WO2002059040A1 - Particule de graphite artificiel et son procede de production, electrode negative de batterie secondaire a electrolyte non aqueux et son procede de production et batterie secondaire au lithium - Google Patents
Particule de graphite artificiel et son procede de production, electrode negative de batterie secondaire a electrolyte non aqueux et son procede de production et batterie secondaire au lithium Download PDFInfo
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- WO2002059040A1 WO2002059040A1 PCT/JP2002/000564 JP0200564W WO02059040A1 WO 2002059040 A1 WO2002059040 A1 WO 2002059040A1 JP 0200564 W JP0200564 W JP 0200564W WO 02059040 A1 WO02059040 A1 WO 02059040A1
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/23—Oxidation
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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
- C01B32/20—Graphite
- C01B32/21—After-treatment
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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
- H01M4/362—Composites
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
Definitions
- the present invention relates to artificial graphite particles and a method for producing the same, a negative electrode for a nonaqueous electrolyte secondary battery, a method for producing the same, and a lithium secondary battery.
- graphite powder such as natural graphite, artificial graphite obtained by graphitizing coke, and artificial graphite obtained by graphitizing an organic polymer pitch is used.
- An organic polymer is added as a binder to these graphite powders, an organic solvent and water are added to form a paste, the graphite paste is applied to the surface of a copper foil current collector, and the solvent is dried to form a paste for a lithium secondary battery.
- the use of black bell as the negative electrode active material solves the problem of internal short circuit due to lithium dendrite-like precipitation and improves cycle characteristics. I have.
- the lithium secondary battery using graphite for the negative electrode has greatly improved cycle characteristics compared to the lithium secondary battery using the lithium metal-lithium alloy for the negative electrode, the following two problems have been solved. It has not been.
- the first problem is that the electrolyte is decomposed on the graphite surface during the initial charging (first Li occlusion reaction to graphite).
- a lithium secondary battery stores or releases lithium between a positive electrode and a negative electrode, and performs charge and discharge.For example, in the first charge, the positive electrode releases 100 of lithium, and the electricity corresponding to 20 is released. Electricity ratio When consumed for liquid decomposition, the amount of lithium stored in the negative electrode becomes 80. If electrolyte decomposition does not occur, a maximum of 100 lithium can be used for charging and discharging, but in the above example, only a maximum of 80 lithium can be used. The decomposition reaction causes the battery capacity to decrease.
- the second problem is that natural graphite particles developed with graphite crystals, which are considered to have a large amount of lithium occlusion and release, or artificial graphite particles obtained by graphitizing Kotas, break the interlayer bond between graphite layers by grinding.
- Graphite particles with a large scale-like aspect ratio are obtained.
- the scale-like graphite particles are kneaded with a binder and applied to a current collector to produce an electrode, the scale-like graphite particles are oriented in the plane direction of the current collector.
- the graphite layer expands and contracts due to repeated insertion and extraction of lithium into and from the graphite particles, resulting in distortion and a decrease in the adhesion between the oriented graphite particles and the current collector.
- the characteristics and rapid charge / discharge characteristics deteriorate.
- Japanese Patent No. 2643035 discloses that the surface of graphite is coated with an amorphous carbon layer to suppress decomposition of an electrolytic solution.
- Japanese Patent Application Laid-Open No. Hei 10-158005 discloses the use of graphite particles obtained by assembling flat graphite particles so as to be non-oriented.
- Japanese Patent Application Laid-Open No. Hei 11-263612 discloses cabbage. It is disclosed that flaky natural black bell-modified particles having an external appearance and a circularity of 0.86 or more are used. Disclosure of the invention
- Japanese Patent No. 2643035 which covers the graphite surface with an amorphous carbon layer to suppress the decomposition of the electrolytic solution, cannot necessarily increase the capacity of the lithium secondary battery.
- Graphite coated with amorphous carbon has a higher charge / discharge average voltage than graphite, and under actual conditions of use, the amount of lithium stored and released is reduced.
- a new problem arises due to amorphous carbon, such as a decrease in carbon dioxide.
- an object of the present invention is to reduce the irreversible capacity by suppressing the electrolyte decomposition reaction at the first charge without losing the characteristics of a graphite anode having a large lithium storage / release amount, thereby achieving a high capacity lithium ion secondary battery.
- An object of the present invention is to provide a used lithium secondary battery.
- the present inventors have conducted intensive studies to achieve the above object.
- the electrolytic solution decomposition reaction at the first charge of the graphite negative electrode penetrates between the graphite layers in a state where the solvent molecules are coordinated to lithium ions (cointerlayer). It has been found that, at this time, the solvent molecule itself is decomposed due to the large steric hindrance of the solvent (Journal Off-Paper Sources, Vol. 54, 288, p. Year)).
- the present inventors first made improvements in the black sharp surface portion where lithium invaded so that the above-mentioned decomposition reaction of the electrolytic solution can be suppressed in the present invention. If the black tin crystals were high near the surface, the decomposition reaction of the electrolyte was considered to be high, and an attempt was made to make the surface of the graphite particles amorphous. Electrolytic solution decomposition reaction was reduced by mixing carbonaceous material into graphite and refiring, or by coating amorphous carbon on the surface by chemical vapor deposition (CVD). As a result, the average charge / discharge voltage is higher than that of graphite, and the amount of lithium stored and released is reduced under practical use conditions, and the true specific gravity is reduced.
- CVD chemical vapor deposition
- lithium secondary batteries cannot be increased in capacity due to new problems caused by amorphous carbon, such as the occurrence of such problems. Accordingly, the present inventors have further studied and found that graphite particles having only a very low crystallinity on the surface layer were replaced with lithium secondary particles in order to suppress the electrolytic solution decomposition reaction without deteriorating the high capacity characteristics of graphite. It has been found that the object of the present invention can be achieved by using it for a negative electrode material of a battery. In addition, such graphitic particles can be manufactured by a specific manufacturing method. Was found.
- the artificial graphite particles of the present invention have a secondary particle structure in which a plurality of primary particles made of graphite aggregate or combine, and have a layer structure in which the edge portion of the primary particles is bent into a polygonal shape. It is characterized by the following.
- the method for producing artificial graphite particles of the present invention is characterized in that raw graphite particles are passed through the gap between two members which are positioned with a gap and one or both of which rotate.
- the negative electrode for a non-aqueous electrolyte secondary battery according to the present invention is a non-aqueous electrolyte secondary battery having graphite particles that release or occlude alkali metal ions fixed to the surface of a metal foil with an organic binder.
- the negative electrode is characterized in that the graphite particles comprise the artificial graphite particles of the present invention, and the method of manufacturing a negative electrode for a non-aqueous electrolyte secondary battery of the present invention comprises releasing an alkali metal ion.
- the graphite particles are produced by the method for producing artificial graphite particles of the present invention.
- the lithium secondary battery of the present invention provides a laminated body and a non-aqueous electrolyte in which a negative electrode capable of occluding and releasing lithium, a separator, and a positive electrode capable of occluding and releasing lithium are sequentially stacked in a container.
- the negative electrode comprises the negative electrode of the present invention.
- FIG. 1 is a cross-sectional view showing an example of the cylindrical lithium secondary battery of the present invention.
- FIG. 2 is a cross-sectional view showing one example of a coin-type lithium secondary battery of the present invention.
- FIG. 3 is a view corresponding to a scanning electron microscope (SEM) photograph of the raw graphite particles of the present invention.
- FIG. 4 is a view corresponding to a scanning electron microscope (SEM) photograph of the artificial graphite particles of the present invention.
- FIG. 5 is a schematic cross-sectional view of the artificial graphite particles of the present invention.
- FIG. 6 is a schematic cross-sectional view of the artificial graphite particles of the present invention.
- FIG. 7 is a view corresponding to a transmission electron microscope (TEM) photograph of the artificial graphite particles of the present invention.
- TEM transmission electron microscope
- FIG. 8 is a graph showing the thermogravimetric change (TG) of the artificial black hull particles of the present invention and the conventional graphite particles.
- FIG. 9 is a view showing the differential calorie change (D T A) of the artificial graphite particles of the present invention and the conventional graphite particles.
- FIG. 10 is a diagram showing the electrochemical cell used in the present invention.
- FIG. 11 is a diagram showing cyclic portograms measured in Example 2 and Comparative Example 2.
- FIG. 12 is a diagram corresponding to a scanning electron microscope (SEM) photograph of the negative electrode of the lithium secondary battery of the present invention in an overcharged state.
- SEM scanning electron microscope
- FIG. 13 is a diagram corresponding to a scanning electron microscope (SEM) photograph of a conventional lithium secondary battery negative electrode in an overcharged state.
- FIG. 14 is a diagram corresponding to a scanning electron microscope (SEM) photograph of an unused lithium secondary battery negative electrode of the present invention.
- FIG. 15 is a diagram corresponding to a scanning electron microscope (SEM) photograph of an unused conventional lithium secondary battery negative electrode.
- SEM scanning electron microscope
- the artificial graphite particles of the present invention have a secondary particle structure in which a plurality of primary particles made of black bells are aggregated or bonded, and have a layer structure in which the wedge portion of the primary particles is bent into a polygonal shape. I have.
- the artificial black belly particles of the present invention are applied to the negative electrode of a non-aqueous electrolyte secondary battery, the irreversible capacity in the first charge / discharge is small, the rapid discharge load characteristics are excellent, and the charge / discharge cycle life is long. In addition to having the characteristics described above, charge acceptability is improved. This is because, for example, in a lithium secondary battery, when overcharged, lithium was precipitated in the form of dendrite in the conventional negative electrode material, whereas in the artificial graphite particles of the present invention, the lithium was precipitated in the form of particles or mossy. It is presumed that this is the case, and is effective in improving safety in overcharging.
- the artificial graphite particles of the present invention preferably have a surface layer in which the outermost surface of the secondary particles is in a low crystalline or amorphous state.
- TEM transmission electron microscope
- ISSOciif 1 near the peak by Ramansu Bae-vector measurement of artificial graphite particles of the present invention (1 136.) And 1580Cm- 1 near the peak (I 158.) And a peak intensity ratio of the (R I / I 1580) is , 0.1 ⁇ R ⁇ 0.5, more preferably 0.1 and 0.1
- ⁇ R ⁇ 0.3 is more preferable, and 0.1 ⁇ R ⁇ 0.2 is particularly preferable.
- the secondary particle structure is a secondary particle structure in which a plurality of graphite primary particles are aggregated or bonded to each other in a non-parallel manner, and have a void in the secondary particles. Is preferred.
- the void existing inside the artificial graphite particles can be measured by the pore volume measured by the mercury intrusion method, and the pore volume by such a method is from 0.1 to 0.5 cm 3 / g. It is preferred that there be.
- the pore volume is within the above range, rapid discharge characteristics tend to be excellent.
- the pore volume is less than 0.5 LcmVg, nonaqueous rapid discharge characteristics liquid retention amount of electrolyte is small electrolyte solution for a secondary battery is decreased, and 0.5 greater than 5 cm 3 / g
- artificial black The binder that forms the negative electrode for non-aqueous electrolyte secondary batteries when mixed with the particles permeates the pores and reduces the adhesion between the artificial graphite particles and the current collector. It becomes difficult to obtain good cycle characteristics as a liquid secondary battery.
- the artificial graphite particles of the present invention preferably have a bulk density of O. Sg / cm 3 or more.
- the bulk density is not less than the above, the electrode coating property for a non-aqueous electrolyte secondary battery is excellent, and the adhesion to a current collector is excellent. That is, when the force density is less than O.Sg/cm 3 , the electrode coatability tends to decrease.
- the force density refers to a value obtained by placing black-aged particles in a container and repeatedly tapping until the particle volume does not change.
- the artificial graphite particles of the present invention preferably have a specific surface area of 3 to 6 tn 2 / g.
- the specific surface area is within the above range, the non-aqueous electrolyte secondary battery tends to have excellent rapid charge / discharge characteristics and high safety. That is, when the specific surface area is less than 3 m 2 / g, the rapid charge / discharge characteristics tend to decrease, and when the specific surface area exceeds 6 raVg, the safety of the battery tends to decrease.
- the surface oxygen concentration of the artificial graphite particles of this light is preferably 1.0 ⁇ 0atom% (more 1. 0 ⁇ 3.0 a t O m%) it is. Surface oxygen concentration can be measured by X-ray photoelectron spectroscopy (XPS).
- the surface oxygen concentration is 1.0 ⁇ 4.0 a t O tn%
- the artificial graphite particles having a surface oxygen concentration within the above range can be easily obtained by the method for producing artificial graphite belly particles of the present invention described in detail below.
- Such a production method is a method of performing a grinding treatment (friction and grinding treatment) of the raw graphite particles, and the surface oxygen concentration in the above range is such that the surface of the graphite particles is oxidized by heat generated by the grinding and surrounding oxygen. It is thought that it is achieved by doing.
- the artificial graphite particles have the above requirements. That is, the bulk density is 0.8 g / cm 3 or more, the specific surface area is ⁇ 2 / ⁇ , and the surface oxygen concentration measured by X-ray photoelectron spectroscopy (XPS) is 1.0 to 4.0. It is preferably atm%.
- the artificial graphite particles of the present invention lose weight and generate heat at a temperature of 640 ° C. or more,
- the weight loss by heating at ° C for 30 minutes is less than 3%.
- the weight loss of the conventional carbon material at the time of the above measurement is 5 ° / 0 or more
- the weight loss of the artificial graphite particles of the present invention is smaller than that of the conventional carbon material.
- the carbon material used in conventional lithium secondary batteries has low crystallinity of graphite and contains many amorphous portions and defects in which the crystal has not yet developed. It is considered that the exothermic onset temperature is lower and the weight loss is greater.
- the present invention Since the artificial graphite particles have high crystallinity and only a very small surface of the particles are bent into a polygonal shape and become amorphous, the heat generation start temperature is high and the weight loss is considered to be small.
- the artificial graphite particles exhibiting such a weight reduction can be produced by the method for producing artificial graphite belly particles of the present invention described later, and the artificial graphite particles obtained by this method can be used at 640 ° C. or higher. A decrease and a thermal behavior are observed. On the other hand, in the carbon material used in the conventional lithium secondary battery, the exothermic behavior is observed at around 600 ° C. Therefore, the artificial black belly particles of the present invention start generating heat as compared with the conventional carbon material. Temperature is high.
- the artificial black belly particles of the present invention have an average particle diameter of 10 to 50 m and a true density of 2.2 gm m 3 or more.
- the spacing d002 of the (002) plane of graphite is preferably less than 0.337 nm. If the average particle size of the artificial graphite particles is larger than 50 im, irregularities are likely to be generated on the electrode surface, which may cause a short circuit when applied to a non-aqueous electrolyte secondary battery. On the other hand, when the average particle size is less than 10 zm, the specific surface area of the black-bellish particles becomes large, so that the electrode coatability tends to decrease, and the fine particles tend to decrease the battery safety.
- the true density is less than 2.2 g / cm 3 and d002 is 0.337 nra or more, it means that the crystallinity of graphite is low, and the amount of occluded and released lithium decreases. Tend to decrease the charge and discharge capacity.
- the artificial graphitic particles of the present invention have a viscosity of 0.degree. C. at a temperature of 25.degree. C. and a shear rate of 4 seconds- 1 of a paste (electrode mixture paste) obtained by kneading with the following binder (a) and solvent (b). 3 to 1.6 Pas (preferably 0.6 to 1.3 Pa's, more preferably 1.0 to 1.3 Pa ⁇ s).
- Examples of the polyvinylidene fluoride in (a) above include polyvinylidene fluoride (# 1120) manufactured by Kureha Chemical Co., Ltd.
- the viscosity of the electrode mixture paste in the present invention is the same as that measured by the following method. I do. That is, graphite particles and polyvinylidene fluoride (# 1120, manufactured by Niwa Chemical Co., Ltd.) are mixed at a weight ratio of 90:10, and the solid content of the graphite particles and polyvinylidene fluoride is combined. But 45 weight. N-methyl-2-pyrrolidone is added so that the ratio becomes / 0, and an electrode mixture paste is prepared. The viscosity is measured at 25 ° C and a shear rate of 4 seconds- 1 using a model DV-III manufactured by BR00KFIELD.
- the artificial graphite particles of the present invention are also kneaded with the following binder (a) and solvent (b) to have a viscosity of 1. OP a ⁇ s at 25 ° C. and a shear rate of 4 seconds- 1 . —
- the shear rate dependence of viscosity at 25 ° C (TI) is defined as It is preferably 2.0 to 4.0 (preferably 2.0 to 3.5, more preferably 2.6 to 3.0).
- polyvinylidene fluoride of the above (a) examples include polyvinylidene fluoride 1120 manufactured by Niwa Chemical Co., Ltd., and the shear rate dependence (TI) in the present invention is determined by the following method. I do. That is, black matter particles and polyvinylidene fluoride (# 1120 manufactured by Kureha Chemical Co., Ltd.) were mixed at a weight ratio of 90:10, and the mixture was mixed with 25 ° C by BR00 KFIELD model DV-III. C, N-methyl-2-pyrrolidone is added to prepare an electrode mixture paste so that the viscosity at a shear rate of 4 seconds- 1 is 1.0 Pas.
- TI shear rate dependence
- the artificial graphite particles of the present invention preferably have at least one of the above-mentioned preferable characteristics, and have all the characteristics. Are particularly preferred.
- the method for producing artificial graphite particles of the present invention is characterized in that raw graphite particles are passed through the gap between two members that are positioned with a gap and one or both of which rotate. According to such a production method, the artificial graphite particles of the present invention having the above characteristics can be easily produced.
- the raw graphite particles are placed such that their planes face each other. It is preferable that at least one of the two members disposed with a desired gap is passed between the above-mentioned gaps that rotate relatively to grind at least the surface of the raw graphite particles.
- a fixing member is provided at a position corresponding to the rotation center of the rotating member, between a fixing member arranged with a desired gap with the planes facing each other and a rotating member arranged below the fixing member and rotating. It is preferable that at least the surface of the raw graphite particles is ground by supplying the raw graphite particles through the supply port of the fixed member and passing the raw graphite particles through the gap.
- the two members in the above manufacturing method rotate in directions opposite to each other, and the materials of the two members are not particularly limited, but a ceramic material such as alumina, silicon carbide ', or silicon nitride is treated after the treatment. This is preferable in that there is little impurity contamination of the graphite particles.
- a millstone type grinding device or the like constituted by two upper and lower grinders whose two plates can freely adjust the interval
- the raw material is sent into the gap between the upper and lower grinders by centrifugal force, and the compression, shearing, rolling friction, etc. generated there enable grinding (grinding and crushing) of the raw graphite particles.
- Commercially available products with the above-mentioned structure include Glo-Ichi Engineering Co., Ltd. stone grinder (Gro-Mill), Chuo Kakeki Shoji Co., Ltd., Premax, and Masuko Sangyo Co., Ltd. Super Masco. Mouth Idar, selenium debiter and the like.
- the size of the gap between the two members is preferably 0.5 to 20 times the average particle diameter of the raw graphite particles.
- the average particle size can be measured by a particle size distribution measuring device using a laser light scattering method (for example, SALD-300 ° manufactured by Shimadzu Corporation).
- the size of the gap between the members is controlled as a talliance between the upper and lower members (for example, a plate of a grinder or the like), and the point at which the upper and lower members come into light contact is arbitrarily set to 0.
- the number of rotations of the two members, which are positioned with a gap and one or both of which rotate, when the graphite particles pass through the gap, is the gap between the rotating members, and the size (diameter) of the member. At the same time, it affects the grinding speed of the raw graphite particles, and the grinding speed increases as the rotation speed increases.
- the rotation speed is not particularly limited, but it is preferable that the outer peripheral linear velocity when the member is a disk is 15 to 40 m / sec . When the peripheral line speed is low, the milling speed decreases, and the production efficiency tends to decrease.
- the milling treatment of passing the raw graphite particles through the gap between two members that are positioned with a gap and one or both of which rotate can be performed once or a plurality of times.
- the grinding conditions the size of the gap between the two members, one or both of which rotate, the number of rotations of the members, the material supply speed, etc.
- the grinding conditions may be the same as or different from the conditions of the immediately preceding process .
- the production method of the present invention can be performed by either a dry method or a wet method.
- the dry method is a method in which raw graphite particles are passed through a gap between two members, one or both of which rotate
- the wet method is a method in which raw graphite particles dispersed in an appropriate solvent are dispersed.
- the wet method requires an operation to separate the artificial graphite particles in the solvent after the treatment.
- an organic solvent such as water or alcohol can be used as the solvent.
- the dry method is preferable because the bulk density can be increased as compared with the wet method, and artificial graphite particles excellent in electrode coating properties and electrode adhesion can be obtained.
- the dry method does not include a step of dispersing the solvent and the raw graphite particles before the grinding treatment and a step of separating the solvent and the artificial sharp particles after the grinding treatment, so that low cost is achieved. Manufacture of artificial graphite particles is possible.
- the raw graphite particles are preferably a mass of artificial graphite, and the raw graphite particles have a secondary particle structure in which a plurality of primary particles made of graphite are aggregated or bonded.
- the primary particles in the secondary particles have non-parallel orientation planes. In this case, it is preferable that the aspect ratio of the primary particles is 5 or less.
- the raw graphite particles have a structure in which a plurality of flat graphite particles are aggregated or bonded to each other in a non-parallel manner, and the aspect ratio is 5 or less (preferably 1 to 3). It is particularly preferable that the material has a void.
- the aspect ratio is obtained by measuring the minor axis and major axis of each particle from the SEM photograph of the graphite particles, and calculating the ratio of the major axis to the minor axis. The average value of these ratios obtained by selecting 1 0 arbitrary particles in this way is determined as the aspect ratio.
- the massive raw graphite particles having voids inside the particles in advance can be obtained by combining a graphitizable aggregate, a graphitization catalyst and a binder binding these, pre-firing, and graphitizing.
- Various cokes such as fluid coaters and needle coaters can be used as the graphitizable aggregate.
- the binder petroleum, coal, artificial pitch and tar can be used, and a material that can be graphitized as with aggregate is desirable.
- Carbide such as silicon, iron, nickel, titanium, and boron, oxide, and nitride can be used as the blackening catalyst.
- the pre-firing and graphitization are desirably performed in an atmosphere in which the aggregate and binder are unlikely to be oxidized, for example, in a nitrogen atmosphere, an argon atmosphere, or a vacuum, and the pre-firing is performed in a temperature range of 400 ° C to: L000 ° C.
- Graphitization is preferably performed at a temperature of 2000 ° C or higher.
- the graphitization catalyst escapes at a temperature of 2000 ° C or more, and then pores are formed.
- the graphitization temperature is more preferably 2500 ° C. or higher, and most preferably 2800 ° C. or higher because graphite having high crystallinity can be obtained. If the graphitization temperature is lower than 2000 ° C, As the development worsens, the charge / discharge capacity tends to decrease because the graphitization catalyst remains in the produced graphitic particles.
- the amount of the graphitizing catalyst to be added is preferably 1 to 50 parts by weight based on 100 parts by weight of the total amount of the graphitizable aggregate or graphite and the binder which can be graphitized. If the amount is less than 1 part by weight, the development of artificial graphite particles becomes poor, and the charge / discharge capacity tends to decrease when applied to a non-aqueous electrolyte secondary battery. On the other hand, if it exceeds 50 parts by weight, it becomes difficult to mix uniformly, and the workability tends to decrease.
- the graphitized material obtained as described above is in a block state, it is preferable to grind it once.
- the pulverization method There is no particular limitation on the pulverization method, but a jet mill, a vibrating mill, a hammer mill or the like can be used.
- the average particle size after pulverization is desirably ⁇ or less, and more preferably in the range of 10 to 50 m because of good coating properties.
- the pulverized powder may be subjected to cold isostatic pressing. It is desirable to use the massive artificial graphite produced as described above as the raw black belly particles.
- the negative electrode for a non-aqueous electrolyte secondary battery according to the present invention is a negative electrode for a non-aqueous electrolyte secondary battery having graphite particles that release or occlude metal ions fixed to an outer surface of a metal foil by an organic binder.
- the above-mentioned graphite particles are characterized by comprising the above-mentioned artificial graphite particles of the present invention.
- the artificial graphite particles of the present invention are preferably artificial graphite filler particles produced by the above-described method of producing the artificial graphite particles of the present invention.
- the electrolyte of the non-aqueous electrolyte secondary battery (ethylene carbonate (EC) and ethyl methyl carbonate (EMC) having a volume ratio of 1: 1) is used.
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- a mixed solvent of degradation of L i PF 6 a lmo 1 dm 3 dissolved solution or the like is less likely to occur.
- the discharge capacity of the non-aqueous electrolyte secondary battery can be increased, and the irreversible capacity can be reduced.
- the present invention also provides a method for producing a negative electrode for a non-aqueous electrolyte secondary battery having graphite particles that release or occlude alkali metal ions, wherein the graphite particles are produced as described above.
- the lithium secondary battery of the present invention includes a container in which a negative electrode capable of absorbing and releasing lithium, a separator, and a positive electrode capable of absorbing and releasing lithium are sequentially laminated, and a nonaqueous electrolyte.
- the negative electrode comprises the nonaqueous electrolyte secondary battery negative electrode of the present invention.
- the lithium deposited on the surface of the graphitic particles be granular or mossy (meaning that the deposited metallic lithium covers the surface of the negative electrode material particles almost uniformly).
- the lithium deposition shape is granular or mossy, in addition to the features such as low irreversible capacity at the first charge / discharge, excellent rapid discharge load characteristics, and long charge / discharge cycle life, charging Acceptability tends to be improved.
- FIG. 1 is a cross-sectional view showing an example of a lithium secondary battery using the artificial black belly particles of the present invention for a negative electrode.
- the positive electrode 10, the separator 11, and the negative electrode 12 are stacked in the order of positive electrode 1 ⁇ , separator 11, negative electrode 12, and separator 11 and wound and stored in the battery can 13. .
- the positive electrode 10 has a positive electrode tab 14 attached to the negative electrode 12, and the negative electrode tab 15 has a negative electrode tab 15 attached to the negative electrode 12 .
- the positive electrode tab 14 is connected to the battery inner lid 16, and the negative electrode tap 15 is connected to the battery can 13. I have.
- FIG. 2 is a sectional front view of a coin-type lithium secondary battery which is another example of the present invention.
- a pellet-shaped positive electrode 21 and a pellet-shaped negative electrode 22 are laminated with a separator 23 interposed therebetween, and the positive electrode and the negative electrode are brought into contact with the positive electrode can 24 and the negative electrode can 25, respectively, so that conduction is obtained.
- the can is oaked via gasket 26.
- the negative electrode used in the lithium secondary battery of the present invention can be obtained by adding an organic binder to the artificial graphite particles of the present invention, kneading the mixture, and forming the mixture into a sheet-like or pellet-like shape.
- the organic binder include polyethylene, polypropylene, ethylene propylene polymer, butadiene rubber, styrene-butadiene rubber, and ptynole rubber.
- lithium ion conductive polymer compounds such as polyvinylidene fluoride, polyethylene oxide, polyepiclohydrin, polyphosphazene, and polyacrylonitrile are also suitable as the organic binder.
- the content of the organic binder is preferably 1 to 20 parts by weight based on 100 parts by weight of the mixture of the artificial graphite particles and the organic binder.
- the sheet-shaped negative electrode is made into a paste by adding water or an organic solvent to a mixture of artificial graphite particles and an organic binder, adjusting the paste viscosity, applying the paste to a current collector, drying the solvent, and then, for example, using a mouth press.
- a paste by adding water or an organic solvent to a mixture of artificial graphite particles and an organic binder, adjusting the paste viscosity, applying the paste to a current collector, drying the solvent, and then, for example, using a mouth press.
- it can be manufactured by pressure molding.
- the current collector for example, foil or mesh of copper, nickel, stainless steel, or the like can be used.
- the pellet-shaped negative electrode can be manufactured by press-molding a mixture of the above-mentioned graphite particles and an organic binder.
- the active material is not particularly limited, but a lithium-containing transition metal oxide is desirable.
- a sheet-like or pellet-like positive electrode can be manufactured using the above-mentioned active material in the same manner as the negative electrode. ⁇ , current collection Aluminum foil or mesh is used for the body.
- Examples of the solvent for the organic electrolyte used in the lithium secondary battery of the present invention include:
- the carbonates include at least dimethyl / recarbonate, ethynolecarbonate, ethynole meth ⁇ ⁇ carbonate, y-petit mouth ratataton, sulfolane, methyl acetate, ethetyl acetate / le, methyl propionate, ethyl propionate, dimethoxetane, 2- Methinolete A mixed solvent containing one or more of trihydrofuran. It is desirable that the volume fraction of ethylene carbonate is 0.1 or more and 0.6 or less. On the other hand, in the present invention.
- L i PF 6 as the lithium salt, L i BF 4, L i A s F 6, L i C L_ ⁇ 4, (C 2 F 5 S0 3) 2 NL i, (CF 3 S0 3 ) 2 NL i using at least one or more, desirably in the range of its concentration from 0.5 to 1. 5mo 1 Zdm 3.
- separator used in the lithium secondary battery of the present invention for example, a nonwoven fabric, a cloth, a microporous film, or a combination thereof, containing polyolefin such as polyethylene or polypropylene as a main component can be used.
- polyolefin such as polyethylene or polypropylene
- a mixture of 100 parts by weight of a powder having an average particle size of 5 ⁇ , 30 parts by weight of tar pitch, 30 parts by weight of silicon carbide having an average particle size of 48 / tti, and 20 parts by weight of coal tar, 270 ° C For 1 hour.
- the obtained mixture was pulverized, pressure-formed into pellets, pre-fired at 900 ° C in nitrogen, and then graphite-dried at 2800 ° C using an Acheson furnace.
- the black forceps block obtained as described above was pulverized using a hammer mill, and passed through a 20 ° mesh standard sieve to produce massive raw graphite particles.
- the point where the upper and lower grinders come into light contact is set to 0, and the clearance between the grinders (clearance) is 60 ⁇ m
- the above-mentioned raw graphite particles were subjected to grinding treatment (grinding treatment) through the gaps to obtain artificial graphite particles of the present invention.
- the upper grinder was fixed and the lower grinder was rotated at 150 Orpra, and the raw graphite particles were supplied from the supply port provided in the upper grinder at the part corresponding to the center of the lower grinder.
- the artificial graphite particles of the present invention were obtained by performing a treatment of passing twice, and as the upper and lower grinders, those having opposing surfaces each having fine irregularities were used.
- the raw graphite particles and the artificial graphite particles of the present invention are shown below in (1) to (1).
- Average particle diameter Measured using a laser diffraction particle size distribution analyzer (SALD-3000), Shimadzu Corporation.
- the ratio of the major axis to the minor axis of the 100 graphite particles was determined, and the average value was used as the representative value.
- Black 10 interlayer distance (hereinafter also referred to as “surface spacing d002”): Using a X-ray diffractometer PW1730 (goniometer PW1050) manufactured by PHILIPS, monochromatic Cu- ⁇ ⁇ rays with a Ni filter to produce high-purity silicon. As an internal standard sample, the d002 of the (002) plane of graphite was measured.
- Pore volume Using Autoscan 33 manufactured by Yuasa Ionitas, pores in the range of 10 to 10 m were measured by the mercury intrusion method.
- Viscosity of electrode mixture paste Graphite particles and polyvinylidene fluoride (# 1120 manufactured by Kureha Chemical Co., Ltd.) are mixed so that the weight ratio becomes 90:10, and the graphite particles are further mixed. N-methyl_2_pyrrolidone was added to make an electrode mixture paste so that the concentration of the solid content of the mixture of styrene and vinylidene polyfluoride was 45% by weight.
- the viscosity of the electrode mixture paste was measured at 25 ° C and a shear rate of 4 seconds- 1 .
- Table 1 shows the physical property values of the raw black belly particles and the artificial black filler particles of the present invention.
- the artificial black belly particles of this effort have increased bulk density, increased peak strength ratio (R2 1360 / I 1580 ), increased surface oxygen concentration, increased electrode mixture paste compared to raw black particles. It can be seen that the viscosity decreases.
- the viscosity of the electrode mixture paste was measured as an index of electrode coatability and electrode adhesion, and the artificial graphite particles of the present invention had lower viscosity than the raw graphite particles. The strike viscosity is reduced, electrode coatability is improved, and electrode adhesion is improved. (table 1 )
- the artificial graphite particles of the present invention were obtained in the same manner as in Example 1d, except that the gap between the grinders was set to 80 ⁇ , 200 ⁇ m, and 300 ⁇ m.
- the artificial graphite particles of the present invention all have an average particle diameter in the range of 10 to 50 ⁇ m, the true density is 2.2 g / cm 3 or more, and the plane spacing d 002 of the (002) plane of graphite is less than 0.337 nm.
- the artificial graphite particles of the present invention have a lower electrode mixture paste viscosity, improved electrode coating properties, and improved electrode adhesion as compared with the raw graphite particles shown in Table 1.
- examples in Table 2 ld, le, 1: 1 ⁇ Pi 1 ⁇ is, since the magnitude of Gurain Zehnder gap to the average particle diameter of the raw graphite powder in the range from 0.5 to 20 times, especially electrode mixture It was found that the paste had a low viscosity and was desirable.
- Example 1a The raw graphite particles produced in Example 1a were subjected to a pole mill treatment, and the obtained graphite particles were examined for physical properties (1) to (10) in the same manner as in Example la.
- Example 3 shows each physical property value of the graphite particles in Comparative Example 1 ad. (Table 3)
- Example 1d massive raw belly particles were produced. According to the SEM photograph, the obtained raw graphite particles had a structure in which flat particles were aggregated or bonded so that a plurality of oriented planes became non-parallel.
- the raw graphite particles are gently connected to the upper and lower grinder gaps (clearance) using a Mascolloider (MK10-20J) manufactured by Takayuki Sangyo Co., Ltd. equipped with a grinder GA10-120. 40 (Example lh), 80 im (Example li), 200 ⁇ ( Examples 1j) and 300 / zm (Example lk) were opened and subjected to grinding processing (milling processing).
- MK10-20J Mascolloider
- Example 1h Comparative Example 1e
- Example 1k The rotation speed of the lower grinder under the Masco mouth whatsoever
- Example la The physical properties of (10) were examined.
- Table 4 shows the respective physical property values.
- Example 1d massive raw graphite particles were produced.
- the raw black bell-like particles are formed by flat particles having a plurality of orientation planes that are non-parallel. It had an aggregated or bonded structure.
- the raw graphite particles were subjected to a grinding treatment (milling treatment) using a super masco mouth ider (MKZA 10-15J) manufactured by Masuko Sangyo Co., Ltd. equipped with a grinder MK GC 10-120.
- the rotation speed of the lower grinder was set to 1,500 rpm, and the upper and lower grinders were lightly brought into contact with the upper and lower grinders (clearance) (Examples lo and 1), 60 ⁇ m (Examples 1q and 1). r) and 80 m (Examples 1 s and 1 t) were opened.
- the graphite particles that had been subjected to the grinding process were put into a regenerator, and the grinding process was performed twice (milling process). Was done.
- Example la the physical properties of (1) to (10) were examined for the artificial black particles of the present invention obtained in Examples 1o to 1t.
- Example la the physical properties of (1) to (10) were examined for the artificial black particles of the present invention obtained in Examples 1o to 1t.
- the shear rate dependence (TI) of the paste viscosity of the electrode mixture was measured by the method of (11). Table 5 summarizes these physical properties.
- Comparative Example 1f The raw graphite particles in Example 1o were designated as Comparative Example 1f.
- Comparative Example 1 g is the raw material graphite particles of Comparative Example 1 f was filled in a rubber mold, pressed at a pressure of 1. 5 t / cm 2 in cold isostatic pressing, the resulting molded body pin mill It was crushed by and passed through a 200 mesh sieve.
- the physical properties of these comparative examples were measured in the same manner as in Example 1 olt. Table 6 shows the results. (Table 6)
- the raw graphite particles obtained in Example 1a and the artificial graphite particles of the present invention were observed by a scanning electron microscope (SEM) photograph.
- Fig. 3 shows the raw graphite particles
- Fig. 4 shows the artificial graphite particles of the present invention.
- the primary particles in the secondary particles of the artificial black belly particles of the present invention have a structure in which secondary particles are aggregated or bonded so that the orientation planes are non-parallel to each other (secondary particles).
- Particle structure Particle structure
- Fig. 5 shows the state of the secondary particles.
- the secondary particles have a secondary particle structure in which primary particles made of graphite 1 are aggregated or bonded, and the primary particles have non-parallel orientation planes.
- the secondary particles have voids 2 surrounded by the primary particles.
- the edges of the primary particles of the artificial graphite particles of the present invention were observed with a transmission electron microscope (TEM). As shown in the schematic diagram of FIG. 6 and the TEM of FIG. It was found that the graphite layer had a polygonal layer structure at the edge portion. When lithium infiltrates the artificial graphite particles of the present invention, even if the solvent molecules are intercalated between the graphite layers, the edges have a structure in which the graphite layer is bent into a polygonal shape, so that graphite having high crystallinity is obtained. As compared with the above, the graphite layer is more likely to spread, so that the influence of steric hindrance is reduced and solvent decomposition is suppressed.
- TEM transmission electron microscope
- the artificial graphite particles of the present invention obtained in Example 1a (61 in FIG. 8 and 71 in FIG. 9) and the artificial graphite particles of Comparative Example 1a (62 in FIG. 8 and 72 in FIG. 9) ) And the graphite particles (63 in FIG. 8 and 73 in FIG. 9) obtained by coating the natural graphite of Example 2 with amorphous carbon in a thermogravimetric air-differential thermal analysis.
- the measurement (TG-DTA measurement) was performed using TG / DTA6200 manufactured by Seiko Instruments Inc. The measurement was performed at room temperature to 900 ° C at a flow rate of air of 200 cm 3 / min and a heating rate of 5 ° C / min.
- Example 1a of the present invention should have a temperature at which the weight loss due to combustion and the onset temperature of heat generation are higher than the graphite particles of Comparative Examples 1a and 1b and about 640 ° C or higher. I understood. Next, heating was performed from room temperature to 650 ° C at a heating rate of 5 ° C / min, and the weight loss was measured when the temperature was maintained at 650 ° C for 30 minutes.
- Example 1 a of graphite particles, Comparative Example 1 a of artificial graphite particles and Comparative Example 1 b graphite particles naturally black coated with amorphous carbon of the present invention were 2.8%, It was 5.1% and 18.5%.
- the carbon materials of Comparative Examples 1a and 1b have low crystallinity of graphite and include many amorphous portions and defects whose crystal has not been fully determined, so that the carbon materials of the carbon materials of Comparative Examples 1a and 1b are compared with the artificial graphite particles of the present invention. It is considered that the exothermic onset temperature is low and the weight loss is large.
- the artificial graphite particles of the present invention had high crystallinity and only the surface of the particles was amorphous.
- Table 7 shows the results of TG-DTA measurement of the artificial graphite particles of the present invention and the carbon materials of Comparative Examples 1c and 1d produced in Examples 1d to 1g by the same method as described above. As shown, in the artificial graphite particles of the present invention, It was found that the weight loss when kept at 65 ° C. for 30 minutes was less than 3%, and that the carbon material of the comparative example was 5% or more.
- a negative electrode was produced by the following method. 90% by weight of the artificial graphitic particles of the present invention were added with 10% by weight of polyvinylidene fluoride (PVDF) as a binder material, and an appropriate amount of N-methinole-12-pyrrolidone (NMP) was added as a solvent to form a paste. . The paste was applied on a Cu foil as a current collector at lmg / cm 2 per unit area, and then the NMP was dried. Thereafter, the density of the negative electrode mixture is 1. pressure molding so as to be 5 g / C m 3, was used as the negative electrode.
- PVDF polyvinylidene fluoride
- NMP N-methinole-12-pyrrolidone
- FIG. 10 shows a model cell used for performing the electrochemical characteristics of the negative electrode in the present invention.
- reference numeral 81 denotes a negative electrode
- 82 denotes a Li metal counter electrode
- 83 denotes a Li metal reference electrode
- 84 denotes an electrolytic solution
- 85 denotes a glass container
- Li metal is used as a reference potential.
- Evaluation was performed using a three-electrode electrochemical cell. Volume ratio in the electrolyte solution 8 4 1: a mixed solvent of 1 E Ji Ren carbonate (EC) and E chill methyl carbonate (E MC), using L i PF s was dissolved 1 mo 1 / dm 3 solution did.
- Fig. 11 shows a cyclic voltammogram showing the decomposition reaction of the electrolytic solution.
- 91 is the result of Example 2
- 92 is the result of Comparative Example 5. Comparing the magnitude of the reduction current due to the decomposition of the electrolytic solution at around 0.8 V, the case of Example 2 was smaller than that of Comparative Example 2, and therefore, the artificial graphite particles of the present invention were The decomposition reaction was found to be small.
- a negative electrode was produced in the same manner as in Example 2, and the charge / discharge characteristics were evaluated using the electrochemical cell used in Example 2.
- the case where lithium is occluded in the negative electrode is referred to as charging, and the case where lithium is released from the negative electrode is referred to as discharging.
- the negative electrode is charged at a constant current of 0.5 raA / cm 2 , and when the negative electrode potential reaches 5 mV, it is charged at a constant voltage of 5 mV.When the charge current is reduced to 0.02 mA / cm 2, the negative electrode is charged. Finished.
- the negative electrode was discharged at a constant current of 0.5 mA / cm 2 , and was terminated when the negative electrode potential reached 1.5 V. At this time, the irreversible capacity was obtained by subtracting the initial discharge capacity from the initial charge capacity.
- Example 3a the charge / discharge characteristics evaluation results regarding the initial discharge capacity and the irreversible capacity when the artificial black powder particles of the present invention were used, and the first time when the conventional graphite particles were used in Comparative Example 3a.
- Table 8 shows the results of the evaluation of the charge and discharge characteristics for the discharge capacity and the irreversible capacity.
- Each of the graphite particles of the present invention has a smaller irreversible capacity than the graphite particles produced in the artificial graphite of Comparative Example la, 1c and 1d, and has a larger discharge capacity than Comparative Example 1b, and has excellent negative electrode characteristics. It was found to have. Further, the artificial graphite of the present invention In the particle production, Examples 1a, 1d, 1e, 1; 1 and 1 £, in which the size of the grinder gap was 0.5 to 20 times the average particle diameter of the raw black filler powder, had a large discharge capacity. In addition, the irreversible capacity is particularly small and desirable.
- Example 1 o-; Lt and Comparative Example 1 f Graphite particles of 1 g to 1 g are shown in Table 9 above. Under such conditions, evaluation as a lithium ion secondary battery negative electrode was performed. Table 11 shows the results.
- a lithium secondary battery of the present invention was prepared as follows.
- PVDF Polyvinylidene fluoride
- NMP N-methyl-2-pyrrolidone
- the mixture-applied part and the uncoated part were made to coincide with each other on both sides of the Cu foil.
- the coated electrode was pressure-formed by a roll press so that the density of the negative electrode mixture became 1.5 g / cm 3 , thereby producing a negative electrode sheet.
- the negative electrode sheet was cut into strips, and one end of the cut negative electrode sheet was used as an uncoated portion of the Cu foil. .
- the negative electrode tab was attached to the Cu foil portion by ultrasonic welding.
- an active material represented by the chemical formula LiCo02 is used for the positive electrode
- PVDF polyvinylidene fluoride
- a car pump rack is used as the conductive material.
- the mixture was blended at a ratio of 5%, and N-methyl-2-pyrrolidone (NMP) was added as a solvent to prepare a positive electrode mixture paste.
- NMP N-methyl-2-pyrrolidone
- the positive electrode mixture paste thickness 20 per unit area 24rag / C m 2 was applied to one side of A1 foil xm, it was intermittently coated fabric providing uncoated portions at regular intervals. Thereafter, the positive electrode mixture in the applied positive electrode mixture paste was dried to form a positive electrode mixture film.
- a positive electrode mixture film was formed on the other side of the A1 foil in the same manner, and a coated electrode was obtained. At this time, the mixture-applied portion and the non-applied portion were made to coincide with each other on both sides of the A1 foil. Thereafter, the coated electrode was pressure-formed by a roll press so that the density of the positive electrode mixture became 3.3 g / cra 3 , thereby producing a positive electrode sheet. Further, the positive electrode sheet was cut into strips, and one end of the cut positive electrode sheet was made to be an uncoated A1 foil. A positive electrode tab was attached to the A1 foil portion by ultrasonic welding.
- the negative electrode, the separator, the positive electrode, and the separator were laminated in this order and spirally wound to form an electrode group.
- the positive electrode tab and the negative electrode tap were arranged above and below the wound group.
- the electrode group was placed in a battery can, and a positive electrode tap was connected to the battery inner lid and a negative electrode tab was connected to the battery can by spot welding.
- volume ratio in the electrolytic solution is 1: a mixed solvent of 1 ethylene carbonate (EC) and Echirumechiruka Boneto (E MC), were used the L i PF 6 lmol Z dm 3 The dissolved dissolved solution.
- EC ethylene carbonate
- E MC Echirumechiruka Boneto
- Comparative Example 1a AA-size cylindrical lithium secondary batteries were produced in the same manner as in Example 4a, using conventional graphite particles of 1 d.
- a charge / discharge test was performed using the lithium secondary batteries produced in Example 4a and Comparative Example 4a.
- the initial charge is constant current charging at 120 mA (equivalent to 0.2 C)
- constant voltage charging is performed at 4.2 V after battery voltage reaches 4.2 V
- charging time reaches 7 hours It ended at that point.
- the first discharge was performed at a constant current of 120 mA (corresponding to 0.2 C), and ended when the battery voltage reached 3.0 V.
- the discharge current was changed to 60 O mA (equivalent to 1 C) and 1200 mA (equivalent to 2 C).
- the load characteristics were examined.
- the charging current is 60 O mA (equivalent to 1 C)
- the duration time is 2.5 hours
- the discharge current is 60 O mAdC
- Tables 12 and 13 show that the lithium secondary batteries prepared in Example 4a and Comparative Example 4a have the initial discharge capacity, the initial charge / discharge coulombic efficiency, and the 1 C against 0.2 C discharge, respectively.
- the capacity retention rate at 2 C discharge and the capacity retention rate after 300 cycles from the first discharge are shown. It has been found that the lithium secondary battery of the present invention has a larger discharge capacity, higher initial coulomb efficiency, and superior load characteristics and cycle characteristics as compared with the conventional lithium secondary battery. .
- Example 4a and Comparative Example 4a were charged with a large current of 120 OmA (corresponding to 2C), and a constant current was applied until the charging voltage reached 4.2 V.
- the charge acceptability was evaluated based on the size of the chargeable capacity.
- Table 14 shows the rapid charging capacity when charged by the above method. Table 14 shows that the lithium secondary battery of the present invention has a larger charging capacity and better charge acceptability than the conventional lithium secondary battery.
- Example 4a a lithium secondary battery of the present invention manufactured using the negative electrode material of Example 1a, and in Comparative Example 4a, a conventional lithium secondary battery manufactured using the artificial graphite of Comparative Example 1a
- the form of lithium deposition on the negative electrode surface during overcharge was examined by the following method. Using the above-described lithium secondary battery of the present invention and the conventional lithium secondary battery, first, a constant current charge of 120 niA (corresponding to 0.2 C) was performed. The battery was charged at a constant voltage of 2 V and ended when the charging time reached 7 hours. Next, the battery was charged at a constant current of 1200 mA (corresponding to 2C) for 5 minutes to make it overcharged. These batteries were disassembled, the negative electrode was taken out, and the shape of lithium deposited on the negative electrode surface was observed using a scanning electron microscope (SEM).
- SEM scanning electron microscope
- FIG. 12 shows the state of the negative electrode of the lithium secondary battery of the present invention in an overcharged state
- FIG. 13 shows the state of the negative electrode of the conventional lithium secondary battery.
- FIGS. 14 and 15 show the unused electrodes on which lithium is not deposited for reference. Comparing the SEM images before and after overcharge, in the overcharged state, precipitated lithium was observed on the negative electrode.From the SEM image in FIG. 12, lithium was precipitated in the negative electrode of the lithium secondary battery of the present invention in the form of particles. While these particles adhere to each other and form a moss, conventional lithium secondary batteries In the negative electrode, lithium is precipitated in a dendrite shape. Thus, it was found that the use of the artificial black sharp particles of the present invention as a negative electrode material was effective in suppressing the precipitation of lithium dendrite. Industrial applicability
- the lithium ion secondary Artificial graphite particles capable of increasing the capacity of a battery and a method for producing the same, a non-aqueous electrolyte secondary battery negative electrode using the artificial graphite particles, a method for producing the same, and a non-aqueous electrolyte secondary battery negative electrode
- the lithium secondary battery of the present invention using the artificial graphite particles of the present invention as a negative electrode material of a lithium secondary battery has high capacity, excellent rapid charge / discharge characteristics, and little cycle deterioration. Furthermore, the artificial black belly particles of the present invention have a small electrolyte solution decomposition, a small irreversible capacity, and are excellent in electrode coating properties and electrode adhesion, so that the above-mentioned improvement can be made in a lithium secondary battery. Further, the production process of the artificial graphite belly particles of the present invention is easy in the production process, and enables the mass production of artificial graphite particles.
- the coatability and adhesion of the negative electrode active material can be improved, and the rapid charge / discharge characteristics and cycle characteristics can be improved. Therefore, portable devices such as mobile phones and notebook personal computers, and electric vehicles Thus, a lithium secondary battery suitable for a power supply for power storage and the like can be provided.
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Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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EP02716390.6A EP1361194B1 (en) | 2001-01-25 | 2002-01-25 | Artificial graphite particle and method for producing the same, nonaqueous electrolyte secondary battery negative electrode and method for producing the same, and lithium secondary battery |
JP2002559347A JP4448279B2 (ja) | 2001-01-25 | 2002-01-25 | 人造黒鉛質粒子及びその製造方法、非水電解液二次電池負極及びその製造方法、並びにリチウム二次電池 |
KR1020037009738A KR100597065B1 (ko) | 2001-01-25 | 2002-01-25 | 인조흑연질 입자 및 그 제조방법, 비수전해액 2차전지음극 및 그 제조방법, 및 리튬 2차전지 |
CA002435980A CA2435980C (en) | 2001-01-25 | 2002-01-25 | Artificial graphite particles and method for manufacturing same, nonaqueous electrolyte secondary cell negative electrode and method for manufacturing same, and lithium secondary cell |
US10/470,076 US7829222B2 (en) | 2001-01-25 | 2002-01-25 | Artificial graphite particles and method for manufacturing same, nonaqueous electrolyte secondary cell, negative electrode and method for manufacturing same, and lithium secondary cell |
US12/938,673 US8211571B2 (en) | 2001-01-25 | 2010-11-03 | Artificial graphite particles and method for manufacturing same, nonaqueous electrolyte secondary cell negative electrode and method for manufacturing same, and lithium secondary cell |
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JP2001-017141 | 2001-01-25 | ||
JP2001017141A JP2002222650A (ja) | 2001-01-25 | 2001-01-25 | 非水電解液二次電池負極用黒鉛質粒子及びその製造法、非水電解液二次電池負極並びに非水電解液二次電池 |
JP2001270099 | 2001-09-06 | ||
JP2001-270099 | 2001-09-06 | ||
JP2001341754 | 2001-11-07 | ||
JP2001-341754 | 2001-11-07 |
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US10470076 A-371-Of-International | 2002-01-25 | ||
US12/938,673 Division US8211571B2 (en) | 2001-01-25 | 2010-11-03 | Artificial graphite particles and method for manufacturing same, nonaqueous electrolyte secondary cell negative electrode and method for manufacturing same, and lithium secondary cell |
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US (2) | US7829222B2 (ja) |
EP (1) | EP1361194B1 (ja) |
JP (1) | JP4448279B2 (ja) |
KR (1) | KR100597065B1 (ja) |
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Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2007069664A1 (ja) * | 2005-12-14 | 2007-06-21 | Mitsui Mining Co., Ltd. | 黒鉛粒子、炭素-黒鉛複合粒子及びそれらの製造方法 |
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JP2018006072A (ja) * | 2016-06-29 | 2018-01-11 | オートモーティブエナジーサプライ株式会社 | リチウムイオン二次電池用負極 |
JP2018006071A (ja) * | 2016-06-29 | 2018-01-11 | オートモーティブエナジーサプライ株式会社 | リチウムイオン二次電池用負極 |
JP7375568B2 (ja) | 2020-01-17 | 2023-11-08 | 株式会社Gsユアサ | 負極活物質、負極、非水電解質蓄電素子及びその製造方法 |
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Publication number | Publication date |
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CA2435980A1 (en) | 2002-08-01 |
EP1361194A4 (en) | 2006-06-07 |
KR100597065B1 (ko) | 2006-07-06 |
US20110045354A1 (en) | 2011-02-24 |
EP1361194A1 (en) | 2003-11-12 |
US20040115117A1 (en) | 2004-06-17 |
JPWO2002059040A1 (ja) | 2004-06-03 |
US8211571B2 (en) | 2012-07-03 |
JP4448279B2 (ja) | 2010-04-07 |
CN1315722C (zh) | 2007-05-16 |
CA2435980C (en) | 2008-07-29 |
EP1361194B1 (en) | 2014-06-25 |
CN1527795A (zh) | 2004-09-08 |
US7829222B2 (en) | 2010-11-09 |
KR20040012713A (ko) | 2004-02-11 |
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