D50 or more.
- the upper limit is less than 2 ⁇ D50, but is preferably 1 ⁇ D50 or less.
- D50 represents a 50% particle diameter (median diameter) in a volume-based cumulative particle size distribution measured by a laser diffraction particle size distribution meter, and indicates an apparent particle diameter.
- the laser diffraction type particle size distribution analyzer for example, Mastersizer (registered trademark) manufactured by Malvern can be used.
- D50 of the carbon material is 1 ⁇ m or more and 30 ⁇ m or less.
- D50 In order to make D50 less than 1 ⁇ m, it is necessary to pulverize with special equipment at the time of pulverization, and more energy is required. In addition, handling such as agglomeration and coatability is difficult, and if the surface area is excessively increased, the initial charge / discharge efficiency is lowered.
- D50 is too large, it takes time to diffuse lithium in the negative electrode material, and the input / output characteristics deteriorate.
- More preferable D50 is 5 ⁇ m or more and 20 ⁇ m or less. This granularity facilitates handling and improves input / output characteristics, and can withstand a large current required when used as a driving power source for automobiles and the like.
- the aspect ratio AROP of the carbon material is 1.5 or more and 6.0 or less, preferably 2.0 or more and 4.0 or less, more preferably 2.0 or more and 2.3 or less.
- the aspect ratio is larger than the lower limit, it is preferable because the structure slips and a high-density electrode is easily obtained.
- the aspect ratio is lower than the upper limit, the energy required for synthesizing the raw materials is small and preferable.
- the optical tissue observation and analysis method is as follows. [Preparation of polarizing microscope observation sample]
- the “cross section of the carbon material” in the present invention is prepared as follows. A double-sided tape is affixed to the bottom of a plastic sample container having an internal volume of 30 cm 3 , and about 2 cups of spatula (about 2 g) are placed on the sample.
- Cold embedding resin (trade name: cold embedding resin # 105, manufacturer: Japan Composite Co., Ltd., sales company: Marumoto Struers Co., Ltd.)
- curing agent trade name: curing agent (M agent), Manufacturing company: Nippon Oil & Fats Co., Ltd., sales company: Marumoto Struers Co., Ltd.) and knead for 30 seconds.
- the obtained mixture (about 5 ml) is slowly poured into the sample container until it reaches a height of about 1 cm, and allowed to stand for 1 day to solidify.
- the solidified sample is taken out and the double-sided tape is peeled off.
- the surface to be measured is polished using a polishing plate rotating type polishing machine.
- Polishing is performed by pressing the polished surface of the sample against the rotating surface.
- the polishing plate is rotated at 1000 rpm.
- the grain size (count) of the polishing plate is # 500, # 1000, # 2000 in order, and finally alumina (trade name: Baikalox; registered trademark) type 0.3CR, particle size 0.3 ⁇ m, manufacturer: Mirror polishing using Baikowski, sales company: Baikowski Japan).
- the polished sample is fixed with clay on a preparation and observed using a polarizing microscope (OLYMPUS, BX51).
- Statistic processing for the detected organization is performed using an external macro.
- the black portion that is, the portion corresponding to the resin portion instead of the optical structure is excluded from the statistical object, and the area and aspect ratio of each structure are calculated for each of the blue, yellow, and red optical structures.
- the carbon particles according to the embodiment of the present invention are made of non-flaky carbon particles. This is to prevent the orientation of the carbon network layer during electrode preparation. Orientation is used as an index for evaluation of scalyness. That is, the carbon material according to the embodiment of the present invention has a ratio I110 / I004 of the peak intensity I110 of the (110) plane and the peak intensity I004 of the (004) plane in the XRD pattern obtained from the powder X-ray diffraction measurement. It is 0.10 or more and 0.35 or less. The ratio is preferably 0.18 or more and 0.30 or less, and more preferably 0.21 or more and 0.30 or less.
- a carbon material having a value lower than 0.10 is too high in orientation, so that the electrode is likely to expand during the first charge / discharge, and the carbon network surface is parallel to the electrode plate, so that Li insertion hardly occurs and rapid charge / discharge characteristics. Becomes worse. Since the carbon material having a value higher than 0.35 has too low orientation, it is difficult to increase the electrode density when pressing is performed during electrode production. In addition, since the bulk density becomes small when it becomes scale-like, it becomes difficult to handle, and when it is made into a slurry for electrode production, the affinity with a solvent is low, and the peel strength of the electrode may be weakened.
- the orientation of the particles is also related to the optical structure described above.
- the carbon material according to the embodiment of the present invention has an average circularity of particles of 0.80 to 0.95.
- the average circularity is small, but when it is scale-like, the rapid charge / discharge performance is reduced as described above, and when it is irregular, the electrode is produced. Occasionally, the gap between particles becomes large, and the electrode density is difficult to increase.
- the average circularity is too high, the contact between the particles becomes small when the electrode is produced, the resistance is high, and the input / output characteristics are deteriorated. It is preferably 0.83 to 0.93, more preferably 0.85 to 0.90.
- the average circularity is calculated from the frequency distribution of circularity analyzed for 10,000 or more particles in the LPF mode using FPIA-3000 manufactured by sysmex.
- the carbonaceous layer present on the surface of the carbon material according to the embodiment of the present invention has an intensity ID of a peak derived from an amorphous component in the range of 1300 to 1400 cm ⁇ 1 and 1580 to 1620 cm ⁇ as measured by Raman spectroscopy.
- the ratio ID / IG (R value) to the peak intensity IG derived from the graphite component in the range of 1 is preferably 0.08 or more and 0.18 or less, and more preferably 0.09 or more and 0.16 or less. If it is less than 0.08, the rapid charge / discharge characteristics are impaired because the graphite crystallinity is too high. When it exceeds 0.18, side reactions are likely to occur during charge and discharge due to the presence of many defects, and cycle characteristics are impaired. By having an appropriate R value, it becomes a carbon material with less self-discharge and deterioration of the battery during holding after charging.
- the Raman spectrum can be measured, for example, by observing with an attached microscope using NRS-5100 manufactured by JASCO Corporation
- an average interplanar spacing d002 of the (002) plane by an X-ray diffraction method is 0.337 nm or less. This increases the amount of lithium inserted and desorbed per mass of the carbon material, that is, the weight energy density increases.
- the thickness Lc in the C-axis direction of the crystallite is preferably 50 nm or more and 1000 nm from the viewpoint of weight energy density and collapsibility. More preferably, d002 is 0.3365 nm or less, and Lc is 100 nm or more and 1000 nm or less.
- d002 and Lc can be measured by a known method using a powder X-ray diffraction (XRD) method (Inayoshi Noda, Michio Inagaki, Japan Society for the Promotion of Science, 117th Committee Material, 117-71-A-1) (1963), Michio Inagaki et al., Japan Society for the Promotion of Science, 117th Committee Materials, 117-121-C-5 (1972), Michio Inagaki, “Carbon”, 1963, No. 36, pages 25-34).
- XRD powder X-ray diffraction
- Carbon material in a preferred embodiment of the present invention for the BET specific surface area, 3.0 m 2 / g or more 9.0 m 2 / g or less, and more is 3.0 m 2 / g or more 7.5 m 2 / g or less preferable. More preferably not more than 3.0 m 2 / g or more 6.5m 2 / g.
- the BET specific surface area is within this range, an irreversible side reaction on the active material surface can be suppressed without excessive use of the binder, and a large area in contact with the electrolyte can be secured. Output characteristics are improved.
- the BET specific surface area is measured by a general method of measuring the amount of adsorption / desorption of gas per unit mass.
- NOVA-1200 can be used as the measuring device.
- the total pore volume of pores having a diameter of 0.4 ⁇ m or less by a nitrogen gas adsorption method under liquid nitrogen cooling is 25.0 ⁇ L / g or more and 40.0 ⁇ L / g or less.
- the electrolytic solution can easily penetrate and the rapid charge / discharge characteristics are improved.
- generation and expansion of pores occur, and a carbon material having a total pore volume in the above range can be produced.
- the total pore volume is 25.0 ⁇ L / g or more, the negative electrode obtained from the carbon material becomes a negative electrode with few side reactions and high initial charge / discharge efficiency.
- the pore volume is preferably 27.5 ⁇ L / g to 35.0 ⁇ L / g, more preferably 28.0 ⁇ L / g to 33.0 ⁇ L / g. This aspect is excellent in terms of charging / discharging speed, and is particularly suitable for use as a power tool.
- the carbon material in a preferred embodiment of the present invention is not pulverized after graphitization. Therefore, the rhombohedral peak ratio is 5% or less, more preferably 1% or less. By making such a range, the formation of intercalation compounds with lithium is smooth, and when this is used as a negative electrode material in a lithium ion secondary battery, the lithium occlusion / release reaction is not easily inhibited, and rapid charge / discharge characteristics Will improve.
- the carbon material in a preferred embodiment of the present invention can be produced by heating particles obtained by pulverizing coke having a heat history of 1000 ° C. or less.
- a raw material for coke for example, petroleum pitch, coal pitch, coal pitch coke, petroleum coke, and a mixture thereof can be used. Among these, those subjected to delayed coking under specific conditions are desirable.
- decant oil obtained by removing the catalyst after carrying out fluidized bed catalytic cracking on heavy distillate during refining of crude oil, or coal tar extracted from bituminous coal, etc. has a temperature of 200 ° C or higher. And those having sufficient fluidity by raising the temperature of the tar obtained to 100 ° C. or higher.
- these liquids are heated to 450 ° C. or higher, more preferably 500 ° C., and even more preferably 510 ° C. or more at least at the inlet in the drum, so The charcoal rate is increased and the yield is improved.
- the pressure in the drum is preferably maintained at normal pressure or higher, more preferably 300 kPa or higher, and further preferably 400 kPa or higher. Thereby, the capacity
- coke is performed under conditions severer than usual, so that the liquid can be reacted more and coke having a higher degree of polymerization can be obtained.
- the obtained coke is cut out from the drum by a jet water flow, and the obtained lump is roughly pulverized to about 5 cm with a hammer.
- a biaxial roll crusher or a jaw crusher can be used, but pulverization is preferably performed so that the amount on a 1 mm sieve is 90% by mass or more. If excessive pulverization is performed to such an extent that fine powder with a particle size of 1 mm or less is generated in large quantities, there is a risk that in the subsequent heating process, after drying, coke powder will rise or burnout will increase. There is.
- the coke preferably has a specific optical texture area and aspect ratio in a specific range.
- the area and aspect ratio of the optical structure can be calculated by the above-mentioned method. However, when coke is obtained as a mass of several centimeters in size, it is embedded in resin as it is and mirror-finished. The cross section is observed with a polarizing microscope, and the area and aspect ratio of the optical structure are calculated.
- an optical structure in which the area is accumulated from a small area, and the accumulated area is 60% of the total optical structure area preferably the area of is 50 [mu] m 2 or more 5000 .mu.m 2 or less, more preferably 100 [mu] m 2 or more 3000 .mu.m 2 or less, and most preferably 100 [mu] m 2 or more 160 .mu.m 2 or less.
- the number of tissues is counted from a structure with a small aspect ratio, and the aspect ratio in the 60th tissue of the total number of tissues is 1.5 or more and 6 or less. It is more preferably 0.0 or more and 3.0 or less, and most preferably 2.3 or more and 2.6 or less.
- the coke is ground.
- the pulverization is preferably performed so that D50 is 1 ⁇ m or more and 30 ⁇ m or less. More preferably, it grind
- Graphitization is preferably performed at a temperature of 2400 ° C. or higher, more preferably 2800 ° C. or higher, more preferably 3050 ° C. or higher, and most preferably 3150 ° C. or higher.
- the treatment is performed at a higher temperature, a graphite crystal grows more, and an electrode capable of storing lithium ions at a higher capacity can be obtained.
- the graphitization temperature is preferably 3600 ° C. or lower.
- the carbon raw material is calcined prior to graphitization and the organic volatiles are removed, that is, the fixed carbon content is 95% or more, more preferably 98% or more, More preferably, it is 99% or more.
- This calcination can be performed by heating at 700 to 1500 ° C., for example. Since the mass reduction at the time of graphitization is reduced by firing, it is possible to increase the amount of treatment once in the graphitization apparatus.
- graphitization is performed in an oxygen-free atmosphere, for example, in a nitrogen gas-filled environment or an argon-filled environment, but the graphitization treatment in the present invention is performed in an environment containing a constant concentration of oxygen gas or a graphitization process. It is preferable that an oxidation treatment is performed after this.
- graphite has a highly active site on the surface, and this highly active site causes a side reaction in the battery, causing a decrease in initial charge / discharge efficiency, cycle characteristics, and power storage characteristics.
- this highly active site is removed by an oxidation reaction, the number of highly active sites on the surface of the graphite particles constituting the carbon material is small, and side reactions in the battery are suppressed. A carbon material with improved efficiency, cycle characteristics, and power storage characteristics can be obtained.
- the method of producing a carbon material of the present invention comprising the step of contacting at 500 ° C. or higher temperature and oxygen gas (O 2).
- the temperature for contact with oxygen gas is more preferably 1000 ° C. or higher.
- the upper limit temperature is the temperature during graphitization.
- a separate heat treatment can be performed and contacted with oxygen.
- the graphitization treatment and the oxidation treatment can be performed in the same equipment.
- the surface of the graphite particles is oxidized, thereby removing high active sites on the surface and improving battery characteristics.
- the process and equipment can be simplified, economic efficiency, safety and mass productivity are improved.
- the graphitization treatment is not limited as long as it can be performed in an environment containing a certain concentration of oxygen.
- the graphite crucible is filled with a material to be graphitized and covered. Without contacting the upper portion with the gas containing oxygen gas, with a graphite crucible provided with a plurality of oxygen inlet holes with a diameter of 1 mm to 50 mm, or with a plurality of cylindrical oxygens with a diameter of 1 mm to 50 mm connected to the outside of the graphite crucible It can be performed by a method of energizing and generating heat with the inflow cylinder provided.
- carbonization or graphitization is performed on the upper part of the crucible.
- Oxygen gas-containing gas may be lightly blocked by covering with felt or a porous plate.
- argon or nitrogen gas may be allowed to flow in
- the oxygen concentration in the vicinity of the surface of the material to be graphitized is preferably 1% or more in the graphitization step without being completely replaced with argon or nitrogen gas. Is preferably adjusted to 1 to 20%.
- the oxygen gas-containing gas is preferably air, but a low oxygen concentration gas whose oxygen concentration is adjusted within the above concentration can also be used.
- a large amount of argon or nitrogen gas requires energy for gas concentration, and if gas is circulated, the heat necessary for graphitization is exhausted out of the system, and more energy is required. To do. Therefore, it is preferable to perform graphitization in an open atmosphere environment from the viewpoint of effective use of energy and economical efficiency.
- the surface oxidation occurs after the cooling process of the graphitization process or after the graphitization process.
- the furnace it is preferable to design the furnace so that air flows in when the graphitization furnace is cooled and the oxygen concentration in the furnace becomes 1 to 20%.
- air can enter and exit during and before and after the graphitization treatment, so that oxidation occurs in the cooling process after the graphitization treatment.
- the temperature becomes 3000 ° C. or higher, so that not only oxidation but a combustion reaction occurs.
- the treatment is performed at a temperature of 500 ° C. or higher in the presence of oxygen gas at an appropriate oxygen gas concentration and heating time according to the temperature.
- the removal method include a method of removing graphite material in a range from a portion in contact with the oxygen gas-containing gas to a predetermined depth. That is, a graphite material having a depth thereafter is obtained.
- the predetermined depth is 2 cm from the surface, more preferably 3 cm, and even more preferably 5 cm.
- the pulverization treatment is not performed after graphitization. However, it can be crushed to such an extent that the particles are not crushed after graphitization.
- an electrode is produced using a carbon material produced by modifying the surface shape and surface activity of particles through an appropriate oxidation treatment in a preferred embodiment of the present invention as an active material, It is possible to make the contact between adjacent particles stable and make the electrode suitable for repeated charge and discharge of the battery.
- Carbon material for battery electrodes in a preferred embodiment of the present invention comprises the above carbon material.
- a battery electrode having low resistance and high input / output characteristics can be obtained while maintaining high capacity, high energy density, high coulomb efficiency, and high cycle characteristics.
- the carbon material for battery electrodes for example, it can be used as a negative electrode active material and a negative electrode conductivity imparting material for lithium ion secondary batteries.
- the carbon material for battery electrodes in a preferred embodiment of the present invention only the carbon material can be used, but spherical natural graphite or artificial graphite having d002 of 0.3370 nm or less with respect to 100 parts by mass of the carbon material. 0.01 to 200 parts by mass, preferably 0.01 to 100 parts by mass, or 0.01 to 120 parts by mass of natural graphite or artificial graphite having a d002 of 0.3370 nm or less and an aspect ratio of 2 to 100 Part, preferably 0.01 to 100 parts by mass, can also be used.
- the mixing can be performed by appropriately selecting a mixed material according to the required battery characteristics and determining the mixing amount.
- carbon fibers can be blended with the carbon material for battery electrodes.
- the blending amount is 0.01 to 20 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the carbon material.
- carbon fibers examples include organic carbon fibers such as PAN-based carbon fibers, pitch-based carbon fibers, and rayon-based carbon fibers, and vapor grown carbon fibers.
- organic carbon fibers such as PAN-based carbon fibers, pitch-based carbon fibers, and rayon-based carbon fibers
- vapor grown carbon fibers having high crystallinity and high thermal conductivity is particularly preferable.
- carbon fibers are adhered to the particle surface of the carbon material, vapor grown carbon fibers are particularly preferable.
- Vapor-grown carbon fiber is produced, for example, by using an organic compound as a raw material, introducing an organic transition metal compound as a catalyst into a high-temperature reactor together with a carrier gas, and subsequently heat-treating it (Japanese Patent Laid-Open No. No. 60-54998, Japanese Patent No. 2778434, etc.).
- the fiber diameter is 2 to 1000 nm, preferably 10 to 500 nm, and the aspect ratio is preferably 10 to 15000.
- organic compound used as a raw material for carbon fiber examples include gases such as toluene, benzene, naphthalene, ethylene, acetylene, ethane, natural gas, carbon monoxide, and mixtures thereof. Of these, aromatic hydrocarbons such as toluene and benzene are preferred.
- the organic transition metal compound contains a transition metal serving as a catalyst.
- the transition metal include metals of groups IVa, Va, VIa, VIIa, and VIII of the periodic table.
- compounds such as ferrocene and nickelocene are preferable.
- the carbon fiber may be one obtained by pulverizing or pulverizing long fibers obtained by a vapor phase method or the like. Further, the carbon fibers may be aggregated in a flock shape.
- the carbon fiber is preferably one having no thermal decomposition product derived from an organic compound or the like on its surface or one having a high carbon structure crystallinity.
- Carbon fibers to which no pyrolyzate is attached or carbon fibers having a high carbon structure crystallinity are obtained by, for example, firing (heat treatment) carbon fibers, preferably vapor grown carbon fibers, in an inert gas atmosphere. It is done. Specifically, carbon fibers to which no pyrolyzate is attached can be obtained by heat treatment at about 800 to 1500 ° C. in an inert gas such as argon.
- the carbon fiber having high carbon structure crystallinity is preferably obtained by heat treatment in an inert gas such as argon at 2000 ° C. or higher, more preferably 2000 to 3000 ° C.
- the carbon fiber preferably contains a branched fiber. Further, there may be a portion where the entire fiber has a hollow structure communicating with each other. Therefore, the carbon layer which comprises the cylindrical part of a fiber is continuing.
- a hollow structure is a structure in which a carbon layer is wound in a cylindrical shape, and includes a structure that is not a complete cylinder, a structure that has a partial cut portion, and a structure in which two stacked carbon layers are bonded to one layer. .
- the cross section of the cylinder is not limited to a perfect circle, but includes an ellipse or a polygon.
- the carbon fiber has an (002) plane average plane distance d002 of preferably 0.344 nm or less, more preferably 0.339 nm or less, and particularly preferably 0.338 nm or less, as determined by X-ray diffraction. Further, it is preferable that the thickness Lc in the C-axis direction of the crystallite is 40 nm or less.
- Electrode paste in a preferred embodiment of the present invention comprises the battery electrode carbon material and a binder.
- This electrode paste is obtained by kneading the carbon material for battery electrodes and a binder.
- known apparatuses such as a ribbon mixer, a screw kneader, a Spartan rewinder, a ladyge mixer, a planetary mixer, and a universal mixer can be used.
- the electrode paste can be formed into a sheet shape, a pellet shape, or the like.
- binder used for the electrode paste examples include fluorine-based polymers such as polyvinylidene fluoride and polytetrafluoroethylene, and rubber-based materials such as SBR (styrene butadiene rubber).
- the amount of the binder used is suitably 1 to 30 parts by mass with respect to 100 parts by mass of the carbon material for battery electrodes, but about 3 to 20 parts by mass is particularly preferable.
- a solvent can be used when kneading.
- the solvent include known solvents suitable for each binder, such as toluene and N-methylpyrrolidone in the case of a fluoropolymer; water in the case of SBR; and dimethylformamide and isopropanol.
- a binder using water as a solvent it is preferable to use a thickener together. The amount of the solvent is adjusted so that the viscosity is easy to apply to the current collector.
- Electrode in a preferred embodiment of the present invention is composed of a molded body of the electrode paste.
- the electrode is obtained, for example, by applying the electrode paste onto a current collector, drying, and pressure-molding.
- the current collector examples include aluminum, nickel, copper, stainless steel foil, mesh, and the like.
- the coating thickness of the paste is usually 50 to 200 ⁇ m. If the coating thickness becomes too large, the negative electrode may not be accommodated in a standardized battery container.
- the method for applying the paste is not particularly limited, and examples thereof include a method in which the paste is applied with a doctor blade or a bar coater and then molded with a roll press or the like.
- Examples of the pressure molding method include molding methods such as roll pressing and press pressing.
- the pressure during pressure molding is preferably about 1 to 3 t / cm 2 .
- the electrode density of the electrode increases, the battery capacity per volume usually increases. However, if the electrode density is too high, the cycle characteristics usually deteriorate.
- the electrode paste according to a preferred embodiment of the present invention is used, a decrease in cycle characteristics is small even when the electrode density is increased, so that an electrode having a high electrode density can be obtained.
- the maximum value of the electrode density of the electrode obtained using this electrode paste is usually 1.6 to 1.9 g / cm 3 .
- the electrode thus obtained is suitable for a negative electrode of a battery, particularly a negative electrode of a secondary battery.
- Electrode Using the electrode as a constituent element (preferably a negative electrode), a battery or a secondary battery can be used.
- a battery or a secondary battery in a preferred embodiment of the present invention will be described by taking a lithium ion secondary battery as a specific example.
- a lithium ion secondary battery has a structure in which a positive electrode and a negative electrode are immersed in an electrolytic solution or an electrolyte.
- the electrode in a preferred embodiment of the present invention is used for the negative electrode.
- a lithium-containing transition metal oxide is usually used as the positive electrode active material, preferably at least selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mo and W.
- An oxide mainly containing at least one transition metal element selected from Fe, Co, and Ni and lithium and having a molar ratio of lithium to transition metal of 0.3 to 2.2 is used.
- Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P, B, or the like may be contained within a range of less than 30 mol% with respect to the transition metal present mainly.
- the value of x is a value before the start of charging / discharging, and increases / decreases by charging / discharging.
- the D50 of the positive electrode active material is not particularly limited, but is preferably 0.1 to 50 ⁇ m.
- the volume of particles having a particle size of 0.5 to 30 ⁇ m is preferably 95% or more. More preferably, the volume occupied by a particle group having a particle size of 3 ⁇ m or less is 18% or less of the total volume, and the volume occupied by a particle group having a particle size of 15 ⁇ m or more and 25 ⁇ m or less is 18% or less of the total volume.
- the specific surface area of the positive electrode active material is not particularly limited, but is preferably 0.01 ⁇ 50m 2 / g by BET method, in particular 0.2m 2 / g ⁇ 1m 2 / g are preferred.
- the pH of the supernatant when 5 g of the positive electrode active material is dissolved in 100 ml of distilled water is preferably 7 or more and 12 or less.
- a separator may be provided between the positive electrode and the negative electrode.
- the separator include non-woven fabric, cloth, microporous film, or a combination thereof, mainly composed of polyolefin such as polyethylene and polypropylene.
- organic electrolytes As the electrolyte and electrolyte constituting the lithium ion secondary battery in a preferred embodiment of the present invention, known organic electrolytes, inorganic solid electrolytes, and polymer solid electrolytes can be used. From the viewpoint of electrical conductivity, organic electrolytes are used. preferable.
- organic electrolyte examples include diethyl ether, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, ethylene glycol phenyl ether, 1 , 2-dimethoxyethane, diethoxyethane, etc.
- carbonates such as ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, vinylene carbonate, ⁇ -butyrolactone, 1,3-dioxolane, diethyl ether, diethoxyethane, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, etc.
- nonaqueous solvents such as carbonates such as ethylene carbonate and propylene carbonate. These solvents can be used alone or in admixture of two or more.
- Lithium salts are used as solutes (electrolytes) for these solvents.
- Commonly known lithium salts include LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCl, LiCF 3 SO 3 , LiCF 3 CO 2 , LiN (CF 3 SO 2 ) 2 and the like. is there.
- polymer solid electrolyte examples include a polyethylene oxide derivative and a polymer containing the derivative, a polypropylene oxide derivative and a polymer containing the derivative, a phosphate ester polymer, a polycarbonate derivative and a polymer containing the derivative.
- Paste preparation Aqueous solution 3 in which 1.5 parts by mass of carboxymethyl cellulose (CMC) and water are appropriately added to 100 parts by mass of a carbon material to adjust the viscosity, and styrene-butadiene rubber (SBR) fine particles having a solid content ratio of 40% are dispersed. .8 parts by mass was added and stirred and mixed to prepare a slurry-like dispersion having sufficient fluidity, which was used as the main agent stock solution.
- CMC carboxymethyl cellulose
- SBR styrene-butadiene rubber
- Negative electrode production The main agent stock solution was applied on a high-purity copper foil to a thickness of 150 ⁇ m using a doctor blade, and vacuum-dried at 70 ° C. for 12 hours. After punching out so that the coating area becomes 20 cm 2 , the sheet is sandwiched between super steel press plates, and the press pressure is about 1 ⁇ 10 2 to 3 ⁇ 10 2 N / mm 2 (1 ⁇ 10 3 to 3 ⁇ 10 3 kg / It pressed so that it might become cm ⁇ 2 >), and the negative electrode 1 was produced. Further, after punching out the coated part to 16 mm ⁇ , it was pressed by the same method as that of the negative electrode 1 so that the pressing pressure was 1 ⁇ 10 2 N / mm 2 (1 ⁇ 10 3 kg / cm 2 ). 2 was produced.
- Electrolyte LiPF 6 as an electrolyte was dissolved in a mixed solution of 8 parts by mass of EC (ethylene carbonate) and 12 parts by mass of DEC (diethyl carbonate) to a concentration of 1 mol / liter.
- Measurement test of charge / discharge cycle capacity maintenance rate Tests were performed using a bipolar cell. Charging was carried out at a constant current value of 50 mA (corresponding to 2C) with an upper limit voltage of 4.15 V from the rest potential, and then charged at a cutoff current value of 1.25 mA in the CV mode. The discharge was performed at a lower limit voltage of 2.8 V and 50 mA was discharged in the CC mode. Under the above conditions, 500 cycles of charge and discharge were repeated in a constant temperature bath at 25 ° C.
- Electrode density The main agent stock solution was applied on a high-purity copper foil to a thickness of 150 ⁇ m using a doctor blade, and vacuum dried at 70 ° C. for 12 hours. This was punched to 15 mm ⁇ , the punched electrode was sandwiched between super steel press plates, and pressed so that the pressing pressure was 1 ⁇ 10 2 N / mm 2 (1 ⁇ 10 3 kg / cm 2 ) with respect to the electrode, The electrode density was calculated from the electrode weight and electrode thickness.
- Example 1 A crude oil produced in Liaoningzhou, China (API28, wax content 17% by mass, sulfur content 0.66% by mass) was distilled at atmospheric pressure, using a sufficient amount of Y-type zeolite catalyst for heavy distillate, 510 Fluidized bed catalytic cracking was performed at °C and normal pressure. The solid content of the catalyst and the like was centrifuged until the obtained oil became clear to obtain a decant oil. This oil was put into a small delayed coking process. The drum inlet temperature was maintained at 505 ° C. and the drum internal pressure was maintained at 600 kPa (6 kgf / cm 2 ) for 10 hours, and then cooled with water to obtain a black lump.
- API28 wax content 17% by mass, sulfur content 0.66% by mass
- the resulting black mass was crushed with a hammer to a maximum of about 5 cm and then dried at 200 ° C. in a kiln. This was designated as coke 1.
- the coke 1 was observed and image-analyzed with the above-mentioned polarizing microscope, and the area was accumulated from a small area of tissue, and the area of the tissue when measuring 60% of the total area was 153 ⁇ m 2 .
- the tissues having a small aspect ratio were arranged in order, and the aspect ratio of the structure that became 60% of the whole particles was 2.41.
- a polarizing microscope photograph (480 ⁇ m ⁇ 640 ⁇ m) of the coke 1 is shown in FIG.
- the black part is the embedded resin, and the gray part is the optical structure.
- the coke 1 was pulverized with a bantam mill manufactured by Hosokawa Micron, and then coarse powder was cut using a sieve having an opening of 45 ⁇ m.
- the pulverized coke 1 was further pulverized by a jet mill manufactured by Seishin Corporation.
- This powder coke 1 was filled in a graphite crucible and subjected to heat treatment for 1 week in an Atchison furnace so that the maximum temperature reached about 3300 ° C. At this time, a plurality of oxygen inflow holes are provided in the graphite crucible so that air can enter and exit during and before and after the graphitization treatment, and the powder is oxidized for about one week in the cooling process so that the particles are non-scaled.
- a carbon material was obtained. After measuring various physical properties of the obtained sample, electrodes were prepared as described above, and cycle characteristics and the like were measured. The results are shown in Table 1.
- FIG. 2 shows a polarizing microscope photograph (480 ⁇ m ⁇ 640 ⁇ m) of the carbon material. The black part is resin and the gray part is optical structure.
- a plurality of oxygen inflow holes are provided in the graphite crucible so that air can enter and exit during and before and after the graphitization treatment, and the powder is oxidized for about one week in the cooling process so that the particles are non-scaled.
- a carbon material was obtained. After measuring various physical properties of the obtained sample, electrodes were prepared as described above, and cycle characteristics and the like were measured. The results are shown in Table 1.
- Comparative Example 2 For the coke 1 described in Example 1, a rotary kiln (electric heater external heating type, aluminum oxide SSA-S, ⁇ 120 mm inner tube) with an outer wall temperature at the center of the inner tube set to 1450 ° C. was used, and the residence time was 15 minutes. The coke was calcined by adjusting the feed amount and the inclination angle so as to be, and heating was performed, whereby calcined coke 1 was obtained. The calcined coke 1 was observed and image-analyzed with a polarizing microscope in the same manner as in Example 1. The results are shown in Table 1.
- the calcined coke 1 was pulverized with a bantam mill manufactured by Hosokawa Micron, and then coarse powder was cut using a sieve having an opening of 45 ⁇ m. Next, air classification was performed with a turbo classifier TC-15N manufactured by Nissin Engineering, and powder calcined coke 1 substantially free of particles having a particle size of 1.0 ⁇ m or less was obtained. This powder calcined coke 1 was filled in a graphite crucible and subjected to heat treatment for 1 week in an Atchison furnace so that the maximum temperature reached about 3300 ° C.
- a plurality of oxygen inflow holes are provided in the graphite crucible so that air can enter and exit during and before and after the graphitization treatment, and the powder is oxidized for about one week in the cooling process, so that the particles are scaly.
- a carbon material was obtained. Table 1 shows the results of measuring various physical properties of this carbon material, preparing electrodes in the same manner as in Example 1, and measuring cycle characteristics and the like. In this example, the particles become scaly, so that the orientation is increased, the resistance is increased, and the rapid charge / discharge characteristics are deteriorated.
- Comparative Example 3 2 mass% of boron carbide was added to the powder coke 2 described in Comparative Example 1 and heat-treated at 2600 ° C. in an argon atmosphere in a high temperature furnace manufactured by Kurata Giken, and then mixed well for use as a sample. After measuring various physical properties of the obtained carbon material, an electrode was produced in the same manner as in Example 1, and cycle characteristics and the like were measured. The results are shown in Table 1.
- Table 1 Although highly active sites on the particle surface disappear due to the addition of boron, since argon is used, it is very expensive.
- the specific surface area and pore volume are significantly reduced due to the influence of heat treatment in an inert gas atmosphere, the charge / discharge characteristics at a high rate are extremely deteriorated. In addition, the long-term cycle characteristics deteriorate due to the influence of residual impurities.
- Comparative Example 4 Coke 1 described in Example 1 was pulverized with a jet mill to obtain carbonaceous particles having a D50 of 10.2 ⁇ m. The particles were mixed with a binder pitch having a softening point of 80 ° C. at a mass ratio of 100: 30, put into a kneader heated to 140 ° C., and mixed for 30 minutes. This mixture was filled in a mold of a mold press machine and molded at a pressure of 0.30 MPa to produce a molded body. The obtained molded body was put into an alumina crucible and kept at 1300 ° C. for 5 hours in a nitrogen stream with a roller hearth kiln to remove volatile matter.
- the graphite was heated in an Atchison furnace so that the maximum temperature reached about 3300 ° C. over one week to perform graphitization to obtain massive graphite.
- the obtained massive graphite was pulverized with a bantam mill manufactured by Hosokawa Micron, and then coarse powder was cut using a sieve having an opening of 45 ⁇ m.
- air classification was performed with a turbo classifier TC-15N manufactured by Nisshin Engineering, and a carbon material substantially free of particles having a particle size of 1.0 ⁇ m or less was obtained.
- an electrode was produced in the same manner as in Example 1, and cycle characteristics and the like were measured.
- Comparative Example 5 Spherical natural graphite having a D50 of 17 ⁇ m, a d002 of 0.3354 nm, a specific surface area of 5.9 m 2 / g, and a circularity of 0.98 is filled in a rubber container and sealed, and the pressure of the liquid is measured by a hydrostatic press. Pressure treatment was performed at 150 MPa (1500 kgf / cm 2 ). The obtained graphite lump was crushed by a pin mill to obtain a graphite powder material. After measuring various physical properties of the obtained carbon material, an electrode was produced in the same manner as in Example 1, and cycle characteristics and the like were measured. The results are shown in Table 1. In this example, since spherical natural graphite is used as a raw material and compression molding is performed, the specific surface area and the total pore volume are large, and the cycle characteristics are poor.
- Comparative Example 6 Residue obtained by vacuum distillation of crude oil from the US West Coast is used as a raw material.
- the properties of the raw material are API18, Wax content of 11% by mass, and sulfur content of 3.5% by mass. This raw material is put into a small delayed coking process.
- the drum inlet temperature was maintained at 490 ° C. and the drum internal pressure was maintained at 200 kPa (2 kgf / cm 2 ) for 10 hours, and then cooled with water to obtain a black lump. After pulverizing with a hammer to a maximum of about 5 cm, drying was performed at 200 ° C. in a kiln. This was designated as coke 3.
- the coke 3 was observed and image-analyzed with a polarizing microscope in the same manner as in Example 1. The results are shown in Table 1.
- the coke 3 was pulverized and classified by the same method as in Example 1 and graphitized by the same method as in Example 1 to obtain a carbon material having non-flaky particles. After measuring various physical properties of the obtained carbon material, an electrode was produced in the same manner as in Example 1, and cycle characteristics and the like were measured. The results are shown in Table 1. In this example, the lithium ion that can be held is small due to the fineness of the optical structure, and the volume capacity density of the electrode is low, and it can be seen that there is a problem in obtaining a high-density battery.
- Comparative Example 7 The mesophase spherical graphite particles manufactured by Osaka Gas Chemical Co., Ltd. were subjected to oxidation treatment at 1100 ° C. for 1 hour in the air with a rotary kiln to obtain a carbon material. After measuring various physical properties of the obtained carbon material, an electrode was produced in the same manner as in Example 1, and cycle characteristics and the like were measured. The results are shown in Table 1. In this example, since the circularity of the particles is high, the resistance in the battery is very high, and the cycle characteristics are also deteriorated due to the influence.
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Abstract
Description
携帯機器用途では、電気・電子機器の小型化、軽量化、また機能の多様化に伴う消費電力の増加等により、より高いエネルギー密度を有するリチウムイオン二次電池が求められている。
また、電動ドリル等の電動工具や、ハイブリッド自動車等の用途で、高出力で大容量の二次電池への要求が高まっている。この分野では従来、鉛二次電池、ニッケルカドミウム二次電池、ニッケル水素二次電池が主に使用されているが、小型軽量で高エネルギー密度のリチウムイオン二次電池への期待は高く、大電流負荷特性に優れたリチウムイオン二次電池が求められている。
これらのうち天然黒鉛は安価に入手でき、黒鉛化度が高い為放電容量や電極密度は高いが、粒子形状が鱗片状であり、大きな比表面積を有することや、反応性の高いグラファイトのエッジ面により電解液が分解され、初回充放電時のクーロン効率が非常に低い、ガスが発生する、ということが問題であった。また、サイクル特性も良くはなかった。これらを解決するため、日本国特許第3534391号公報(米国特許第6632569号、特許文献2)等では、球状に加工した天然黒鉛の表面に、カーボンをコーティングする方法が提案されている。
[1] 粉末XRD測定から得られる黒鉛結晶の(110)面のピーク強度I110と(004)面のピーク強度I004の比I110/I004が0.10以上0.35以下、平均円形度が0.80以上0.95以下、X線回折法による(002)面の平均面間隔d002が0.337nm以下、窒素ガス吸着法によって測定される直径0.4μm以下の細孔の全細孔容積が25.0μL/g以上40.0μL/g以下である非鱗片状炭素材料であって、
前記炭素材料の断面において観察される光学組織について、面積の小さな組織から面積を累積し、その累計面積が全光学組織面積の60%の面積となるときの光学組織の面積をSOPとし、アスペクト比の小さな組織から組織の数を数え組織全体の数の60%番目の組織におけるアスペクト比をAROP、レーザー回析法による体積基準累積粒径分布におけるメジアン径をD50としたとき、
1.5≦AROP≦6.0 および
0.2×D50≦(SOP×AROP)1/2<2×D50
の関係を有する炭素材料。
[2] D50が1μm以上30μm以下である前記1に記載の炭素材料。
[3] BET比表面積が3.0m2/g以上9.0m2/g以下である前記1または2に記載の炭素材料。
[4] ラマン分光スペクトルで観測される1350cm-1付近のピーク強度IDと1580cm-1付近のピーク強度IGの強度比であるR値(ID/IG)が0.08~0.18である前記1~3のいずれか1項に記載の炭素材料。
[5] 前記1~4のいずれか1項に記載の炭素材料の製造方法であって、熱履歴が1000℃以下のコークスをD50が10μm以下となるように粉砕した粒子を2400℃~3600℃で黒鉛化する工程及び加熱下において酸素ガスと接触させる工程を含み、該コークスが、断面において観察される光学組織について、面積の小さな組織から面積を累積し、その累計面積が全光学組織面積の60%の面積となるときの光学組織の面積が50μm2以上5000μm2以下であり、かつアスペクト比の小さな組織から組織の数を数え組織全体の数の60%番目の組織におけるアスペクト比が1.5以上6以下であるコークスを用いる炭素材料の製造方法。
[6] 酸素ガスと接触させる工程が、黒鉛化する工程の加熱時に酸素と接触させるものである前記5に記載の炭素材料の製造方法。
[7] 酸素ガスと接触させる工程が、黒鉛化する工程後に冷却する過程で酸素と接触させるものである前記5に記載の炭素材料の製造方法。
[8] 酸素ガスと接触させる工程が、黒鉛化の工程が完了した後、別途加熱処理を行って酸素と接触させるものである前記5に記載の炭素材料の製造方法。
[9] 前記1~4のいずれか1項に記載の炭素材料を含む電池電極用炭素材料。
[10] 前記9に記載の電池電極用炭素材料とバインダーとを含む電極用ペースト。
[11] 前記10に記載の電極用ペーストの成形体からなるリチウム電池用電極。
[12] 前記11に記載の電極を構成要素として含むリチウムイオン二次電池。
[13] 前記10に記載の電極用ペーストを集電体上に塗布して乾燥した後、1~3t/cm2の圧力により圧縮する工程を含むリチウム電池用電極の製造方法。
また、本発明の炭素材料は経済性、量産性に優れ、安全性の改善された方法により製造することができる。
充電電池の電極は、単位体積あたりにより多くの電気を蓄えられることが要求されている。黒鉛は、初回の充放電のクーロン効率に優れるが、リチウム挿入時の炭素原子に対するリチウム原子の量論比には上限があり、質量あたりのエネルギー密度をこれ以上向上させていくことは困難である。電極のエネルギー密度の向上のためには、電極体積あたりの質量密度の向上が必要となる。このため、一般的に電池の電極として用いるためには活物質を集電板上に塗工乾燥した後、プレスを行い、体積あたりの負極活物質の充填性を向上させる。この際、黒鉛粒子が柔らかく、プレスに伴ってある程度変形すると電極密度を極めて大きくすることが可能である。
1.5≦AROP≦6.0 および
0.2×D50≦(SOP×AROP)1/2<2×D50
より好ましいD50は5μm以上20μm以下である。この粒度ではハンドリングも容易で入出力特性が高くなり、自動車等駆動電源として使う際に必要な大電流に耐えることができる。
[偏光顕微鏡観察試料作製]
本発明における「炭素材料の断面」は以下のようにして作製する。
内容積30cm3のプラスチック製サンプル容器の底に両面テープを貼り、その上にスパチュラ2杯ほど(2g程度)の観察用サンプルを乗せる。冷間埋込樹脂(商品名:冷間埋込樹脂#105、製造会社:ジャパンコンポジット(株)、販売会社:丸本ストルアス(株))に硬化剤(商品名:硬化剤(M剤)、製造会社:日本油脂(株)、販売会社:丸本ストルアス(株))を加え、30秒練る。得られた混合物(5ml程度)を前記サンプル容器に高さ約1cmになるまでゆっくりと流し入れ、1日静置して凝固させる。次に凝固したサンプルを取り出し、両面テープを剥がす。そして、研磨板回転式の研磨機を用いて、測定する面を研磨する。
観察は200倍で行う。偏光顕微鏡で観察した画像は、OLYMPUS製CAMEDIA(登録商標) C-5050 ZOOMデジタルカメラをアタッチメントで偏光顕微鏡に接続し、撮影する。シャッタータイムは1.6秒で行う。撮影データのうち、1200ピクセル×1600ピクセルの画像を解析対象とする。これは480μm×640μmの視野に相当する。解析に使用する画像は多いほど好ましく、40枚以上で測定誤差が小さくなる。画像解析はImageJ(アメリカ国立衛生研究所製)を用いて,青色部,黄色部,赤色部,黒色部を判定した。
各色のImageJ使用時に各色を定義したパラメーターは以下の通りである。
また、鱗片状になると嵩密度が小さくなるので扱いにくくなり、電極作製のためにスラリーにする際に溶媒との親和性が低く、電極の剥離強度が弱くなることもある。
この粒子の配向性は、前述の光学組織とも関わりがある。特に、炭素材を粉砕して作製するような炭素粒子においては、AROPが1.5以上と大きい値の場合は粒子の形状も鱗片状となり配向し易くなる。そのため前述の光学組織を維持しつつ配向性を低下させるためには後述の炭素材料の熱履歴が重要となる。
なお、平均円形度はsysmex社製FPIA-3000を用いてLPFモードで10000個以上の粒子に対して解析された円形度の頻度分布により算出される。ここで円形度とは、観測された粒子像の面積と同面積を有する円の周長を粒子像の周長で割ったものであり、1に近い程真円に近い。粒子像の面積をS、周長をLとすると、以下の式で表わすことができる。
円形度=(4πS)1/2/L
ラマン分光スペクトルは、例えば日本分光社製NRS-5100を用いて、付属の顕微鏡で観察することによって、測定することが可能である。
d002及びLcは、既知の方法により粉末X線回折(XRD)法を用いて測定することができる(野田稲吉、稲垣道夫、日本学術振興会、第117委員会資料、117-71-A-1(1963)、稲垣道夫他、日本学術振興会、第117委員会資料、117-121-C-5(1972)、稲垣道夫、「炭素」、1963、No.36、25-34頁参照)。
上記前記細孔容量は27.5μL/g乃至35.0μL/gであることが好ましく、さらに好ましくは28.0μL/g乃至33.0μL/gである。この態様は充放電の速度の点で優れており、特に電動工具の用途に適している。
このような範囲とすることで、リチウムとの層間化合物の形成がスムーズになり、これを負極材料としてリチウムイオン二次電池に用いた場合、リチウム吸蔵・放出反応が阻害されづらく、急速充放電特性が向上する。
なお、炭素材料中の菱面体晶構造のピーク割合xは、六方晶構造(100)面の実測ピーク強度P1、菱面体晶構造の(101)面の実測ピーク強度P2から、下記式によって求める。
x=P2/(P1+P2)
本発明の好ましい実施態様における炭素材料は、熱履歴が1000℃以下のコークスを粉砕した粒子を加熱することにより製造することができる。
コークスの原料としては、例えば、石油ピッチ、石炭ピッチ、石炭ピッチコークス、石油コークス及びこれらの混合物を用いることができる。これらの中でも、特定の条件下でディレイドコーキングを行ったものが望ましい。
乾式で粉砕を行う場合、粉砕時にコークスに水が含まれていると粉砕性が著しく低下するので、100~1000℃程度で乾燥させることが好ましい。より好ましくは100~500℃である。コークスが高い熱履歴を有していると圧砕強度が強くなり粉砕性が悪くなる。また結晶の異方性が発達してしまうので劈開性が強くなり、鱗片状の粉末になり易くなる。粉砕する手法に特に制限はなく、公知のジェットミル、ハンマーミル、ローラーミル、ピンミル、振動ミル等を用いて行うことができる。
粉砕は、D50が1μm以上30μm以下となるように行うことが好ましい。より好ましくは1μm以上10μm以下となるように粉砕する。
また、黒鉛化炉の空気を窒素ガスやアルゴンで置換しないことによって、黒鉛化処理と酸化処理を同一設備で行うこともできる。このような方法で黒鉛化処理及び酸化処理を行うことで、黒鉛粒子の表面が酸化されることにより表面の高活性部位が除去されるなどして電池特性が改善する。また、工程及び設備を簡略化することができるため経済性、安全性及び量産性が向上する。
上記(c)のように、黒鉛化を行った後に別途酸化処理を行う場合は、酸素ガス存在下で500℃以上の温度で温度に応じて適切な酸素ガス濃度、加熱時間で処理を行う。
本発明の好ましい実施態様における適度な酸化処理を経て、粒子の表面形状及び表面活性を改質することによって製造された炭素材料を活物質として電極を作製した際、該電極を圧縮すると、該電極内部で隣接する粒子間の接触が安定なものとなり、該電極を電池の繰り返しの充放電に適したものとすることが可能である。
本発明の好ましい実施態様における電池電極用炭素材料は、上記炭素材料を含んでなる。上記炭素材料を電池電極用炭素材料として用いると、高容量、高エネルギー密度、高クーロン効率、高サイクル特性を維持したまま、低抵抗、高入出力特性の電池電極を得ることができる。
本発明の好ましい実施態様における電極用ペーストは、前記電池電極用炭素材料とバインダーとを含んでなる。この電極用ペーストは、前記電池電極用炭素材料とバインダーとを混練することによって得られる。混錬には、リボンミキサー、スクリュー型ニーダー、スパルタンリューザー、レディゲミキサー、プラネタリーミキサー、万能ミキサー等公知の装置が使用できる。電極用ペーストは、シート状、ペレット状等の形状に成形することができる。
本発明の好ましい実施態様における電極は前記電極用ペーストの成形体からなるものである。電極は例えば前記電極用ペーストを集電体上に塗布し、乾燥し、加圧成形することによって得られる。
前記電極を構成要素(好ましくは負極)として、電池または二次電池とすることができる。
正極活物質の比表面積は特に限定されないが、BET法で0.01~50m2/gが好ましく、特に0.2m2/g~1m2/gが好ましい。また正極活物質5gを蒸留水100mlに溶かしたときの上澄み液のpHとしては7以上12以下が好ましい。
なお、実施例及び比較例の炭素材料についての、光学組織に関する観察及びデータ解析、X線回折法による平均面間隔d002、R値、D50、BET法による比表面積は、本明細書の「発明を実施するための形態」に詳述した方法により測定する。また、その他の物性の測定方法は以下の通りである。
炭素粉末試料をガラス製試料板(試料板窓18×20mm、深さ0.2mm)に充填し、以下のような条件で測定を行った。
XRD装置:リガク製SmartLab(登録商標)
X線種:Cu-Kα線
Kβ線除去方法:Niフィルター
X線出力:45kV、200mA
測定範囲:5.0~10.0deg.
スキャンスピード:10.0deg./min.
得られた波形に対し、平滑化、バックグラウンド除去、Kα2除去を行い、プロファイルフィッティングを行った。その結果得られた(004)面のピーク強度I004と(110)面のピーク強度I110から配向性の指標となる強度比I110/I004を算出した。なお、各面のピークは以下の範囲のうち最大の強度のものをそれぞれのピークとして選択した。
(004)面:54.0~55.0deg
(110)面:76.5~78.0deg
炭素材料を106μmのフィルターに通して微細なゴミを取り除いて精製し、その試料0.1gを20mlのイオン交換水中に添加し、界面活性剤0.1~0.5質量%を加えることによって均一に分散させ、測定用試料溶液を調製した。分散は超音波洗浄機UT-105S(シャープマニファクチャリングシステム社製)を用い、5分間処理することにより行った。
得られた測定用試料溶液をフロー式粒子像分析装置FPIA-2100(シスメックス社製)に投入し、LPFモードで10000個の粒子に対して粒子の画像解析を行い、得られた各々の粒子の円形度の中央値を平均円形度とした。
炭素材料約5gをガラス製セルに秤量し、1kPa以下の減圧下300℃で約3時間乾燥して、水分等の吸着成分を除去した後、炭素材料の質量を測定した。その後、液体窒素冷却下における乾燥後の炭素材料の窒素ガスの吸着等温線をカンタクローム(Quantachrome)社製Autosorb-1で測定した。得られた吸着等温線のP/P0=0.992~0.995での測定点における窒素吸着量と乾燥後の炭素材料の質量から直径0.4μm以下の全細孔容積を求めた。
a)ペースト作製:
炭素材料100質量部に増粘剤としてカルボキシメチルセルロース(CMC)1.5質量部及び水を適宜加えて粘度を調節し、固形分比40%のスチレン-ブタジエンゴム(SBR)微粒子が分散した水溶液3.8質量部を加え攪拌・混合し、充分な流動性を有するスラリー状の分散液を作製し、主剤原液とした。
主剤原液を高純度銅箔上でドクターブレードを用いて150μm厚に塗布し、70℃で12時間真空乾燥した。塗布部が20cm2となるように打ち抜いた後、超鋼製プレス板で挟み、プレス圧が約1×102~3×102N/mm2(1×103~3×103kg/cm2)となるようにプレスし、負極1を作製した。また、前記の塗布部を16mmφに打ち抜いた後、負極1と同様の方法で、プレス圧が1×102N/mm2(1×103kg/cm2)となるようにプレスし、負極2を作製した。
Li3Ni1/3Mn1/3Co1/3O2(D50:7μm)を90g、導電助剤としてのカーボンブラック(TIMCAL社製、C45)を5g、結着材としてのポリフッ化ビニリデン(PVdF)を5gをN-メチル-ピロリドンを適宜加えながら攪拌・混合し、スラリー状の分散液を作製した。
この分散液を厚み20μmのアルミ箔上に厚さが均一となるようにロールコーターにより塗布し、乾燥後、ロールプレスを行い、塗布部が20cm2となるように打ち抜き、正極を得た。
[二極セル]
上記負極1、正極に対し、それぞれAl箔にAlタブ、Cu箔にNiタブを取り付けた。ポリプロピレン製フィルム微多孔膜を介してこれらを対向させ積層、アルミラミネートによりパックし電解液を注液後、開口部を熱融着により封止し、電池を作製した。
[対極リチウムセル]
ポリプロピレン製のねじ込み式フタ付きのセル(内径約18mm)内において、上記負極2と16mmφに打ち抜いた金属リチウム箔をセパレーター(ポリプロピレン製マイクロポーラスフィルム(セルガード2400))で挟み込んで積層し、電解液を加えて試験用セルとした。
EC(エチレンカーボネート)8質量部及びDEC(ジエチルカーボネート)12質量部の混合液に、電解質としてLiPF6を1モル/リットルの濃度になるように溶解した。
対極リチウムセルを用いて試験を行った。レストポテンシャルから0.002Vまで0.2mAでCC(コンスタントカレント:定電流)充電を行った。次に0.002VでCV(コンスタントボルト:定電圧)充電に切り換え、カットオフ電流値25.4μAで充電を行った。
上限電圧1.5VとしてCCモードで0.2mAで放電を行った。
試験は25℃に設定した恒温槽内で行った。この際、初回放電時の容量を放電容量とした。また初回充放電時の電気量の比率、すなわち放電電気量/充電電気量を百分率で表した結果を初回クーロン効率とした。
二極セルを用いて試験を行った。充電はレストポテンシャルから上限電圧を4.15Vとして定電流値50mA(2C相当)でCCモード充電を行ったのち、CVモードでカットオフ電流値1.25mAで充電を行った。
放電は下限電圧2.8Vとして、CCモードで50mAの放電を行った。
上記条件で、25℃の恒温槽中で500サイクル充放電を繰り返した。
初期電池容量で得られた電池容量(1C=25mAh)を基準として、満充電状態から3時間30分0.1CのCC放電をし(SOC50%)、30分休止後、25mAを5秒放電することによって、電圧降下量からオームの法則(R[Ω]=ΔV[V]/0.025[A])により電池内抵抗DC-IRを測定した。
二極セルを用いて試験を行った。セルを上限電圧4.15V、カットオフ電流値1.25mAとしてCC、CVモードにより0.2C(0.2C=約5mA)で充電後、下限電圧2.8VでCCモードにより10C(約250mA)放電し、0.2C放電容量を基準として、10Cにおける放電容量の比を算出した。
また、セルを下限電圧2.8VとしてCCモードにより0.2Cで放電後、上限電圧4.15VとしてCCモードにより10Cで充電し、0.2C充電容量を基準として、10Cにおける充電容量の比を算出した。
主剤原液を高純度銅箔上でドクターブレードを用いて150μm厚に塗布し、70℃で12時間真空乾燥した。これを15mmφに打ち抜き、打ち抜いた電極を超鋼製プレス版で挟み、プレス圧が電極に対して1×102N/mm2(1×103kg/cm2)となるようにプレスし、電極重量と電極厚みから電極密度を算出した。
中国遼寧省産原油(API28、ワックス含有率17質量%、硫黄含有率0.66質量%)を常圧蒸留し、重質溜分に対して、十分な量のY型ゼオライト触媒を用い、510℃、常圧で流動床接触分解を行った。得られたオイルが澄明となるまで触媒等の固形分を遠心分離し、デカントオイルを得た。このオイルを小型ディレイドコーキングプロセスに投入した。ドラム入り口温度は505℃、ドラム内圧は600kPa(6kgf/cm2)に10時間維持した後、水冷して黒色塊を得た。得られた黒色塊を最大5cm程度になるように金槌で粉砕した後キルンにて200℃で乾燥を行った。これをコークス1とした。
コークス1を前述の偏光顕微鏡により観察及び画像解析を行い、小さい面積の組織から面積を累積し、総面積の60%となるときの組織の面積を測定したところ、153μm2であった。また、検出された組織のうち、アスペクト比が小さな組織のものから並べていき、粒子全体の60%番目になった組織のアスペクト比は2.41であった。
また、このコークス1についての偏光顕微鏡写真(480μm×640μm)を図1に示す。黒い部分が埋込樹脂であり、灰色の部分が光学組織である。
このコークス1をホソカワミクロン製バンタムミルで粉砕し、その後45μmの目開きの篩を用いて粗粉をカットした。この粉砕後のコークス1をさらにセイシン企業製ジェットミルで粉砕した。次に、日清エンジニアリング製ターボクラシファイアーTC-15Nで気流分級し、粒径が1.0μm以下の粒子を実質的に含まない粉末コークス1(D50=6.3μm)を得た。
この粉末コークス1を黒鉛るつぼに充填し、アチソン炉にて最高到達温度が約3300℃となるように1週間かけて加熱処理を行った。このとき、黒鉛るつぼに複数の酸素流入孔を設け、黒鉛化処理の最中及び前後で空気が出入りできるようにし、冷却過程において約1週間をかけて粉体の酸化を行い、粒子が非鱗片状の炭素材料を得た。
得られた試料について各種物性を測定後、上記のように電極を作製し、サイクル特性等を測定した。結果を表1に示す。
また、その炭素材料についての偏光顕微鏡写真(480μm×640μm)を図2に示す。黒い部分が樹脂であり、灰色の部分が光学組織である。
実施例1記載のコークス1をホソカワミクロン製バンタムミルで粉砕し、その後45μmの目開きの篩を用いて粗粉をカットした。次に、日清エンジニアリング製ターボクラシファイアーTC-15Nで気流分級し、粒径が1.0μm以下の粒子を実質的に含まない粉末コークス2(D50=17.3μm)を得た。
この粉末コークス2を黒鉛るつぼに充填し、アチソン炉にて最高到達温度が約3300℃となるように1週間かけて加熱処理を行った。このとき、黒鉛るつぼに複数の酸素流入孔を設け、黒鉛化処理の最中及び前後で空気が出入りできるようにし、冷却過程において約1週間をかけて粉体の酸化を行い、粒子が非鱗片状の炭素材料を得た。
得られた試料について各種物性を測定後、上記のように電極を作製し、サイクル特性等を測定した。結果を表1に示す。
実施例1に記載のコークス1に対し、内筒中心部外壁温度を1450℃に設定したロータリーキルン(電気ヒーター外熱式、酸化アルミニウムSSA-S、φ120mm内筒管)を用い、滞留時間が15分となるようにフィード量及び傾斜角を調整し、加熱を行うことでコークスをか焼し、か焼コークス1を得た。
か焼コークス1を実施例1と同様に偏光顕微鏡により観察及び画像解析を行った。結果を表1に示す。
このか焼コークス1をホソカワミクロン製バンタムミルで粉砕し、その後45μmの目開きの篩を用いて粗粉をカットした。次に、日清エンジニアリング製ターボクラシファイアーTC-15Nで気流分級し、粒径が1.0μm以下の粒子を実質的に含まない粉末か焼コークス1を得た。
この粉末か焼コークス1を黒鉛るつぼに充填し、アチソン炉にて最高到達温度が約3300℃となるように1週間かけて加熱処理を行った。このとき、黒鉛るつぼに複数の酸素流入孔を設け、黒鉛化処理の最中及び前後で空気が出入りできるようにし、冷却過程において約1週間をかけて粉体の酸化を行い、粒子が鱗片状である炭素材料を得た。
この炭素材料について各種物性を測定後、実施例1と同様に電極を作製し、サイクル特性等を測定した結果を表1に示す。
この例では粒子が鱗片状になることで配向性が高くなり、抵抗が高くなり、また急速充放電特性が悪くなっている。
比較例1に記載の粉末コークス2に対し、炭化ホウ素を2質量%添加し倉田技研製高温炉でアルゴン雰囲気中2600℃において熱処理を行った後、試料として使用するためによく混合を行った。
得られた炭素材料について各種物性を測定後、実施例1と同様に電極を作製し、サイクル特性等を測定した。結果を表1に示す。
本例においては、ホウ素添加により粒子表面の高活性部位は消えているものの、アルゴンを用いているため非常にコストがかかる。また、不活性ガス雰囲気での熱処理の影響で比表面積及び細孔容積が著しく小さくなるため、高レートにおける充放電特性が非常に悪くなってしまう。また、残留不純物の影響により長期のサイクル特性が悪くなる。
実施例1に記載のコークス1をジェットミルで粉砕し、D50が10.2μmである炭素質粒子を得た。この粒子を軟化点80℃のバインダーピッチと100:30の質量比で混合し、140℃に加熱されたニーダーに投入して30分間混合した。
この混合物をモールドプレス機の金型に充填し、0.30MPaの圧力で成形し、成形体を作製した。
得られた成形体をアルミナ製るつぼに入れ、ローラーハースキルンにて窒素気流中、1300℃で5時間保持し揮発分を除去した。その後、黒鉛るつぼ内に入れ蓋で密閉した後、アチソン炉にて最高到達温度が約3300℃となるように1週間かけて加熱することで黒鉛化処理を行い、塊状の黒鉛を得た。
得られた塊状黒鉛をホソカワミクロン製バンタムミルで粉砕し、その後45μmの目開きの篩を用いて粗粉をカットした。次に、日清エンジニアリング製ターボクラシファイアーTC-15Nで気流分級し、粒径が1.0μm以下の粒子を実質的に含まない炭素材料を得た。
得られた炭素材料について各種物性を測定後、実施例1と同様に電極を作製し、サイクル特性等を測定した。結果を表1に示す。
本例においては黒鉛化後粉砕処理を行うことにより粒子表面が荒れ、活性なエッジ部は処理され初回クーロン効率は高いものの、全細孔容積が大きくサイクル特性が悪くなっている。また細孔は大きいものの黒鉛化後に粉砕処理を行っていることで菱面体晶が存在し、急速充放電特性も低い値となった。
D50が17μm、d002が0.3354nm、比表面積が5.9m2/g、円形度が0.98である球状天然黒鉛をゴム製の容器に充填、密閉し、静水圧プレス機により液体の圧力150MPa(1500kgf/cm2)で加圧処理を行った。得られた黒鉛塊はピンミルにて解砕を行い、黒鉛粉末材料を得た。
得られた炭素材料について各種物性を測定後、実施例1と同様に電極を作製し、サイクル特性等を測定した。結果を表1に示す。
本例においては球状天然黒鉛を原料とし、圧縮成形をしているため比表面積と全細孔容積が大きく、サイクル特性が悪くなっている。
アメリカ西海岸産原油を減圧蒸留した残渣を原料とする。本原料の性状は、API18、Wax含有率11質量%、硫黄含有率は3.5質量%である。この原料を、小型ディレイドコーキングプロセスに投入する。ドラム入り口温度は490℃、ドラム内圧は200kPa(2kgf/cm2)に10時間維持した後、水冷して黒色塊を得た。最大5cm下程度になるように金槌で粉砕した後、キルンにて200℃で乾燥を行った。これをコークス3とした。
コークス3を実施例1と同様に偏光顕微鏡により観察及び画像解析を行った。結果を表1に示す。
このコークス3を実施例1と同様な手法により粉砕・分級し、実施例1と同様の手法で黒鉛化を行い、粒子が非鱗片状である炭素材料を得た。
得られた炭素材料について各種物性を測定後、実施例1と同様に電極を作製し、サイクル特性等を測定した。結果を表1に示す。
本例においては、光学組織の細かさから保持できるリチウムイオンが少なく電極の体積容量密度が低くなっており、高密度の電池を得るためには不都合が生じていることがわかる。
大阪ガスケミカル(株)製メソフェーズ球状黒鉛粒子をロータリーキルンにて空気中において1100℃で1時間酸化処理を施し、炭素材料を得た。
得られた炭素材料について各種物性を測定後、実施例1と同様に電極を作製し、サイクル特性等を測定した。結果を表1に示す。
本例においては、粒子の円形度が高いため電池内抵抗が非常に高く、その影響でサイクル特性も悪くなっている。
Claims (13)
- 粉末XRD測定から得られる黒鉛結晶の(110)面のピーク強度I110と(004)面のピーク強度I004の比I110/I004が0.10以上0.35以下、平均円形度が0.80以上0.95以下、X線回折法による(002)面の平均面間隔d002が0.337nm以下、窒素ガス吸着法によって測定される直径0.4μm以下の細孔の全細孔容積が25.0μL/g以上40.0μL/g以下である非鱗片状炭素材料であって、
前記炭素材料の断面において観察される光学組織について、面積の小さな組織から面積を累積し、その累計面積が全光学組織面積の60%の面積となるときの光学組織の面積をSOPとし、アスペクト比の小さな組織から組織の数を数え組織全体の数の60%番目の組織におけるアスペクト比をAROP、レーザー回析法による体積基準累積粒径分布におけるメジアン径をD50としたとき、
1.5≦AROP≦6.0 および
0.2×D50≦(SOP×AROP)1/2<2×D50
の関係を有する炭素材料。 - D50が1μm以上30μm以下である請求項1に記載の炭素材料。
- BET比表面積が3.0m2/g以上9.0m2/g以下である請求項1または2に記載の炭素材料。
- ラマン分光スペクトルで観測される1350cm-1付近のピーク強度IDと1580cm-1付近のピーク強度IGの強度比であるR値(ID/IG)が0.08~0.18である請求項1~3のいずれか1項に記載の炭素材料。
- 請求項1~4のいずれか1項に記載の炭素材料の製造方法であって、熱履歴が1000℃以下のコークスをD50が10μm以下となるように粉砕した粒子を2400℃~3600℃で黒鉛化する工程及び加熱下において酸素ガスと接触させる工程を含み、該コークスが、断面において観察される光学組織について、面積の小さな組織から面積を累積し、その累計面積が全光学組織面積の60%の面積となるときの光学組織の面積が50μm2以上5000μm2以下であり、かつアスペクト比の小さな組織から組織の数を数え組織全体の数の60%番目の組織におけるアスペクト比が1.5以上6以下であるコークスを用いる炭素材料の製造方法。
- 酸素ガスと接触させる工程が、黒鉛化する工程の加熱時に酸素と接触させるものである請求項5に記載の炭素材料の製造方法。
- 酸素ガスと接触させる工程が、黒鉛化する工程後に冷却する過程で酸素と接触させるものである請求項5に記載の炭素材料の製造方法。
- 酸素ガスと接触させる工程が、黒鉛化の工程が完了した後、別途加熱処理を行って酸素と接触させるものである請求項5に記載の炭素材料の製造方法。
- 請求項1~4のいずれか1項に記載の炭素材料を含む電池電極用炭素材料。
- 請求項9に記載の電池電極用炭素材料とバインダーとを含む電極用ペースト。
- 請求項10に記載の電極用ペーストの成形体からなるリチウム電池用電極。
- 請求項11に記載の電極を構成要素として含むリチウムイオン二次電池。
- 請求項10に記載の電極用ペーストを集電体上に塗布して乾燥した後、1~3t/cm2の圧力により圧縮する工程を含むリチウム電池用電極の製造方法。
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- 2016-02-08 KR KR1020177020682A patent/KR101994801B1/ko active IP Right Grant
- 2016-02-08 WO PCT/JP2016/053665 patent/WO2016129557A1/ja active Application Filing
- 2016-02-08 CN CN201680010205.5A patent/CN107250037B/zh not_active Expired - Fee Related
- 2016-02-08 JP JP2016574793A patent/JP6605512B2/ja not_active Expired - Fee Related
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US11899038B2 (en) | 2019-12-20 | 2024-02-13 | Resonac Corporation | Acceleration sensor, acceleration evaluation method using same, and load provided with acceleration sensor |
Also Published As
Publication number | Publication date |
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JP6605512B2 (ja) | 2019-11-13 |
CN107250037A (zh) | 2017-10-13 |
KR20170100606A (ko) | 2017-09-04 |
KR101994801B1 (ko) | 2019-07-01 |
US10377633B2 (en) | 2019-08-13 |
JPWO2016129557A1 (ja) | 2017-11-16 |
DE112016000661T5 (de) | 2017-10-26 |
US20180009665A1 (en) | 2018-01-11 |
CN107250037B (zh) | 2019-07-19 |
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