WO2014119960A1 - 구형 천연 흑연을 포함하는 음극 및 이를 포함하는 리튬 이차 전지 - Google Patents
구형 천연 흑연을 포함하는 음극 및 이를 포함하는 리튬 이차 전지 Download PDFInfo
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- WO2014119960A1 WO2014119960A1 PCT/KR2014/000906 KR2014000906W WO2014119960A1 WO 2014119960 A1 WO2014119960 A1 WO 2014119960A1 KR 2014000906 W KR2014000906 W KR 2014000906W WO 2014119960 A1 WO2014119960 A1 WO 2014119960A1
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- natural graphite
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- H—ELECTRICITY
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- 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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- 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
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- 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
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- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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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- H—ELECTRICITY
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H—ELECTRICITY
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- 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
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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
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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
Definitions
- the present invention relates to a negative electrode including spherical natural graphite and a lithium secondary battery including the same.
- Lithium secondary batteries are the batteries that can best meet these demands, and research on these is being actively conducted.
- graphite often exhibits a shape close to the scale, and the layer plane is deposited parallel to the collector surface during cathode formation. Therefore, there is a problem that the edge of the graphite layer is disposed perpendicular to the anode so that lithium ions detached from the anode during charging cannot smoothly intrude between the graphite layers.
- lithium ions do not sufficiently diffuse into graphite, resulting in a low discharge capacity.
- lithium secondary batteries generally adopt a constant current-constant voltage charging method, and a discharge adopts a constant current discharge method, lithium ions inserted deep in the graphite crystal at low current during constant voltage charging are completely discharged at high rate discharge. Since it remains in graphite without being, it became one cause of cycling deterioration of graphite.
- the problem to be solved of the present invention is to provide a negative electrode for a lithium secondary battery excellent in initial efficiency, electrode adhesion and capacity characteristics, and a lithium secondary battery comprising the same.
- the present invention provides a negative electrode having a spherical natural graphite coated with an amorphous carbon layer on the surface, the orientation index is 0.06 to 0.08 at a compression density of 1.40 g / cc to 1.85 g / cc.
- the present invention provides a lithium secondary battery including a positive electrode, the negative electrode, a separator interposed between the positive electrode and the negative electrode and an electrolyte in which lithium salt is dissolved.
- the present invention can improve the initial efficiency, electrode adhesion and capacity characteristics of the lithium secondary battery by controlling the orientation index of the negative electrode by coating the spherical natural graphite surface with amorphous carbon.
- FIG. 1 shows the hardness of the spherical natural graphite according to the surface, and the hard spherical natural graphite (a) and the soft spherical natural graphite (b) according to the degree to which the amorphous carbon layer is coated on the surface. ).
- FIG. 2 is a graph showing the initial efficiency characteristics of the lithium secondary battery according to the orientation index of the lithium secondary batteries of Examples 1 to 3 and Comparative Examples 1 and 2 according to Experimental Example 2 of the present invention.
- FIG. 3 is a graph showing the capacity characteristics of lithium secondary batteries according to the orientation index of the lithium secondary batteries of Examples 1, 3 and 4, and Comparative Examples 3 to 5 according to Experimental Example 3 of the present invention.
- the negative electrode according to the embodiment of the present invention includes spherical natural graphite coated with an amorphous carbon layer on the surface thereof, and has an orientation index of 0.06 to 0.08 at a compression density of 1.40 g / cc to 1.85 g / cc.
- the spherical natural graphite surface with amorphous carbon to adjust the orientation index of the negative electrode, it is possible to improve the initial efficiency, electrode adhesion and capacity characteristics of the lithium secondary battery.
- amorphous carbon or crystalline carbon is used as a negative electrode material of a lithium secondary battery, and crystalline carbon is mainly used because of its high capacity.
- Such crystalline carbons include natural graphite or artificial graphite.
- natural graphite exhibits high voltage flatness and high capacity close to the theoretical capacity at low cost, and thus has high utility as an active material.
- natural graphite exhibits a high crystalline plate shape, when it is manufactured as a pole plate, the active material is compactly compressed to a high density, so that impregnation of the electrolyte is not easy, and thus high rate charge and discharge characteristics may be degraded.
- the electrode plate when the electrode plate is manufactured using only natural graphite in a high crystalline plate shape, there may be problems such as dropping of the active material from the current collector, bending of the electrode plate, difficulty in controlling the thickness of the electrode plate, low adhesion between the active material and the current collector, and impregnation of the electrolyte.
- the present invention solved the above problems by spherical shape while using a natural graphite that can exhibit a high capacity.
- the spherical natural graphite is about 1000 times the electrical resistivity in the in-plane direction of the graphite layer surface, if the orientation direction of the spherical natural graphite can control the anisotropy of the electrical resistivity of the graphite-containing composition ( ⁇ Since it is possible to alleviate the property, it can be applied to various electronic devices in addition to the battery.
- the spherical natural graphite may vary in hardness depending on the surface thereof, and the hard spherical natural graphite (a) has a lower cathode orientation index after pressing in manufacturing a cathode. By forming a low electrode density, the energy density per unit volume can be lowered.
- the soft spherical natural graphite (b) may have a higher negative electrode orientation index after rolling, thereby increasing the peel strength of the negative electrode.
- the surface hardness of such spherical natural graphite may be influenced by the degree of surface coating of spherical natural graphite.
- the negative electrode according to an embodiment of the present invention may utilize the advantages of spherical natural graphite which may exhibit high capacity and at the same time coat the surface of the spherical natural graphite with amorphous carbon to adjust the surface hardness of the spherical natural graphite particles.
- spherical natural graphite which may exhibit high capacity and at the same time coat the surface of the spherical natural graphite with amorphous carbon to adjust the surface hardness of the spherical natural graphite particles.
- a method for producing high-crystalline plate-shaped natural graphite into spherical natural graphite for example, by introducing the plate-shaped graphite particles into the spheronizing device to determine the rotor speed and the rotor time By adjusting, spherical natural graphite having a desired particle size can be obtained.
- the method for coating the surface of spherical natural graphite according to one embodiment of the present invention with an amorphous carbon layer is selected from the group consisting of methane, ethane, ethylene, butane, acetylene, carbon monoxide, propane, polyvinyl alcohol and propylene, for example.
- the carbon source or pitch may be placed in a firing furnace together with spherical natural graphite, for example, by firing and coating in a temperature range of 300 ° C to 1400 ° C.
- the pitch may be a coal-based pitch or a petroleum-based pitch.
- the orientation index of the negative electrode including spherical natural graphite coated with amorphous carbon on the surface is preferably 0.06 to 0.08 at a compression density of 1.40 g / cc to 1.85 g / cc. If the orientation index is less than 0.06, there is a problem that the spherical natural graphite coated with amorphous carbon during rolling is broken and the amorphous carbon layer is broken, so that the spherical natural graphite is exposed out of the amorphous carbon layer, in which case the initial efficiency of the lithium secondary battery is remarkably increased. May decrease. When the orientation index is more than 0.08, the excessive amorphous carbon layer acts as a resistance, thereby causing a problem that the high temperature storage characteristics of the lithium secondary battery are significantly reduced.
- the orientation index of the negative electrode may depend on the coating amount of the amorphous carbon layer on the spherical natural graphite surface and the compressive force applied when the negative electrode active material is applied and rolled on the negative electrode current collector.
- the amorphous carbon layer for spherical natural graphite may be 0.1% to 28% with respect to the spherical natural graphite as a whole. If the amorphous carbon layer is too small, there is a problem that the hardness and negative electrode density of the spherical natural graphite cannot be increased and the orientation of the negative electrode is lowered. On the contrary, if the amorphous carbon layer is too large, the mobility of lithium ions may be impeded. .
- the thickness of the amorphous carbon layer may be 50 nm to 700 nm.
- the average particle diameter (D 50 ) of the spherical natural graphite coated with an amorphous carbon layer on the surface having the thickness range is 12 ⁇ m to 18 ⁇ m.
- the average particle diameter of the spherical natural graphite coated with the amorphous carbon layer may be advantageous as the particle size is made smaller in order to maximize the disorder in the expansion direction for each of the particles to prevent the particles from expanding due to the charging of lithium ions. Can be.
- the particle diameter of the spherical natural graphite coated with the amorphous carbon layer is less than 12 ⁇ m, a large amount of binder is required due to the increase in the number of particles per unit volume, and the degree of sphericity and spheronization yield may be lowered.
- the maximum particle diameter exceeds 18 ⁇ m, as the expansion becomes severe and charge and discharge are repeated, binding between particles and binding between the particles and the current collector may be degraded, thereby significantly reducing cycle characteristics.
- the orientation index indicates that the crystal structures of spherical natural graphite included in the negative electrode are arranged in a predetermined direction, and may be measured by X-ray diffraction (XRD).
- Orientation index of the negative electrode according to an embodiment of the present invention is the (110) and (004) plane after measuring the (110) and (004) plane of the spherical natural graphite contained in the negative electrode, more specifically, the negative electrode after XRD Area ratio ((110) / (004)) obtained by integrating the peak intensity. More specifically, XRD measurement conditions are as follows.
- Measuring zone and step angle / measuring time Measuring zone and step angle / measuring time:
- (004) plane 53.5 degrees ⁇ 2 ⁇ ⁇ 56.0 degrees, 0.01 degrees / 3 seconds, where 2 ⁇ represents the diffraction angle.
- the XRD measurement is one example, other measurement methods may also be used, and the orientation index of the negative electrode may be measured by the above method.
- the spherical natural graphite coated with an amorphous carbon layer on the surface according to an embodiment of the present invention preferably has a specific surface area of 1.5 m 2 / g to 4.0 m 2 / g.
- the negative electrode according to an embodiment of the present invention can be prepared by conventional methods known in the art.
- a slurry is prepared by mixing and stirring a solvent, a binder, and a conducting agent in the negative electrode active material of spherical natural graphite, and then applying (coating) to a current collector of a metal material, compressing, and drying the negative electrode. It can manufacture.
- the binder is used to bind the negative electrode active material particles to maintain the molded body, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), styrene butadiene rubber Binders) are used.
- PTFE polytetrafluoroethylene
- PVdF polyvinylidene fluoride
- styrene butadiene rubber Binders styrene butadiene rubber Binders
- the binder is a solvent-based binder represented by polyvinylidene fluoride (PVdF) (i.e., a binder using an organic solvent as a solvent), acrylonitrile-butadiene rubber, styrene-butadiene rubber (SBR), and It is divided into an aqueous binder (that is, a binder using water as a solvent) which is any one selected from the group consisting of acrylic rubbers or a mixture of two or more thereof.
- PVdF polyvinylidene fluoride
- SBR styrene-butadiene rubber
- Aqueous binders unlike solvent binders, are economical, environmentally friendly, harmless to the health of workers, and have a greater binding effect than solvent-based binders. It is preferable that it is SBR as an aqueous binder.
- the negative electrode of the lithium secondary battery may further include a thickener for viscosity control.
- the thickener may be a cellulose-based compound, and may be, for example, any one selected from the group consisting of carboxy methyl cellulose (CMC), hydroxy methyl cellulose, hydroxy ethyl cellulose, and hydroxy propyl cellulose, or a mixture of two or more thereof. have.
- the thickener is preferably carboxy methyl cellulose (CMC), the spherical natural graphite and the binder can be applied to the cathode by dispersing in water with carboxy methyl cellulose.
- the conductive agent is natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, summer black, carbon nanotube, fullerene, carbon fiber, It may be any one selected from the group consisting of metal fibers, carbon fluoride, aluminum, nickel powder, zinc oxide, potassium titanate, titanium oxide and polyphenylene derivatives, or a mixture of two or more thereof, preferably carbon black. .
- Non-limiting examples of the negative electrode current collector according to an embodiment of the present invention is a foil made by copper, gold, nickel or a copper alloy or a combination thereof.
- the present invention provides a lithium secondary battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode and an electrolyte in which lithium salt is dissolved.
- the lithium secondary battery according to the exemplary embodiment of the present invention may include all conventional lithium secondary batteries, such as a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
- the lithium secondary battery of the present invention can be prepared according to conventional methods known in the art. For example, a porous separator may be placed between the positive electrode and the negative electrode, and an electrolyte in which lithium salt is dissolved may be added.
- a positive electrode according to an embodiment of the present invention can be prepared by conventional methods known in the art.
- a positive electrode may be prepared by mixing and stirring a solvent, a binder, a conductive agent, and a dispersant in a positive electrode active material, if necessary, and then applying the coating (coating) to a current collector of a metal material, compressing it, and drying the same. have.
- the positive electrode is manufactured by applying a positive electrode active material on a positive electrode current collector and then drying.
- the current collector of the metal material is a metal having high conductivity, and any metal can be used as long as the slurry of the electrode active material is a metal that can be easily adhered.
- Non-limiting examples of the positive electrode current collector include a foil made of aluminum, nickel, or a combination thereof.
- the solvent for forming the positive electrode includes an organic solvent such as NMP (N-methyl pyrrolidone), DMF (dimethyl formamide), acetone, dimethyl acetamide or water, and these solvents alone or in combination of two or more. Can be mixed and used. The amount of the solvent used is sufficient to dissolve and disperse the electrode active material, the binder, and the conductive agent in consideration of the coating thickness of the slurry and the production yield.
- NMP N-methyl pyrrolidone
- DMF dimethyl formamide
- acetone dimethyl acetamide or water
- the separator may be a conventional porous polymer film conventionally used as a separator, for example, polyolefin such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer
- the porous polymer film made of the polymer may be used alone or by laminating them, or a conventional porous nonwoven fabric, for example, a non-woven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, or the like may be used. It is not.
- the lithium salt which can be included as an electrolyte used in the present invention can be used without limitation, those which are commonly used in a lithium secondary battery electrolyte, such as the lithium salt, the anion is F -, Cl -, Br -, I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 - may be any one
- Examples of the electrolyte used in the present invention include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like, which can be used in manufacturing a lithium secondary battery. no.
- the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be cylindrical, square, pouch type or coin type using a can.
- the lithium secondary battery of the present invention can be used as a power source for various electronic products.
- the present invention may be used in a portable telephone, a mobile phone, a game console, a portable television, a laptop computer, a calculator, and the like, but is not limited thereto.
- the prepared negative electrode active material slurry was coated on one surface of a copper current collector to a thickness of 65 ⁇ m, dried and rolled, and then punched to a predetermined size to prepare a negative electrode.
- the orientation index of the negative electrode at a compression density of 1.6 g / cc was 0.061.
- LiCoO 2 was used as a positive electrode active material, acetylene black as a conductive agent, SBR was mixed with a binder in a weight ratio of 94: 3.5: 2.5, and then added to NMP to prepare a positive electrode active material slurry.
- the prepared slurry was coated on one surface of an aluminum foil, dried and rolled, and then punched to a predetermined size to prepare a positive electrode.
- an electrolyte containing 1 M LiPF 6 dissolved in a solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed in a volume ratio of 30:70 was injected to form a coin-type lithium secondary.
- the battery was prepared.
- Spherical natural graphite (13 ⁇ m) having about 2.3% of the amorphous carbon layer was prepared with respect to the entire spherical natural graphite coated with the amorphous carbon layer by mixing petroleum pitch and spherical natural graphite at 15: 100 wt%, and 1.6 g
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that an anode having an orientation index of 0.063 at a compression density of / cc was used.
- spherical natural graphite 16 ⁇ m
- amorphous carbon layer of about 4.1% based on the entire spherical natural graphite coated with the amorphous carbon layer.
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that an anode having an orientation index of 0.078 at a compression density of / cc was used.
- Spherical natural graphite (15 ⁇ m) having an amorphous carbon layer of about 3.4% was prepared with respect to the entire spherical natural graphite coated with the amorphous carbon layer by mixing petroleum pitch and spherical natural graphite at 20: 100 wt%, and 1.6 g
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that a negative electrode having an orientation index of 0.07 was used at a compression density of / cc.
- Spherical natural graphite (20 ⁇ m) coated with amorphous carbon was prepared by mixing petroleum pitch and spherical natural graphite at 30: 100 wt%, using a negative electrode having an orientation index of 0.092 at a compression density of 1.6 g / cc.
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that.
- Spherical natural graphite (19 ⁇ m) coated with amorphous carbon was prepared by mixing petroleum pitch and spherical natural graphite at 50: 100 wt%, using a negative electrode having an orientation index of 0.118 at a compression density of 1.6 g / cc.
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that.
- Spherical natural graphite (8 ⁇ m) coated with amorphous carbon was prepared by mixing petroleum pitch and spherical natural graphite in a ratio of 5: 100 wt%, using a negative electrode having an orientation index of 0.034 at a compression density of 1.6 g / cc.
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that.
- Spherical natural graphite (9 ⁇ m) coated with amorphous carbon was prepared by mixing petroleum pitch and spherical natural graphite at 7.5: 100 wt%, using a negative electrode having an orientation index of 0.036 at a compression density of 1.6 g / cc.
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that.
- Spherical natural graphite (10 ⁇ m) coated with amorphous carbon was prepared by mixing petroleum pitch and spherical natural graphite in a ratio of 1 to 100 wt%, using a negative electrode having an orientation index of 0.055 at a compression density of 1.6 g / cc.
- a lithium secondary battery was manufactured in the same manner as in Example 1, except that.
- XRD diffraction measurements using Cu were performed on the cathodes prepared according to Examples 1 to 4 and Comparative Examples 1 to 5.
- the orientation index is obtained by measuring the (110) and (004) planes of spherical natural graphite contained in the cathode by XRD and then integrating the peak intensities of the (110) plane and (004) plane ((110) / (004). )). More specifically, XRD measurement conditions are as follows.
- Measuring zone and step angle / measuring time Measuring zone and step angle / measuring time:
- (004) plane 53.5 degrees ⁇ 2 ⁇ ⁇ 56.0 degrees, 0.01 degrees / 3 seconds, where 2 ⁇ represents the diffraction angle.
- the coin-type lithium secondary batteries prepared in Examples 1 to 3, and Comparative Examples 1 and 2 Charged with a constant current (0.1 C) up to 5 mV and then terminated after a power failure at 5 mV until the current reaches 0.005 C.
- the discharge of the battery was discharged at a constant current (0.1 C) up to 1.0 V, and the initial efficiency according to the orientation index was measured. The results are shown in FIG.
- the initial efficiency of the lithium secondary battery can be improved by adjusting the orientation index of the negative electrode, and in particular, it was confirmed that the initial index efficiency of the negative electrode was significantly superior in the range of 0.06 to 0.08.
- the lithium secondary battery was charged to 1 C at 5 ° C./0.005 C at constant current / constant voltage (CC / CV) conditions at 45 ° C., and then discharged at 1 C to 1.0 V under constant current (CC) conditions, and the capacity was measured. This was repeated 1 to 3 cycles, the capacity characteristics according to the orientation index after 4 weeks is shown in FIG.
- the capacity of the secondary battery was about 90% or more, whereas Comparative Examples 3 to 5 having an orientation index of the negative electrode were less than 0.06.
- the capacity of the secondary battery was about 88% or less.
- the capacity of the lithium secondary battery could be improved by adjusting the orientation index of the negative electrode.
- the orientation index of the negative electrode exhibited significantly superior capacity characteristics in the range of 0.06 to 0.08.
- the present invention can improve the initial efficiency, electrode adhesion and capacity characteristics of the lithium secondary battery by coating the spherical natural graphite surface with amorphous carbon to adjust the orientation index of the negative electrode, it can be usefully used in the secondary battery field.
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Abstract
Description
Claims (14)
- 표면에 비정질 탄소층이 코팅된 구형 천연 흑연을 포함하고, 1.40 g/cc 내지 1.85 g/cc의 압축 밀도에서 배향 지수가 0.06 내지 0.08인 음극.
- 제 1 항에 있어서,상기 표면에 비정질 탄소층이 코팅된 구형 천연 흑연은 평균 입경(D50)이 12 ㎛ 내지 18 ㎛인 것을 특징으로 하는 음극.
- 제 1 항에 있어서,상기 배향 지수는 음극에 포함된 구형 천연 흑연의 (110)면과 (004)면을 XRD로 측정하여 각각의 측정된 XRD 피크를 적분하여 얻어진 면적비((110)/(004))인 것을 특징으로 하는 음극.
- 제 1 항에 있어서,상기 표면에 비정질 탄소층이 코팅된 구형 천연 흑연은 1.5㎡/g 내지 4.0㎡/g 의 비표면적을 갖는 것을 특징으로 하는 음극.
- 제 1 항에 있어서,상기 비정질 탄소층은 메탄, 에탄, 에틸렌, 부탄, 아세틸렌, 일산화탄소, 프로판, 폴리비닐알코올 및 프로필렌으로 구성된 군에서 선택된 1 종 이상의 기상 또는 액상 탄소 공급원을 이용하여 열분해 탄소에 의한 코팅; 또는 액상 또는 고상의 핏치에 의한 코팅에 의해 형성된 것을 특징으로 하는 음극.
- 제 5 항에 있어서,상기 핏치는 석탄계 핏치(pitch) 또는 석유계 핏치인 것을 특징으로 하는 음극.
- 제 1 항에 있어서,상기 구형 천연 흑연에 대한 비정질 탄소층은 구형 천연 흑연 전체에 대해 0.1% 내지 28%의 범위로 포함되는 것을 특징으로 하는 음극.
- 제 1 항에 있어서,상기 비정질 탄소층의 두께는 50 nm 내지 700 nm인 것을 특징으로 하는 음극.
- 제 1 항에 있어서,상기 음극은 수계 바인더를 포함하는 것을 특징으로 하는 음극.
- 제 9 항에 있어서,상기 수계 바인더는 아크릴로나이트릴-부타디엔고무, 스티렌-부타디엔 고무(styrene-butadiene rubber; SBR) 및 아크릴 고무로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 음극.
- 제 1 항에 있어서,상기 음극은 증점제를 더 포함하는 것을 특징으로 하는 음극.
- 제 11 항에 있어서,상기 증점제는 셀룰로오스계 화합물인 것을 특징으로 하는 음극.
- 제 12 항에 있어서,상기 셀룰로오스계 화합물은 카르복시 메틸 셀룰로오스, 하이드록시 메틸 셀룰로오스, 하이드록시 에틸 셀룰로오스 및 하이드록시 프로필 셀룰로오스로 이루어진 군에서 선택된 어느 하나 또는 이들 중 2 종 이상의 혼합물인 것을 특징으로 하는 음극.
- 양극, 음극, 상기 양극과 음극 사이에 개재된 세퍼레이터 및 리튬염이 용해되어 있는 전해질을 포함하는 리튬 이차 전지에 있어서, 상기 음극이 제 1 항에 따른 음극인 것을 특징으로 하는 리튬 이차 전지.
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EP14726065.7A EP2790252B1 (en) | 2013-02-04 | 2014-02-03 | Anode comprising spherical natural graphite and lithium secondary battery including same |
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US10026956B2 (en) | 2018-07-17 |
KR20140099987A (ko) | 2014-08-14 |
TW201503473A (zh) | 2015-01-16 |
KR101582718B1 (ko) | 2016-01-06 |
US20140227588A1 (en) | 2014-08-14 |
CN104106160B (zh) | 2016-11-30 |
EP2790252A4 (en) | 2015-01-21 |
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JP6070724B2 (ja) | 2017-02-01 |
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