WO2010073931A1 - 負極炭素材料の製造方法 - Google Patents
負極炭素材料の製造方法 Download PDFInfo
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- WO2010073931A1 WO2010073931A1 PCT/JP2009/070830 JP2009070830W WO2010073931A1 WO 2010073931 A1 WO2010073931 A1 WO 2010073931A1 JP 2009070830 W JP2009070830 W JP 2009070830W WO 2010073931 A1 WO2010073931 A1 WO 2010073931A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a method for producing a negative electrode carbon material, and particularly relates to a simple method for producing a negative electrode carbon material.
- Non-aqueous electrolyte lithium secondary battery using a carbonaceous material as a negative electrode has been widely studied.
- Non-aqueous electrolyte lithium secondary batteries are still in high demand as power sources for portable devices, but new applications include electric vehicles (EVs) driven only by motors and hybrid types that combine motors with internal combustion engines. Development as a battery for an electric vehicle such as an electric vehicle (HEV) is also active.
- EVs electric vehicles
- HEV electric vehicle
- a carbon-based material As a material constituting the negative electrode of the lithium secondary battery, a carbon-based material is mainly used, and other than that, a material made of a metal element or a semi-metal element such as Zn, Al, Si, Ge, Sn, Sb, or the like can be given. It is done.
- the carbon-based material non-graphitizable carbon (also referred to as hard carbon) having a potential that discharge capacity per gram of carbon greatly exceeds the theoretical value of 372 mAh / g of graphite is also widely used.
- non-graphitizable carbon has attracted attention from the viewpoint of high input and output characteristics that repeatedly supply and accept large power in a short time.
- FIG. 1 shows a conventional typical process for producing a desired negative electrode material for a battery from pitch raw materials.
- a 2- or 3-ring aromatic compound having a boiling point of 200 ° C. or higher is added as an additive to a petroleum-based or coal-based pitch material, heated, and melt-mixed.
- a melt-mixing / molding process for forming a pitch molded body by molding a product, a porous pitch molded body by extracting and removing an additive from the pitch molded body with a solvent having a low solubility with respect to pitch and a high solubility with respect to the additive
- Extraction / drying step for obtaining a powder oxidation step for obtaining an infusible pitch by oxidizing the porous pitch formed body with an oxidant such as air, and the infusible pitch at 600 ° C.
- a detarring step in which the organic component (tar content) is removed by heating to 0 ° C. to obtain a carbon precursor with a small amount of volatile matter
- a pulverizing step in which the carbon precursor is pulverized to obtain a powdery carbon precursor, the powder Carbon precursor
- the main baking step of carbonizing the heat-treated in an inert gas of about 800 ⁇ 1500 ° C. the negative electrode carbon material is produced.
- the main object of the present invention is particularly suitable for high-current input / output non-aqueous electrolyte secondary battery applications represented by non-aqueous electrolyte secondary batteries for hybrid electric vehicles (HEVs), with reduced irreversible capacity and charge. It is providing the negative electrode material obtained by the manufacturing method of the negative electrode material for nonaqueous electrolyte secondary batteries excellent in discharge efficiency, and the said manufacturing method.
- HEVs hybrid electric vehicles
- the present inventors have conducted intensive research.
- the inert gas is not flowed or is flowed at a space velocity of 120 (min ⁇ 1 ) or less.
- the pitch after infusibilization with an oxygen content of 5 to 20 wt% to a temperature of 480 ° C to 700 ° C, the irreversible capacity is reduced and the charge / discharge efficiency is improved. It has been found that a negative electrode material can be obtained.
- the pitch after the infusibilization treatment with an oxygen content of 5 to 20 wt% is set to 480 ° C. to 700 ° C. without flowing an inert gas or at a space velocity of 120 (min ⁇ 1 ) or less.
- a method for producing a negative electrode carbon material which includes a detarring step of heating to the above temperature.
- the state where “the inert gas does not flow” refers to a state where the inert gas in the initial atmosphere of the detarring process is in a normal pressure state and does not actively generate an inert gas flow.
- the pitch after infusibilization treatment that can be used in the production method of the present invention preferably has an oxygen content of 5 to 20 wt%, more preferably 6 to 19 wt%, and still more preferably 8 to 12 wt%. If the oxygen content is less than 5 wt%, the degree of infusibilization will be insufficient and problems such as melting and adhesion will occur, and if it exceeds 20 wt%, the irreversible capacity will increase in the battery performance as the negative electrode material, and the initial charge / discharge The decrease in efficiency becomes significant.
- the pitch after the infusibilization treatment used in the detarring step is preferably in the form of particles having an average particle diameter (median diameter) of 1 to 3000 ⁇ m, more preferably an average particle diameter (median diameter) of 1 to 2000 ⁇ m, and still more preferably.
- the average particle diameter (median diameter) is a pitch of 1 to 1000 ⁇ m. If the average particle size is less than 1 ⁇ m, it is a fine powder, so that it is difficult to transfer during the manufacturing process and handling during heat treatment, and the powder is scattered and easily discharged out of the reaction system. On the other hand, if the average particle size is larger than 3000 ⁇ m, there is a problem that the infusibilization reaction does not proceed to the inside of the particles.
- the heating temperature in the detarring step is preferably 480 ° C to 700 ° C, more preferably 500 ° C to 700 ° C.
- the temperature is lower than 480 ° C., a large amount of volatile components remain, so that agglomeration of particles derived from tar generated in the next main firing step occurs and becomes a problem.
- the temperature exceeds 700 ° C., activation occurs particularly in an atmosphere where water vapor is present, and the irreversible capacity increases when used as a battery material.
- an inert gas in the detarring step of the present invention, it is preferable to use nitrogen, helium, argon or the like as the inert gas in order to prevent oxidation of the object to be fired during heat treatment.
- Any gas that does not react with the pitch after the infusibilization treatment at a temperature lower than the upper limit temperature and exists in a gaseous state at a temperature higher than the lower temperature limit of the detarring step can be used as an inert gas.
- Such inert gases include nitrogen and noble gases (such as helium, neon, and argon), organic hydrocarbon gases (such as methane, ethane, propane, butane, and pentane), gases generated during incomplete combustion of hydrogen gas, and water vapor Etc.
- the reason why a negative electrode material for a nonaqueous electrolyte secondary battery excellent in charge and discharge efficiency can be obtained is not clear, but it is considered as follows. ing. In other words, there was no clear standard for the input amount of inert gas, but rather volatile tar content is unnecessary, and a large amount of inert gas is allowed to flow out of the system. It was thought to be discharged. However, as in the present invention, the space velocity of the inert gas is 0 (min ⁇ 1 ), that is, the state where the inert gas is not flown, or the space velocity is 120 (min ⁇ 1 ) at the maximum even if the inert gas is flowed.
- the infusible pitch itself is exposed to an atmosphere where the concentration of volatile gas generated at a temperature of 700 ° C. or less from the infusible pitch is high, and smooth lithium ions are suppressed while suppressing the infusible pitch activation. This may have led to the formation of a carbon surface structure that promotes the deinsertion of.
- the inert gas is preferably a gas that does not react with the pitch after the infusibilization treatment below the upper limit temperature of the detarring step and exists in a gaseous state above the lower limit temperature of the detarring step.
- Nitrogen, helium, argon Alternatively, a mixed gas of hydrogen / butane incomplete combustion gas and water vapor is more preferable.
- processes other than a detarring process can use the manufacturing process of the conventional negative electrode material suitably.
- FIG. 1 shows a flowchart of a manufacturing process of a conventional negative electrode carbon material.
- FIG. 2 is a graph showing the relationship between space velocity and irreversible capacity.
- FIG. 3 is a graph showing the relationship between space velocity and initial charge / discharge efficiency.
- FIG. 4 is a graph showing measurement results of irreversible capacity.
- FIG. 5 is a graph showing the measurement results of the initial charge / discharge efficiency.
- the measurement items and measurement methods in the examples are as follows.
- ⁇ Measurement cell creation method and charge / discharge capacity evaluation> Using each negative electrode material manufactured in each example and comparative example, a non-aqueous electrolyte secondary battery was fabricated and its characteristics were evaluated.
- the carbonaceous material of the present invention is suitable for use as a negative electrode of a non-aqueous solvent secondary battery.
- the charge capacity, discharge capacity, and non-discharge capacity of the battery active material which are the effects of the present invention, vary in the performance of the counter electrode.
- the counter electrode lithium was evaluated. That is, a lithium secondary battery using a lithium metal having stable characteristics as a negative electrode and a negative electrode material produced in each example and comparative example as a positive electrode was constructed, and the characteristics were evaluated.
- LiPF 6 was added at a rate of 1 mol / liter to a mixed solvent in which ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate were mixed at a volume ratio of 3: 4: 4 as an electrolyte.
- a coin-type non-aqueous electrolyte lithium secondary battery of 2016 size was assembled in an Ar glove box using a polypropylene microporous membrane as a separator and a polyethylene gasket.
- lithium was doped / dedoped in the positive electrode (carbonaceous material), and the capacity at that time was determined. Doping was performed by a constant current constant voltage method. Constant current charging was performed until the voltage reached 0 V at a current density of 0.5 mA / cm 2. When the voltage reached 0 V, the current value was attenuated while maintaining a constant voltage, and charging was terminated when the current reached 20 ⁇ A. The value obtained by dividing the amount of electricity by the weight of the carbonaceous material used was defined as the charge capacity, and expressed in units of mAh / g.
- an electric current was passed in the reverse direction to undope lithium doped in the carbonaceous material.
- De-doping was performed at a current density of 0.5 mA / cm 2 , and a terminal voltage of 1.5 V was used as a cutoff voltage.
- the amount of electricity at this time was defined as the discharge capacity, and was expressed in mAh / g.
- Irreversible capacity is the difference between charge capacity and discharge capacity.
- the initial charge / discharge efficiency is a value indicating how effectively the active material was used, and was obtained by multiplying the value obtained by dividing the discharge capacity by the charge capacity by 100.
- SALD-3000J particle size distribution measuring device
- a negative electrode carbon material for a lithium ion secondary battery was manufactured from petroleum pitch as a raw material by the steps of oxidation ⁇ detarring ⁇ pulverization ⁇ main firing.
- the infusibilized pitch was tested by changing the detarring conditions. Note that “a thin layer under an air stream” means that a thin layer of powder is formed on a support plate.
- a fluidized bed is suitable as a structure that positively removes tar components that are generated, but in this experiment, if it is a powder, the powder is scattered, so a thin layer imitating the fluidized bed is used.
- the powder was pulverized after the detarring process to obtain a powder having an average particle diameter (median diameter) of 10 ⁇ m, and then the main baking treatment was performed.
- capacitance, and initial stage charging / discharging efficiency were measured.
- the irreversible capacity is low, the charge / discharge capacity is high in charge capacity and discharge capacity, and the higher the initial charge / discharge efficiency, the better the performance.
- Example 1 ⁇ Detarring step: space velocity 0 (min ⁇ 1 )> A powdery pitch 191.5 g after infusibilization treatment with an oxygen content of 18.7 wt% and an average particle size (median diameter) of 10 ⁇ m was placed in a cylindrical graphite crucible having an inner diameter of 80 mm and a height of 80 mm, and the gas outside the crucible was The graphite plate was covered and sealed so as not to enter the crucible.
- This container is placed in the center of a horizontal cylindrical heating furnace having an inner diameter of 230 mm and a length of 790 mm filled with normal-pressure nitrogen gas, and at a temperature rising rate of 250 ° C./h while maintaining the nitrogen atmosphere inside the heating furnace. The temperature was raised to 680 ° C., and the tar removal treatment was further carried out by holding at 680 ° C. for 1 hour to obtain 142.6 g of a negative electrode material precursor.
- ⁇ Main firing process> 10 g of the obtained negative electrode material precursor was deposited on an alumina plate so as to have a deposition layer height of 2 mm, placed in a horizontal tubular furnace having a diameter of 100 mm, and a rate of 250 ° C./h while flowing 10 liters of nitrogen gas per minute. The temperature was raised to 1200 ° C. and held at 1200 ° C. for 1 hour to produce a negative electrode material (carbonaceous material).
- Example 2 space velocity 0 (min ⁇ 1 )> 351.1 g of an infusible porous pitch molded body having an oxygen content of 18.7 wt% and an average particle diameter (median diameter) of 700 ⁇ m was placed in a columnar graphite crucible having an inner diameter of 80 mm and a height of 80 mm. It was sealed with a graphite plate so that the gas did not enter the crucible.
- This container is placed in the center of a horizontal cylindrical heating furnace having an inner diameter of 230 mm and a length of 790 mm filled with normal-pressure nitrogen gas, and at a temperature rising rate of 250 ° C./h while maintaining the nitrogen atmosphere inside the heating furnace.
- the temperature was raised to 680 ° C., and the tar removal treatment was carried out by holding at 680 ° C. for 1 hour to obtain 253.2 g of a negative electrode material precursor.
- the negative electrode material precursor was pulverized into a powder having an average particle diameter (median diameter) of 10 ⁇ m.
- ⁇ Main firing process> 10 g of the obtained negative electrode material precursor was deposited on an alumina plate so as to have a deposition layer height of 2 mm, placed in a horizontal tubular furnace having a diameter of 100 mm, and a rate of 250 ° C./h while flowing 10 liters of nitrogen gas per minute. The temperature was raised to 1200 ° C. and held at 1200 ° C. for 1 hour to produce a negative electrode material (carbonaceous material).
- Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this example.
- Example 3 space velocity 19 (min ⁇ 1 )>
- a fluidized bed heating apparatus 100,000 g of a porous pitch formed body after infusibilization treatment with an oxygen content of 18.7 wt% and an average particle diameter (median diameter) of 700 ⁇ m was added to butane / hydrogen in a weight ratio of 57:43.
- a gas in which water vapor is mixed at a volume ratio of 2: 8 with respect to the combustion exhaust gas obtained by burning the mixed gas at a fuel air ratio of 0.8 is used as an inert gas, and the inert gas flows at a rate of 1069 NL / min.
- the temperature was raised to 680 ° C.
- the obtained negative electrode material precursor was 80,666 g.
- This negative electrode material precursor was pulverized to an average particle diameter (median diameter) of 9 ⁇ m to form a powder.
- ⁇ Main firing process> 10 g of the obtained negative electrode material precursor was deposited on an alumina plate so as to have a deposition layer height of 2 mm, placed in a horizontal tubular furnace having a diameter of 100 mm, and a rate of 250 ° C./h while flowing 10 liters of nitrogen gas per minute. The temperature was raised to 1200 ° C. and held at 1200 ° C. for 1 hour to produce a negative electrode material (carbonaceous material).
- Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this example.
- Example 4 space velocity 100 (min ⁇ 1 )> Place 100.0 g of a porous pitch formed body after infusibilization treatment with an oxygen content of 18.7 wt% and an average particle diameter (median diameter) of 700 ⁇ m in a cylindrical fluidized bed heating apparatus having an inner diameter of 50 mm and a height of 1000 mm. While flowing normal pressure nitrogen gas from the bottom of the container at a flow rate of 5 NL / min, the temperature was raised to 680 ° C. at a temperature rising rate of 250 ° C./h, and the detarring treatment was carried out by holding at 680 ° C. for 1 hour. 0.7 g of negative electrode material precursor was obtained. The negative electrode material precursor was pulverized into a powder having an average particle diameter (median diameter) of 9 ⁇ m.
- ⁇ Main firing process> 10 g of the obtained negative electrode material precursor was deposited on an alumina plate so as to have a deposition layer height of 2 mm, placed in a horizontal tubular furnace having a diameter of 100 mm, and a rate of 250 ° C./h while flowing 10 liters of nitrogen gas per minute. The temperature was raised to 1200 ° C. and held at 1200 ° C. for 1 hour to produce a negative electrode material (carbonaceous material).
- Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this comparative example.
- Example 5 The same treatment as in Example 1 was performed except that the oxygen content of the infusible pitch was changed to 6.4 wt%. Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this example.
- Example 6 The same treatment as in Example 1 was performed except that the oxygen content of the infusible pitch was changed to 8.2 wt%. Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this example.
- Example 7 The same treatment as in Example 1 was performed except that the oxygen content of the infusible pitch was changed to 10.9 wt%. Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this example.
- Example 8 The same treatment as in Example 2 was performed except that the oxygen content of the infusible pitch was changed to 6.4 wt%.
- Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this example.
- Example 9 The same treatment as in Example 2 was performed except that the oxygen content of the infusible pitch was changed to 8.2 wt%.
- Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this example.
- Example 10 The same treatment as in Example 2 was performed except that the oxygen content of the infusible pitch was changed to 10.9 wt%.
- Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this example.
- Example 11 space velocity 0 (min ⁇ 1 )> 130.7 g of a powdery pitch after infusibilization treatment with an oxygen content of 10.9 wt% and an average particle diameter (median diameter) of 9 ⁇ m was placed in a cylindrical graphite crucible having an inner diameter of 80 mm and a height of 80 mm, and the gas outside the crucible was The graphite plate was covered and sealed so as not to enter the crucible.
- This container is placed in the center of a horizontal cylindrical heating furnace having an inner diameter of 230 mm and a length of 790 mm filled with normal-pressure nitrogen gas, and at a temperature rising rate of 250 ° C./h while maintaining the nitrogen atmosphere inside the heating furnace. The temperature was raised to 500 ° C., and the tar removal treatment was performed by holding at 500 ° C. for 1 hour to obtain 111.8 g of a negative electrode material precursor.
- ⁇ Main firing process> 10 g of the obtained negative electrode material precursor was deposited on an alumina plate so as to have a deposition layer height of 2 mm, placed in a horizontal tubular furnace having a diameter of 100 mm, and a rate of 250 ° C./h while flowing 10 liters of nitrogen gas per minute. The temperature was raised to 1200 ° C. and held at 1200 ° C. for 1 hour to produce a negative electrode material (carbonaceous material).
- Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this example.
- Example 12 space velocity 0 (min ⁇ 1 )> 309.2 g of an infusible porous pitch molded body having an oxygen content of 10.9 wt% and an average particle diameter (median diameter) of 700 ⁇ m was placed in a cylindrical graphite crucible having an inner diameter of 80 mm and a height of 80 mm, It was sealed with a graphite plate so that the gas did not enter the crucible.
- This container is placed in the center of a horizontal cylindrical heating furnace having an inner diameter of 230 mm and a length of 790 mm filled with normal-pressure nitrogen gas, and at a temperature rising rate of 250 ° C./h while maintaining the nitrogen atmosphere inside the heating furnace.
- the temperature was raised to 500 ° C., and the tar removal treatment was carried out by holding at 500 ° C. for 1 hour to obtain 269.0 g of a negative electrode material precursor.
- the negative electrode material precursor was pulverized into a powder having an average particle diameter (median diameter) of 9 ⁇ m.
- ⁇ Main firing process> 10 g of the obtained negative electrode material precursor was deposited on an alumina plate so as to have a deposition layer height of 2 mm, placed in a horizontal tubular furnace having a diameter of 100 mm, and a rate of 250 ° C./h while flowing 10 liters of nitrogen gas per minute. The temperature was raised to 1200 ° C. and held at 1200 ° C. for 1 hour to produce a negative electrode material (carbonaceous material).
- Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this example.
- ⁇ Main firing process> 10 g of the obtained negative electrode material precursor was deposited on an alumina plate so as to have a deposition layer height of 2 mm, placed in a horizontal tubular furnace having a diameter of 100 mm, and a rate of 250 ° C./h while flowing 10 liters of nitrogen gas per minute. The temperature was raised to 1200 ° C. and held at 1200 ° C. for 1 hour to produce a negative electrode material (carbonaceous material).
- Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this comparative example.
- ⁇ Main firing process> 10 g of the obtained negative electrode material precursor was deposited on an alumina plate so as to have a deposition layer height of 2 mm, placed in a horizontal tubular furnace having a diameter of 100 mm, and a rate of 250 ° C./h while flowing 10 liters of nitrogen gas per minute. The temperature was raised to 1200 ° C. and held at 1200 ° C. for 1 hour to produce a negative electrode material (carbonaceous material).
- Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this comparative example.
- Comparative Example 3 The same treatment as in Comparative Example 1 was performed except that the oxygen content of the infusible pitch was changed to 8.2 wt% and the holding temperature of the main firing was changed to 1000 ° C. Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this comparative example.
- Comparative Example 4 The same treatment as in Comparative Example 1 was performed except that the oxygen content of the infusibilized pitch was changed to 10.9 wt% and the holding temperature of the main firing was changed to 1000 ° C. Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this comparative example.
- Comparative Example 5 The same treatment as in Comparative Example 2 was performed except that the oxygen content of the infusible pitch was changed to 8.2 wt% and the holding temperature of the main firing was changed to 1000 ° C. Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this comparative example.
- Comparative Example 6 The same treatment as in Comparative Example 2 was performed except that the oxygen content of the infusible pitch was changed to 10.9 wt% and the holding temperature of the main firing was changed to 1000 ° C. Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this comparative example.
- Example 7 Except for changing the temperature of the detarring treatment from 500 ° C. to 470 ° C., the same treatment as in Example 11 was performed. As a result, the particles aggregated during the main firing, and a material prototype suitable for use could not be produced. Table 1 shows the processing conditions of this comparative example.
- Example 8 The same treatment as in Example 11 was performed except that the temperature of the detarring treatment was changed from 500 ° C to 710 ° C. Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this comparative example.
- Example 9 The same treatment as in Example 11 was performed except that the oxygen content of the infusible pitch was changed to 2.7 wt%.
- Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this comparative example.
- Example 10 The same treatment as in Example 11 was performed except that the oxygen content of the infusible pitch was changed to 21.5 wt%.
- Table 1 shows the processing conditions and characteristic measurement results of the negative electrode material obtained in this comparative example.
- Irreversible capacity with respect to the space velocity when the pitch is detarred at different space velocities after the infusibilization treatment with an oxygen content of 18.7 wt% (corresponding to Examples 1, 2, 3, 4 and Comparative Examples 1 and 2).
- 2 and FIG. 3 show the initial charge / discharge efficiency.
- FIG. 2 shows that when the space velocity is 120 (min ⁇ 1 ) or less, the irreversible capacity tends to decrease to 80 mAh / g or less.
- FIG. 3 also shows that the charge / discharge efficiency tends to improve to 85% or more when the space velocity is 120 (min ⁇ 1 ) or less.
- FIG. 5 show the results of initial charge / discharge efficiency, respectively. It can be seen that the irreversible capacity decreases and the initial charge / discharge efficiency improves as the oxygen content of the pitch after the infusibilization treatment decreases, regardless of the particle size during the detarring treatment.
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Abstract
Description
v=F/L(min-1)
(F:流量(NL/min)、L:サンプルが占めている空間の体積(L)であり、脱タール後のサンプル質量M(g)を脱タール後のサンプル密度ρ(g/cc)で除したものに1000を乗じた値 L=1000×M/ρである。)
により定義される。
CHNアナライザーによる元素分析を行い、酸素含有量は次式で計算した。
100%-C%-H%-N%
各実施例及び比較例で製造した各負極材料を用いて、非水電解質二次電池を作製し、その特性を評価した。本発明の炭素質材料は非水溶媒二次電池の負極として用いるのに適しているが、本発明の効果である電池活物質の充電容量、放電容量及び非放電容量を、対極の性能のバラツキに影響されることなく精度良く評価するために、対極リチウム評価を行った。すなわち特性の安定したリチウム金属を負極とし、各実施例及び比較例で作製した負極材料を正極とするリチウム二次電池を構成し、その特性を評価した。
各実施例及び比較例で製造した負極材料(炭素質材料)を95重量部、ポリフッ化ビニリデン5重量部に、N-メチル-2-ピロリドンを加えてペースト状とし、ペーストを銅箔上に均一に塗布し、窒素ガス雰囲気下、130℃で30分乾燥させた。シート状の電極を直径15mmの円盤状に打ち抜き、これをプレスして電極とした。電極中の炭素質材料(負極材料)の重量は約20mgになるように調整し、炭素質材料の充填率が約67%となるようにプレスを行った。
Arガス雰囲気中のグローブボックス内で行った。予め2016サイズのコイン型電池用缶の外蓋に直径17mmのステンレススチール網円板をスポット溶接した後、厚さ0.5mmの金属リチウム薄板を直径15mmの円板状に打ち抜いたものをステンレススチール網円板に圧着した。
上記のような構成のリチウム二次電池において、正極(炭素質材料)にリチウムのドーピング・脱ドーピングを行い、そのときの容量を求めた。ドーピングは定電流定電圧法により行なった。0.5mA/cm2の電流密度で0Vになるまで定電流充電を行い、0Vに達した時点で一定電圧のまま電流値を減衰させ、20μAとなった時点で充電終了とした。このときの電気量を使用した炭素質材料の重量で除した値を充電容量と定義し、mAh/gを単位として表した。
試料約0.1gに対し分散剤(カチオン系界面活性剤「SNディスパーサント7347-C」(サンノプコ社製))を3滴加え、試料に分散剤を馴染ませる。つぎに、純水30mlを加え、超音波洗浄機で約2分間分散させたのち、粒径分布測定器(島津製作所製「SALD-3000J」)で、粒径0.5~3000μmの範囲の粒径分布を求めた。この粒径分布から、累積容積が50%となる粒径をもって平均粒径Dv50(μm)とした。
JIS R7211に定められた方法に従い、30℃でブタノールを置換媒体として、真密度(ρB)を測定した。
石油ピッチを原料として、酸化→脱タール→粉砕→本焼成の工程により、リチウムイオン二次電池用負極炭素材料を製造した。本実施例および比較例では、脱タール工程に供する不融化処理後のピッチの酸素含有量及び粒径並びに脱タール工程の処理雰囲気が電池性能に及ぼす影響を調べるため、6種の酸素含有量の不融化ピッチについて、脱タール条件を変動させて実験を行った。なお、「気流下の薄層」とは、支持板の上に粉体の薄い層を形成させたことを意味する。実生産装置では発生するタール成分を積極的に除去する構造として流動層が好適であるが、本実験では粉体である場合、粉が飛散してしまうため、流動層を模した薄層とした。また、平均粒径(メディアン径)500~900μmの粒子の場合は、脱タール処理後に粉砕して、平均粒径(メディアン径)10μmの粉体とした後に本焼成処理を行った。得られた各試料について、不可逆容量、充放電容量及び初期充放電効率を測定した。リチウムイオン二次電池負極炭素材料としては、不可逆容量が低く、充放電容量は充電容量と放電容量とが高く、初期充放電効率が高いほど性能が優れていると判断される。
<脱タール工程:空間速度0(min-1)>
酸素含有量18.7wt%、平均粒径(メディアン径)10μmの不融化処理後の粉末状ピッチ191.5gを内径80mm、高さ80mmの円柱状黒鉛製坩堝に入れて、坩堝外部のガスが坩堝内に入らないように黒鉛板で蓋をして密封した。この容器を常圧の窒素ガスで内部を満たした内径230mm、長さ790mmの横型円筒形加熱炉の中央部に入れて、加熱炉内部の窒素雰囲気を保ちながら250℃/hの昇温速度で680℃まで昇温し、さらに680℃で1時間保持して脱タール処理を行い、142.6gの負極材料前駆体を得た。
得られた負極材料前駆体10gをアルミナ製板に堆積層高2mmになるように堆積し、直径100mmの横型管状炉に入れ、1分間に10リットルの窒素ガスを流しながら250℃/hの速度で1200℃まで昇温し、1200℃で1時間保持して、負極材料(炭素質材料)を製造した。
<脱タール工程:空間速度0(min-1)>
酸素含有量18.7wt%、平均粒径(メディアン径)700μmの不融化処理後の多孔性ピッチ成形体351.1gを内径80mm、高さ80mmの円柱状黒鉛製坩堝に入れて、坩堝外部のガスが坩堝内に入らないように黒鉛板で蓋をして密封した。この容器を常圧の窒素ガスで内部を満たした内径230mm、長さ790mmの横型円筒形加熱炉の中央部に入れて、加熱炉内部の窒素雰囲気を保ちながら250℃/hの昇温速度で680℃まで昇温し、さらに680℃で1時間保持して脱タール処理を行い、253.2gの負極材料前駆体を得た。この負極材料前駆体を粉砕し、平均粒径(メディアン径)10μmの粉末状とした。
得られた負極材料前駆体10gをアルミナ製板に堆積層高2mmになるように堆積し、直径100mmの横型管状炉に入れ、1分間に10リットルの窒素ガスを流しながら250℃/hの速度で1200℃まで昇温し、1200℃で1時間保持して、負極材料(炭素質材料)を製造した。
<脱タール工程:空間速度19(min-1)>
流動床型加熱装置を用いて、酸素含有量18.7wt%、平均粒径(メディアン径)700μmの不融化処理後の多孔性ピッチ成形体100,000gを、重量比57:43のブタン・水素の混合ガスを燃料空気比0.8で燃焼させた燃焼排ガスに対して水蒸気を体積比2:8の割合で混合したガスを不活性ガスとし、不活性ガスを1069NL/minの割合で流しながら、600℃/hrの加熱速度で680℃まで昇温し、この温度で1時間保持して、負極材料前駆体を作製した。得られた負極材料前駆体は80,666gであった。この負極材料前駆体を平均粒径(メディアン径)9μmに粉砕し、粉末状にした。
得られた負極材料前駆体10gをアルミナ製板に堆積層高2mmになるように堆積し、直径100mmの横型管状炉に入れ、1分間に10リットルの窒素ガスを流しながら250℃/hの速度で1200℃まで昇温し、1200℃で1時間保持して、負極材料(炭素質材料)を製造した。
<脱タール工程:空間速度100(min-1)>
酸素含有量18.7wt%、平均粒径(メディアン径)700μmの不融化処理後の多孔性ピッチ成形体100.0gを内径50mm、高さ1000mmの円柱状流動床型の加熱装置に入れて、容器下部から常圧の窒素ガスを5NL/minの流量で流しながら、250℃/hの昇温速度で680℃まで昇温し、さらに680℃で1時間保持して脱タール処理を行い、71.7gの負極材料前駆体を得た。この負極材料前駆体を粉砕し、平均粒径(メディアン径)9μmの粉末状とした。
得られた負極材料前駆体10gをアルミナ製板に堆積層高2mmになるように堆積し、直径100mmの横型管状炉に入れ、1分間に10リットルの窒素ガスを流しながら250℃/hの速度で1200℃まで昇温し、1200℃で1時間保持して、負極材料(炭素質材料)を製造した。
不融化ピッチの酸素含有量を6.4wt%に変えた以外は実施例1と同様の処理を行った。本実施例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
不融化ピッチの酸素含有量を8.2wt%に変えた以外は実施例1と同様の処理を行った。本実施例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
不融化ピッチの酸素含有量を10.9wt%に変えた以外は実施例1と同様の処理を行った。本実施例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
不融化ピッチの酸素含有量を6.4wt%に変えた以外は実施例2と同様の処理を行った。本実施例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
不融化ピッチの酸素含有量を8.2wt%に変えた以外は実施例2と同様の処理を行った。本実施例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
不融化ピッチの酸素含有量を10.9wt%に変えた以外は実施例2と同様の処理を行った。本実施例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
<脱タール工程:空間速度0(min-1)>
酸素含有量10.9wt%、平均粒径(メディアン径)9μmの不融化処理後の粉末状ピッチ130.7gを内径80mm、高さ80mmの円柱状黒鉛製坩堝に入れて、坩堝外部のガスが坩堝内に入らないように黒鉛板で蓋をして密封した。この容器を常圧の窒素ガスで内部を満たした内径230mm、長さ790mmの横型円筒形加熱炉の中央部に入れて、加熱炉内部の窒素雰囲気を保ちながら250℃/hの昇温速度で500℃まで昇温し、さらに500℃で1時間保持して脱タール処理を行い、111.8gの負極材料前駆体を得た。
得られた負極材料前駆体10gをアルミナ製板に堆積層高2mmになるように堆積し、直径100mmの横型管状炉に入れ、1分間に10リットルの窒素ガスを流しながら250℃/hの速度で1200℃まで昇温し、1200℃で1時間保持して、負極材料(炭素質材料)を製造した。本実施例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
<脱タール工程:空間速度0(min-1)>
酸素含有量10.9wt%、平均粒径(メディアン径)700μmの不融化処理後の多孔性ピッチ成形体309.2gを内径80mm、高さ80mmの円柱状黒鉛製坩堝に入れて、坩堝外部のガスが坩堝内に入らないように黒鉛板で蓋をして密封した。この容器を常圧の窒素ガスで内部を満たした内径230mm、長さ790mmの横型円筒形加熱炉の中央部に入れて、加熱炉内部の窒素雰囲気を保ちながら250℃/hの昇温速度で500℃まで昇温し、さらに500℃で1時間保持して脱タール処理を行い、269.0gの負極材料前駆体を得た。この負極材料前駆体を粉砕し、平均粒径(メディアン径)9μmの粉末状とした。
得られた負極材料前駆体10gをアルミナ製板に堆積層高2mmになるように堆積し、直径100mmの横型管状炉に入れ、1分間に10リットルの窒素ガスを流しながら250℃/hの速度で1200℃まで昇温し、1200℃で1時間保持して、負極材料(炭素質材料)を製造した。本実施例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
<脱タール工程:空間速度485(min-1)>
酸素含有量18.7wt%、平均粒径(メディアン径)10μmの不融化処理後の粉末状ピッチ200.0gを縦230mm、横500mm、厚み2mmの黒鉛製平板に均一に広げて、これを内径230mm、長さ790mmの横型円筒形加熱炉の中央部に水平に設置した。加熱炉に常圧の窒素を50NL/minの流速(空間速度:485/min)で流しながら250℃/hの昇温速度で680℃まで昇温し、さらに680℃で1時間保持して脱タール処理を行い、147.4gの負極材料前駆体を得た。
得られた負極材料前駆体10gをアルミナ製板に堆積層高2mmになるように堆積し、直径100mmの横型管状炉に入れ、1分間に10リットルの窒素ガスを流しながら250℃/hの速度で1200℃まで昇温し、1200℃で1時間保持して、負極材料(炭素質材料)を製造した。本比較例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
<脱タール工程:空間速度270(min-1)>
酸素含有量18.7wt%、平均粒径(メディアン径)700μmの不融化処理後の多孔性ピッチ成形体300.0gを内径100mm、高さ300mmの円柱状流動床型の加熱装置に入れて、容器下部から常圧の窒素ガスを40NL/minの流量で流しながら、250℃/hの昇温速度で680℃まで昇温し、さらに680℃で1時間保持して脱タール処理を行い、211.5gの負極材料前駆体を得た。この負極材料前駆体を粉砕し、平均粒径(メディアン径)9μmの粉末状とした。
得られた負極材料前駆体10gをアルミナ製板に堆積層高2mmになるように堆積し、直径100mmの横型管状炉に入れ、1分間に10リットルの窒素ガスを流しながら250℃/hの速度で1200℃まで昇温し、1200℃で1時間保持して、負極材料(炭素質材料)を製造した。本比較例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
不融化ピッチの酸素含有量を8.2wt%、本焼成の保持温度を1000℃に変更した以外は比較例1と同様の処理を行った。本比較例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
不融化ピッチの酸素含有量を10.9wt%、本焼成の保持温度を1000℃に変更した以外は比較例1と同様の処理を行った。本比較例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
不融化ピッチの酸素含有量を8.2wt%、本焼成の保持温度を1000℃に変更した以外は比較例2と同様の処理を行った。本比較例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
不融化ピッチの酸素含有量を10.9wt%、本焼成の保持温度を1000℃に変更した以外は比較例2と同様の処理を行った。本比較例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
脱タール処理の温度を500℃から470℃に変更した以外は実施例11と同様の処理を行ったところ、本焼成時には粒子が凝集し、使用に適する材料試作ができなかった。本比較例の処理条件を表1に示す。
脱タール処理の温度を500℃から710℃に変更した以外は実施例11と同様の処理を行った。本比較例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
不融化ピッチの酸素含有量を2.7wt%に変更した以外は実施例11と同様の処理を行った。本比較例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
不融化ピッチの酸素含有量を21.5wt%に変更した以外は実施例11と同様の処理を行った。本比較例により得られた負極材料の処理条件及び特性測定結果を表1に示す。
Claims (4)
- 不活性ガスを流さないか又は120(min-1)以下の空間速度で流しながら、不融化処理後のピッチを480℃~700℃の温度に加熱する脱タール工程を含む、負極炭素材料の製造方法。
- 脱タール工程に供する前記不融化処理後のピッチは酸素含有量5~20wt%である、請求項1に記載の製造方法。
- 前記不活性ガスは、脱タール工程の上限温度以下では不融化処理後のピッチと反応せず、脱タール工程の下限温度以上では気体状態で存在するガスである、請求項1に記載の製造方法。
- 前記不活性ガスは、窒素と、水素およびブタンの不完全燃焼ガスと、水蒸気と、の混合ガスである、請求項3に記載の製造方法。
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JPH07335262A (ja) * | 1994-06-03 | 1995-12-22 | Sony Corp | 非水電解液二次電池 |
JPH08279358A (ja) | 1995-02-09 | 1996-10-22 | Kureha Chem Ind Co Ltd | 電池電極用炭素質材料、その製造方法、電極構造体および電池 |
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JPH0829811A (ja) * | 1994-07-18 | 1996-02-02 | Toshiba Corp | 液晶表示装置 |
JP3502669B2 (ja) * | 1994-08-23 | 2004-03-02 | 呉羽化学工業株式会社 | 二次電池電極用炭素質材料およびその製造法 |
EP0726606B1 (en) | 1995-02-09 | 2002-12-04 | Kureha Kagaku Kogyo Kabushiki Kaisha | Carbonaceous electrode material for battery and process for production thereof |
JP3624578B2 (ja) * | 1995-11-25 | 2005-03-02 | ソニー株式会社 | 非水電解液二次電池用負極材料、その製造方法及び非水電解液二次電池 |
JPH09283145A (ja) * | 1996-04-15 | 1997-10-31 | Petoca:Kk | リチウム系二次電池用炭素材及びその製造方法 |
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CN101323447B (zh) * | 2008-07-21 | 2012-02-22 | 深圳市贝特瑞新能源材料股份有限公司 | 锂离子电池负极的石墨粉及其制备方法 |
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2009
- 2009-12-07 TW TW098141752A patent/TWI445235B/zh not_active IP Right Cessation
- 2009-12-14 WO PCT/JP2009/070830 patent/WO2010073931A1/ja active Application Filing
- 2009-12-14 US US13/141,740 patent/US8470206B2/en not_active Expired - Fee Related
- 2009-12-14 EP EP09834734.7A patent/EP2372820A4/en not_active Withdrawn
- 2009-12-14 CN CN200980152317.4A patent/CN102265435B/zh not_active Expired - Fee Related
- 2009-12-14 KR KR1020117017398A patent/KR101286343B1/ko not_active IP Right Cessation
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JPH07192724A (ja) * | 1993-06-03 | 1995-07-28 | Sony Corp | 非水電解液二次電池 |
JPH07335262A (ja) * | 1994-06-03 | 1995-12-22 | Sony Corp | 非水電解液二次電池 |
JPH08279358A (ja) | 1995-02-09 | 1996-10-22 | Kureha Chem Ind Co Ltd | 電池電極用炭素質材料、その製造方法、電極構造体および電池 |
WO2005098999A1 (ja) | 2004-04-05 | 2005-10-20 | Kureha Corporation | 大電流入出力非水電解質二次電池用負極材料、その製造方法および負極材料を用いる電池 |
WO2007040007A1 (ja) | 2005-09-09 | 2007-04-12 | Kureha Corporation | 非水電解質二次電池用負極材料及びその製造法並びに負極及び非水電解質二次電池 |
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Also Published As
Publication number | Publication date |
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TWI445235B (zh) | 2014-07-11 |
US8470206B2 (en) | 2013-06-25 |
CN102265435B (zh) | 2015-01-14 |
EP2372820A1 (en) | 2011-10-05 |
TW201034275A (en) | 2010-09-16 |
KR101286343B1 (ko) | 2013-07-15 |
JPWO2010073931A1 (ja) | 2012-06-14 |
EP2372820A4 (en) | 2013-09-25 |
CN102265435A (zh) | 2011-11-30 |
JP5606926B2 (ja) | 2014-10-15 |
US20110253928A1 (en) | 2011-10-20 |
KR20110098969A (ko) | 2011-09-02 |
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