WO2016018023A1 - Graphite secondary particle, and lithium secondary battery comprising same - Google Patents
Graphite secondary particle, and lithium secondary battery comprising same Download PDFInfo
- Publication number
- WO2016018023A1 WO2016018023A1 PCT/KR2015/007820 KR2015007820W WO2016018023A1 WO 2016018023 A1 WO2016018023 A1 WO 2016018023A1 KR 2015007820 W KR2015007820 W KR 2015007820W WO 2016018023 A1 WO2016018023 A1 WO 2016018023A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- primary particles
- graphite
- negative electrode
- active material
- particles
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
- C01B32/205—Preparation
-
- 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
-
- 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
-
- 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 is a graphite secondary particles capable of high density of natural graphite primary particles having a high capacity output characteristics and artificial graphite primary particles having excellent cycle characteristics and swelling characteristics are excellent in the rolling property, which is aggregated, bonded or granulated, It relates to a negative electrode used as a negative electrode active material and a lithium secondary battery comprising the negative electrode.
- lithium secondary batteries having high energy density and voltage, long cycle life, and low self discharge rate have been commercially used.
- a lithium secondary battery includes a positive electrode including a positive electrode active material capable of inserting / desorbing lithium ions, a negative electrode containing a negative electrode active material capable of inserting / removing lithium ions, and a microporous separator interposed between the positive electrode and the negative electrode. It means a battery that contains a non-aqueous electrolyte containing lithium ions in the electrode assembly.
- Examples of the positive electrode active material of a lithium secondary battery include transition metal oxides such as lithium cobalt oxide (LiCoO 2 ), lithium-manganese oxide (LiMn 2 O 4 ), or lithium-nickel oxide (LiNiO 2 ), and some of these transition metals are different. Composite oxides substituted with transition metals are used.
- transition metal oxides such as lithium cobalt oxide (LiCoO 2 ), lithium-manganese oxide (LiMn 2 O 4 ), or lithium-nickel oxide (LiNiO 2 ), and some of these transition metals are different.
- Composite oxides substituted with transition metals are used.
- Lithium metal is used as the negative electrode active material, but when lithium metal is used, there is a risk of explosion due to battery short circuit due to dendrite formation, and recently, it has been replaced with a carbon-based material instead of lithium metal.
- crystalline carbon such as natural graphite and artificial graphite
- amorphous carbon such as soft carbon and hard carbon
- Amorphous carbon has an advantage of large capacity, but has a disadvantage of large irreversibility in the charging and discharging process.
- Natural graphite which is a representative crystalline carbon, has a low cost and excellent initial capacity and a relatively high theoretical limit capacity. However, since it has a plate shape, when it is manufactured as a pole plate, it is compressed and oriented flat on the current collector, so that impregnation of the electrolyte is not easy. Its high rate of charge and discharge characteristics is low, the service life is severely degraded, and cycle capacity is low.
- the inventors of the present invention while researching a negative electrode active material having excellent rolling property, high density, high rate charge / discharge characteristics, cycle characteristics, and swelling characteristics, are coated with amorphous carbonaceous primary particles and
- the present invention is made by preparing graphite secondary particles prepared by aggregating, bonding, or granulating artificial graphite primary particles, and confirming that a lithium secondary battery using the same as an anode active material exhibits excellent high rate charge / discharge characteristics, cycle characteristics, and swelling characteristics.
- the present invention is made by preparing graphite secondary particles prepared by aggregating, bonding, or granulating artificial graphite primary particles, and confirming that a lithium secondary battery using the same as an anode active material exhibits excellent high rate charge / discharge characteristics, cycle characteristics, and swelling characteristics.
- An object of the present invention is the natural graphite primary particles coated with amorphous carbon material having high capacity and excellent output characteristics, and the artificial graphite primary particles excellent in cycle characteristics and swelling characteristics are excellent in the rolling property in which the aggregated, bonded or granulated It is to provide a graphite secondary particle capable of densification.
- Another object of the present invention is to provide a negative electrode for a lithium secondary battery, wherein the negative electrode active material slurry containing the graphite secondary particles is coated on a current collector.
- Still another object of the present invention is to provide a lithium secondary battery having excellent high rate charge / discharge characteristics, cycle characteristics, and swelling characteristics, including the negative electrode, the positive electrode, and a separator and an electrolyte interposed between the negative electrode and the positive electrode.
- the present invention is natural graphite primary particles coated with an amorphous carbon material; And a form in which artificial graphite primary particles are aggregated, bonded, or granulated, and the crystallites in the a-axis direction by powder state X-ray diffraction analysis of the natural graphite primary particles are 45 nm to 55 nm, and the c-axis direction
- the crystallite has a size of 25 nm to 35 nm, the crystallite size in the a-axis direction of the artificial graphite primary particles is 35 nm to 45 nm, the crystallite size in the c-axis direction is 15 nm to 30 nm
- Graphite secondary particles are provided.
- the present invention provides a negative electrode for a secondary battery in which the negative electrode active material slurry for a lithium secondary battery including the graphite secondary particles is coated on a current collector.
- the present invention provides a lithium secondary battery including the separator and the electrolyte interposed between the negative electrode and the positive electrode, the negative electrode and the positive electrode for the secondary battery.
- Graphite secondary particles according to the present invention is a natural graphite primary particles exhibiting high capacity and high output characteristics but relatively low cycle characteristics and swelling characteristics, and artificial cycles exhibiting high cycle characteristics and swelling characteristics but relatively low capacity characteristics.
- the graphite primary particles are aggregated, bonded or granulated, not only the high capacity and high output characteristics of the natural graphite primary particles can be exhibited, but also the high cycle characteristics and swelling characteristics of the artificial graphite primary particles can be obtained. Can be represented.
- the graphite secondary particles may be excellent in rollability due to the fine pores present therein, and thus may be densified.
- the lithium secondary battery including the graphite secondary particles as a negative electrode active material has an effect of improving high rate charge / discharge characteristics, cycle characteristics, and swelling characteristics.
- FIG. 1 is a graph illustrating a result of comparing and analyzing swelling characteristics of a coin-type half cell according to an embodiment of the present invention.
- FIG. 2 is a graph showing a result of comparing and analyzing the capacity characteristics of a coin-type half cell according to an embodiment of the present invention.
- Figure 3 shows a result of a comparative analysis of the input and output characteristics of a monocell according to an embodiment of the present invention.
- FIG. 4 is a graph illustrating a result of comparing and analyzing the swelling characteristics according to the heat treatment temperature of the coin-type half cell according to an embodiment of the present invention.
- the present invention is a natural graphite primary particles coated with an amorphous carbon material having a high capacity and excellent output characteristics, easy to use as a negative electrode active material for lithium secondary batteries and artificial graphite primary particles excellent in cycle characteristics and swelling characteristics, Provided graphite secondary particles that can be densified due to excellent rolling or granulated rollability.
- the graphite secondary particles according to an embodiment of the present invention is natural graphite primary particles coated with an amorphous carbon material; And the artificial graphite primary particles are aggregated, bonded or granulated form, the size of crystallites (La) in the a-axis direction by the powder state X-ray diffraction analysis of the natural graphite primary particles is 45 nm to 55 nm, The crystallites in the c-axis direction are 25 nm to 35 nm, the crystallites in the a-axis direction of the artificial graphite primary particles are 35 nm to 45 nm, and the crystallites in the c-axis direction are 15 nm. To 30 nm.
- initial particle refers to an original particle when another type of particle is formed from a particle, and a plurality of primary particles are aggregated, bonded or granulated to form secondary particles. Can be formed.
- secondary paricles refers to physically discernible large particles formed by the aggregation, bonding or granulation of individual primary particles.
- the term “powder state X-ray diffraction analysis” refers to X-ray diffraction analysis using powders (powders) of particles (eg, natural graphite primary particles, artificial graphite primary particles, or graphite secondary particles). It means to carry out.
- electrode state X-ray diffraction analysis means that the particles (eg, natural graphite primary particles, artificial graphite primary particles, or graphite secondary particles) are prepared in an electrode state and subjected to X-ray diffraction analysis. do.
- assembly of primary particles refers to a process in which primary particles spontaneously or artificially aggregate or aggregate to form secondary aggregates by forming an aggregate composed of a plurality of primary particles.
- the terms may be used interchangeably with the same meaning as a set or a combination.
- the natural graphite primary particles coated with the amorphous carbon material may be in a flat form in which an amorphous carbon material is attached or coated on the surface of the natural graphite primary particles, and the natural graphite primary particles
- the method of attaching or coating the amorphous carbon material on the surface is not particularly limited and may be carried out through a method commonly known in the art. For example, it may be prepared by attaching or coating an amorphous carbonaceous precursor material to the flat natural graphite primary particles, followed by heat treatment.
- the amorphous carbon material precursor material is petroleum-based heavy oil and pitch It may be at least one selected from the group consisting of oils. That is, the amorphous carbon material may be derived from at least one material selected from the group consisting of petroleum heavy oil and pitch oil.
- the coating amount of the amorphous carbon material may be more than 0% and 30% or less, and the coating amount may be calculated through Equation 1 below. If the coating amount of the amorphous carbon material is within the above range, in particular, 1% to 5%, as the carbon coating amount increases, the irreversibility of the graphite edge surface may be reduced, thereby including a lithium secondary battery including the negative electrode active material. The characteristics of can be improved. On the other hand, when the coating amount of the amorphous carbon material exceeds 30%, the amount of amorphous carbon compared to natural graphite is too large, making it difficult to easily charge and discharge a lithium secondary battery using the negative electrode active material and insert lithium into the negative electrode during charging. The absolute amount of space that can be reduced may cause a problem that the capacity of the secondary battery is reduced.
- the natural graphite primary particles coated with the amorphous carbon material may be suppressed in shape deformation during rolling by an amorphous carbon material attached or coated on the surface of the natural graphite primary particles, and the natural graphite primary particles and the electrolyte described later Direct contact may be prevented, so that the reaction between the natural graphite primary particles and the electrolyte may be suppressed, thereby improving cycle characteristics of the lithium secondary battery including the negative active material.
- the coating layer is microscopically the primary graphite. It may serve to support the swelling phenomenon of the particle core, the initial swelling characteristics of the lithium secondary battery including this as a negative electrode active material can be improved.
- the natural graphite primary particles coated with the amorphous carbon material may have high crystallinity.
- the crystallinity may be represented by an X-ray diffraction analysis. Specifically, the size of crystallites (La) in the a-axis direction is 45 nm to 55 nm when measuring the powder state of the natural graphite primary particles coated with the amorphous carbon material.
- the size of the crystallite Lc in the c-axis direction may be 25 nm to 35 nm
- the plane spacing d 002 of the (002) plane by X-ray diffraction may be 0.3355 nm to 0.3365 nm
- the electrode state X The peak intensity ratio (I 002 / I 110 ) between the (002) plane and the (110) plane is 550 to 650
- the peak intensity ratio (I 004 / I 110 ) between the (004) plane and the (110) plane by line diffraction analysis. ) May be from 25 to 35.
- the natural graphite primary particles coated with the amorphous carbon material have excellent crystal characteristics such as the crystallite size in the a-axis direction, the crystallite size in the c-axis direction, the interplanar spacing and / or the peak intensity ratio. Dose characteristics can be expressed.
- each X-ray diffraction analysis showing the crystallinity was measured using Cu-K ⁇ ray using the X-ray diffractometer Bruker D4 Endeavor, and the numerical value was corrected through the Topas3 fitting program. It was measured using high-purity silicon as an internal standard sample, and was calculated according to the school method (measurement method set forth by the 17th Committee of the Japan Academic Association).
- the capacity of the natural graphite primary particles coated with the amorphous carbon material may be 355 mAh / g to 365 mAh / g.
- the capacity represents the discharge capacity of the lithium secondary battery (Half-cell) produced using the natural graphite primary particles as a negative electrode active material.
- the average particle diameter of the natural graphite primary particles coated with the amorphous carbon material may be 2 ⁇ m to 10 ⁇ m, and when the average particle diameter is within the above range, the rapid filling property or the cycle characteristic may be excellent.
- the artificial graphite primary particles according to an embodiment of the present invention may be a flat form prepared by heat-treating coal-based heavy oil, petroleum-based heavy oil, tars, pitches, cokes and the like in a temperature range of 500 to 3000. .
- the artificial graphite primary particles may be prepared by heat-treating one or more selected from the group consisting of needle cokes, moxa cokes, and coal tar pitch. That is, the artificial graphite primary particles may be at least one of needle coke-based artificial graphite primary particles, mosaic coke-based artificial graphite primary particles and coal tar pitch artificial graphite primary particles, preferably mosaic coke-based artificial graphite It may be at least one of primary particles and coal tar pitch-based artificial graphite primary particles.
- the coal tar pitch artificial graphite may be MCMB (meso-carbon microbeads) artificial graphite.
- the artificial graphite primary particles may be one having high crystallinity.
- the crystallinity may be expressed by an X-ray diffraction analysis. Specifically, when the powder state of the artificial graphite primary particles is measured, the size (La) of the crystallites in the a-axis direction is 35 nm to 45 nm, and the crystallites in the c-axis direction.
- the size Lc may be 15 nm to 30 nm, and the artificial graphite primary particles may have a plane spacing (d 002 ) of the (002) plane by X-ray diffraction of 0.3365 nm to 0.3380 nm.
- the peak intensity ratio (I 002 / I 110 ) between the (002) plane and the (110) plane by the X-ray diffraction is 50 to 150 in the electrode state
- the peak intensity ratio (the (004) plane and the (110) plane ( I 004 / I 110 ) may be 5 to 15.
- the X-ray diffraction analysis value can be measured through the same method as the above-mentioned method.
- the artificial graphite primary particles have excellent crystallinity characteristics such as crystallite size in the a-axis direction, crystallite size in the c-axis direction, interplanar spacing and / or peak intensity ratio, and thus have excellent capacity characteristics and high c-axis direction. Swelling properties can be expressed.
- the artificial graphite primary particles may have a capacity of 320 mAh / g to 340 mAh / g.
- the capacity represents the discharge capacity of a half-cell produced using the artificial graphite primary particles as a negative electrode active material.
- the average particle diameter of the artificial graphite primary particles may be 2 ⁇ m to 10 ⁇ m, preferably may be the same as or smaller than the natural graphite primary particles coated with the amorphous carbon material. When the average particle diameter is within the above range, the rapid filling property or the cycle characteristic may be excellent.
- the graphite secondary particles according to the present invention include natural graphite primary particles and artificial graphite primary particles coated with the amorphous carbon material, and specifically, natural graphite primary particles coated with the amorphous carbon material. Artificial graphite primary particles may be aggregated, bonded or granulated to form a single mass.
- the weight ratio may be 4: 6 to 6: 4.
- the method of gathering, combining, or granulating the natural graphite primary particles and artificial graphite primary particles coated with the amorphous carbon material is not particularly limited and may be performed by a method commonly known in the art, but for example, heterogeneous A binder, a catalyst, and the like may be mixed with the primary particles and subjected to heat treatment to prepare graphite secondary particles in which the heterogeneous primary particles are aggregated, bonded, or granulated.
- natural graphite primary particles, artificial graphite primary particles, binders and catalysts coated with an amorphous carbon material are introduced into a vacuum reactor under a nitrogen or argon atmosphere, mixed, and heat treated at 1000 to 2800 to produce graphite secondary particles. can do.
- the catalyst may be removed to form pores in the finally produced graphite secondary particles, and the graphite secondary particles having extremely low defects and high crystallinity may be obtained. That is, when heat treatment at a temperature of less than 1000 there is a fear that the capacity does not occur because the graphitization is not normally performed, and if it exceeds 2800, the swelling characteristics may be degraded, if possible in the range of 1000 to 2800 It may be desirable to perform.
- the graphite secondary particles may have a total pore volume of 3 cm 3 / g to 30 cm 3 / g, and a specific surface area of 1 m 2 / g to 10 m 2 / g.
- a lithium secondary battery using the graphite secondary particles having such a specific surface area and / or pore volume as a negative electrode active material can secure a structure having many pores in the negative electrode, thereby improving input / output characteristics and improving swelling characteristics.
- the charge and discharge capacity characteristics can be improved.
- the binder is not particularly limited, and for example, petroleum, coal, artificial pitch, tar, or the like may be used.
- carbides such as silicon, iron, nickel, titanium, and boron, oxides, nitrides, and the like may be used.
- the amount of the catalyst is not particularly limited, but is 1 to 50 parts by weight based on 100 parts by weight of the total amount of the primary particles and the binder. Can be used.
- the graphite secondary particles according to the present invention may be preferably spherical, the aspect ratio may be 1 to 1.5. If the aspect ratio is out of the above range, when the negative electrode is manufactured using the negative electrode active material including the graphite secondary particles, problems such as deformation, stretching, and breakage of the current collector may occur, thereby reducing the density of the active material layer. Can be. In addition, when the graphite secondary particles deviate largely out of the spherical shape outside of the aspect ratio, the orientation in the c-axis direction may be increased, thereby reducing the swelling characteristics of the lithium secondary battery including the negative electrode active material. The negative electrode active material including the graphite secondary particles may adversely affect the distribution of large pores, and as a result, the input / output characteristics of the lithium secondary battery including the graphite secondary particles may also be degraded.
- the average particle diameter of the graphite secondary particles may be 10 ⁇ m to 30 ⁇ m, the peak intensity ratio (I 002 / I 110 ) of the (002) plane and (110) plane by electrode state X-ray diffraction analysis is 200 to 400
- the peak intensity ratio (I 004 / I 110 ) of the (004) plane and the (110) plane may be 10 to 25.
- the peak intensity ratio may be obtained through X-ray diffraction analysis, and X-ray diffraction analysis may be performed by the same method as mentioned above.
- the graphite secondary particles according to the present invention includes natural graphite primary particles coated with a high-capacity, high-output amorphous carbon material in the graphite secondary particles, and artificial graphite primary particles having high cycle characteristics and excellent swelling characteristics. It not only shows high capacity and high power characteristics but also shows excellent cycle characteristics and swelling characteristics.
- the fine pores in the graphite secondary particles can act as a microscopic buffer, so that even when the graphite secondary particles are relatively strong compared to the negative electrode active material using a mixture of different types of graphite May have excellent rollability without being deformed or decomposed, thereby enabling higher density of the active material layer.
- the graphite secondary particles according to the present invention may be included in the negative electrode active material for a secondary battery, and the method for manufacturing the negative electrode active material may be as follows.
- the amorphous carbon material precursor material and the natural graphite primary particles are mixed and heat-treated to prepare natural graphite primary particles coated with the amorphous carbon material; At least one selected from the group consisting of coal-based heavy oil, fibrous heavy oil, tars, pitches, and coke powder is graphitized by heat treatment at 500 to 3000 ° C. to prepare artificial graphite primary particles; Mixing natural graphite primary particles, artificial graphite primary particles, a binder, and a catalyst coated with an amorphous carbon material; It may be prepared including a process of producing a graphite secondary particles by heat treatment at 1000 to 2800 °C.
- the method for producing the negative electrode active material including the graphite secondary particles according to the present invention is not limited to the above method, other methods can be applied, one of the other methods, natural graphite primary particles and digraphitization Mixing the soft carbon particles and assembling them into secondary particles; There may be a method comprising a; to prepare a graphite secondary particles by powder graphitization of the assembled secondary particles by heat treatment at 3000 to 3200 °C.
- the negative electrode active material including the graphite secondary particles manufactured by the two methods exemplified above is composed of natural graphite primary particles, artificial graphite primary particles, and graphite secondary particles coated with an amorphous carbon material as its constituent materials.
- the particles can express excellent capacity characteristics, and can provide a secondary battery with improved swelling characteristics.
- the present invention provides a negative electrode for a secondary battery in which the negative electrode active material slurry for a lithium secondary battery including the graphite secondary particles is coated on a current collector.
- the negative electrode according to an embodiment of the present invention may be prepared by applying a negative electrode active material including the graphite secondary particles to a negative electrode current collector, drying and rolling.
- the negative electrode current collector may be generally used having a thickness of 3 ⁇ m to 500 ⁇ m, and is not particularly limited as long as it has a high conductivity without causing chemical changes in the battery, for example, copper, stainless steel, aluminum, nickel , Titanium, calcined carbon, or a surface treated with carbon, nickel, titanium, silver, or the like on the surface of aluminum or stainless steel may be used.
- the negative electrode active material may be prepared by adding and mixing an additive such as a binder, a conductive material, and a filler to the graphite secondary particles.
- an additive such as a binder, a conductive material, and a filler to the graphite secondary particles.
- a dispersing agent can be added further at the time of organic mixing.
- the binder is a component that assists the bonding of the graphite secondary particles and the conductive material and the bonding to the current collector, and may be generally added in an amount of 1 wt% to 30 wt% based on the total amount of the graphite secondary particles.
- Such binders are not particularly limited and may be conventional ones known in the art, but for example, vinylidene fluoride-hexafluoropropylene copolymer (PVBF-co-HEP), polyvinylidenefluoride, polyacryl Ronitrile (polyacrylonitrile), polymethyl methacrylate (polymethaylmethacrylate), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, poly Propylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene-butyrene rubber (SBR) and fluorine rubber, and may be selected from the group consisting of two or more, especially carboxymethylcellulose (CMC) and styrene-butylene rubber (SBR) can be used in combination.
- the conductive material may typically be added in an amount of 0.05 wt% to 5 wt% based on the total weight of the graphite secondary particles.
- the conductive material is not particularly limited and is not particularly limited as long as it is conductive without causing side reactions with other elements of the battery. Examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black (super-p), acetylene black, ketjen black, channel black, furnace black, lamp black and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives.
- the filler is a component for inhibiting the expansion of the negative electrode and can be used or not as necessary. If the filler is a fibrous material without causing chemical changes in the battery, it is not particularly limited, for example, an olefin polymer such as polyethylene or polypropylene. ; It may be a fibrous material such as glass fiber, carbon fiber.
- the dispersant is not particularly limited, but may be, for example, isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, or the like.
- the coating may be performed by a method commonly known in the art, but for example, the negative electrode active material may be distributed on an upper surface of one side of the negative electrode current collector, and then uniformly dispersed using a doctor blade or the like. have.
- the method may be performed by a die casting method, a comma coating method, a screen printing method, or the like.
- the drying is not particularly limited, but may be performed within one day in a vacuum oven of 50 to 200.
- the present invention provides a lithium secondary battery including the separator and the electrolyte interposed between the negative electrode and the positive electrode, the negative electrode and the positive electrode for the secondary battery.
- the lithium secondary battery according to an embodiment of the present invention is coated with a negative electrode active material including graphite secondary particles formed by the aggregation, bonding or granulation of natural graphite primary particles and artificial graphite primary particles coated with an amorphous carbon material And a separator and an electrolyte interposed between the negative electrode and the positive electrode, the negative electrode and the positive electrode.
- a negative electrode active material including graphite secondary particles formed by the aggregation, bonding or granulation of natural graphite primary particles and artificial graphite primary particles coated with an amorphous carbon material
- a separator and an electrolyte interposed between the negative electrode and the positive electrode, the negative electrode and the positive electrode.
- the positive electrode is not particularly limited, but may be prepared by coating a positive electrode active material on one surface of a positive electrode current collector and then drying the positive electrode active material.
- the positive electrode active material may include additives such as a binder, a conductive material, a filler, and a dispersant.
- the positive electrode current collector may be the same as or included in the aforementioned negative electrode current collector.
- Additives such as binders, conductive materials, fillers, and dispersants used in the positive electrode may be the same as or included in the aforementioned negative electrode.
- the positive electrode active material is not particularly limited and may be a conventional one known in the art, for example, a layered compound such as lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), or one or more transition metals.
- the separator may be an insulating thin film having high ion permeability and mechanical strength, and may generally have a pore diameter of 0.01 ⁇ m to 10 ⁇ m and a thickness of 5 ⁇ m to 300 ⁇ m.
- a porous polymer film such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer and an ethylene / methacrylate copolymer, may be used.
- these may be laminated and used, or a nonwoven fabric made of a conventional porous nonwoven fabric, for example, a high melting glass fiber, polyethylene terephthalate fiber, or the like may be used, but is not limited thereto.
- the electrolyte may include an organic solvent and a lithium salt commonly used in the electrolyte, and are not particularly limited.
- lithium salt of the anion is F -, Cl -, 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 CO 2) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2 ) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, SCN - , and (CF 3 CF 2 SO 2) 2 N - may be at least one member selected from the group consisting of .
- Typical organic solvents include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methylpropyl carbonate, dipropyl carbonate, dimethyl sulfoxide, acetonitrile, dimethoxyethane, diethoxyethane and vinylene. It may be one or more selected from the group consisting of carbonate, sulfolane, gamma-butyrolactone, propylene sulfite and tetrahydrofuran.
- ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, are highly viscous organic solvents, and thus may be preferably used because they dissociate lithium salts in the electrolyte well.
- Such cyclic carbonate dimethylcarboniate and di When a low viscosity, low dielectric constant linear carbonate such as ethyl carbonate is mixed and used in an appropriate ratio, an electrolyte having high electrical conductivity can be prepared, and thus it can be more preferably used.
- the electrolyte may be pyridine, triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexa phosphate triamide, nitrobenzene to improve charge / discharge characteristics, flame retardancy characteristics, etc. as necessary.
- Derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride, and the like. have.
- the solvent may further include a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride to impart nonflammability, may further include carbon dioxide gas to improve high temperature storage characteristics, and may further include fluoro-ethylene carbonate. ), PRS (propene sultone), FPC (fluoro-propylene carbonate) may further include.
- a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride to impart nonflammability
- PRS propene sultone
- FPC fluoro-propylene carbonate
- an electrode assembly is formed by disposing a separator between a positive electrode and a negative electrode, and the electrode assembly may be manufactured by putting an electrolyte into a cylindrical battery case or a square battery case. Alternatively, after stacking the electrode assembly, it may be prepared by impregnating it in an electrolyte and sealing the resultant obtained in a battery case.
- the battery case used in the present invention may be adopted that is commonly used in the art, there is no limitation on the appearance according to the use of the battery, for example, cylindrical, square, pouch type or coin using a can (coin) type and the like.
- the lithium secondary battery according to the present invention may not only be used in a battery cell used as a power source for a small device, but also preferably used as a unit battery in a medium-large battery module including a plurality of battery cells.
- Preferred examples of the medium and large devices include, but are not limited to, electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, power storage systems, and the like.
- Natural graphite coated with amorphous carbon having a grain size of 50 nm in the a-axis direction, 30 nm in the c-axis direction, and a plane spacing (d 002 ) of the (002) plane of 0.3360 nm and a particle diameter of 5 ⁇ m. 50% by weight of the secondary particles (coating amount: 2%) and the crystallite size in the a-axis direction are 30 nm, the crystallite size in the c-axis direction is 20 nm, and the plane spacing (d 002 ) of the (002) plane is 0.3370 nm.
- a binder and a catalyst were added to a mixture composed of 50 wt% of artificial graphite primary particles having a particle diameter of 5 ⁇ m, mixed, and heat-treated at 2800 under a nitrogen atmosphere to prepare graphite secondary particles.
- the artificial graphite primary particles used coke artificial graphite.
- a negative electrode active material slurry was prepared by mixing 96 wt% of the prepared graphite secondary particles with 1 wt% of carbon black conductive material, 1.5 wt% of carboxymethyl cellulose (CMC), and 1.5 wt% of styrene-butadiene rubber (SBR).
- the negative electrode was prepared by coating the copper foil with a thickness of 150 ⁇ m, followed by rolling and drying.
- Graphite secondary particles were prepared in the same manner as in Preparation Example 1, except that artificial graphite primary particles were mother-based artificial graphite, to prepare a negative electrode.
- Graphite secondary particles were prepared in the same manner as in Preparation Example 1, except that the artificial graphite primary particles were MCMB-type artificial graphite, to prepare a negative electrode.
- An anode was manufactured in the same manner as in Preparation Example 1, except that natural graphite coated with amorphous carbon material and artificial graphite were mixed at a weight ratio of 5: 5 instead of the graphite secondary particles.
- a negative electrode was manufactured in the same manner as in Preparation Example 1, except that graphite secondary particles were manufactured using a plurality of artificial graphite primary particles (single material) instead of the natural graphite primary particles coated with an amorphous carbon material. It was.
- a graphite secondary particle was produced in the same manner as in Preparation Example 1 except that the heat treatment temperature was 2500 ° C., and a negative electrode was prepared.
- a graphite secondary particle was prepared in the same manner as in Preparation Example 1 except that the heat treatment temperature was 800 ° C., and a negative electrode was prepared.
- a graphite secondary particle was prepared in the same manner as in Preparation Example 1 except that the heat treatment temperature was 3000 ° C., and a negative electrode was prepared.
- Lithium metal foil was used as a counter electrode, and the counter electrode and the negative electrode prepared in Preparation Example 1-1 were punched into a coin shape, and LiPF6 was 1 mol and 2 wt% of VC (vinyl).
- a coin-type half cell was prepared by injecting a carbonate-based electrolyte solution containing chloride).
- a positive electrode active material slurry was prepared by mixing 96% by weight of LiCoO 2, 2 % by weight of carbon black and 2% by weight of polyfluorovinylidene as a positive electrode active material, and further adding and mixing N-methyl-2-pyrrolidone (NMP). Then, it was coated on an aluminum foil with a thickness of 130 ⁇ m, then rolled and dried to prepare a positive electrode.
- NMP N-methyl-2-pyrrolidone
- a coin-type half cell and a monocell were prepared in the same manner as in Example 1-1, except that the negative electrode prepared in Preparation Example 2 was used as the negative electrode.
- a coin-type half cell and a monocell were prepared in the same manner as in Example 1-1, except that the negative electrode prepared in Preparation Example 3 was used as the negative electrode.
- a coin-type half cell and a monocell were prepared in the same manner as in Example 1-1, except that the negative electrode prepared in Comparative Preparation Example 1 was used as the negative electrode.
- a coin-type half cell and a monocell were prepared in the same manner as in Example 1-1, except that the negative electrode prepared in Comparative Preparation Example 2 was used as the negative electrode.
- a coin-type half cell and a monocell were prepared in the same manner as in Example 1-1, except that the negative electrode prepared in Preparation Example 4 was used as the negative electrode.
- a coin-type half cell and a monocell were manufactured in the same manner as in Example 1-1, except that the negative electrode prepared in Comparative Preparation Example 3 was used as the negative electrode.
- a coin-type half cell and a monocell were prepared in the same manner as in Example 1-1, except that the negative electrode prepared in Comparative Preparation Example 4 was used as the negative electrode.
- Example 4 The swelling characteristics of the coin-type half cells produced in Example 4 and Comparative Examples 3 and 4 were compared and analyzed. The thickness of each cell was measured using a coin-type real-time thickness measurement equipment. The results are shown in FIG.
- the coin-type half cell of Example 4 fabricated using a negative electrode including graphite secondary particles according to the present invention was compared with the coin-type half cells of Comparative Examples 3 and 4. It confirmed that the swelling characteristic was excellent.
- Each battery was charged at a rate of 0.1 C at 25 CC / CV, and then discharged at a rate of 0.1 C at CC up to 1.5 V, thereby measuring charge and discharge capacity, and analyzing charge and discharge efficiency and discharge rate characteristics. The results are shown in FIG.
- the coin type half cells of Examples 1 to 3 manufactured using the negative electrode including the graphite secondary particles according to the present invention are compared with the coin type half cells of Comparative Examples 1 and 2. Overall, the capacity characteristics were somewhat better or similar.
- Each monocell was repeatedly charged and recharged at 25C, 0.2C / 0.2C, 0.2C / 0.5C, 0.2C / 1.0C, and 0.2C / 2.0C under 25 conditions, and the capacity retention rate according to the charge / discharge rate was analyzed. . The results are shown in FIG.
- the monocells of Examples 1 to 3 produced using a negative electrode containing the graphite secondary particles according to the present invention as a negative electrode active material overall capacity compared to the monocells of Comparative Examples 1 and 2 It was confirmed that the retention rate was rather excellent.
Abstract
Description
Claims (23)
- 비정질계 탄소재가 코팅된 천연흑연 1차 입자 및 인조흑연 1차 입자가 조립된 흑연 2차 입자를 포함하고,Natural graphite primary particles coated with an amorphous carbon material and graphite secondary particles assembled with artificial graphite primary particles,상기 천연흑연 1차 입자의 분체 상태 X선 회절 분석에 의한 a축 방향의 결정자의 크기가 45 nm 내지 55 nm이고, c축 방향의 결정자의 크기가 25 nm 내지 35 nm 이며,The size of crystallites in the a-axis direction is 45 nm to 55 nm, the size of the crystallites in the c-axis direction is 25 nm to 35 nm by powder state X-ray diffraction analysis of the natural graphite primary particles,상기 인조흑연 1차 입자의 a축 방향의 결정자의 크기가 35 nm 내지 45 nm이고, c축 방향의 결정자의 크기가 15 nm 내지 30 nm인 것인 음극 활물질.The size of the crystallites in the a-axis direction of the artificial graphite primary particles is 35 nm to 45 nm, the size of the crystallites in the c-axis direction is 15 nm to 30 nm.
- 청구항 1에 있어서,The method according to claim 1,상기 흑연 2차 입자는 총 세공용적이 3 cm3/g 내지 30 cm3/g인 것인 음극 활물질.The graphite secondary particles have a total pore volume of 3 cm 3 / g to 30 cm 3 / g.
- 청구항 1에 있어서,The method according to claim 1,상기 흑연 2차 입자는 비표면적이 1 m2/g 내지 10 m2/g인 것인 음극 활물질.The graphite secondary particles have a specific surface area of 1 m 2 / g to 10 m 2 / g negative electrode active material.
- 청구항 1에 있어서,The method according to claim 1,상기 천연흑연 1차 입자의 용량은 355 mAh/g 내지 365 mAh/g인 것인 음극 활물질.The capacity of the natural graphite primary particles is a negative electrode active material is 355 mAh / g to 365 mAh / g.
- 청구항 1에 있어서,The method according to claim 1,상기 천연흑연 1차 입자는 분체 상태 X선 회절 분석에 의한 (002)면의 면간격(d002)이 0.3355 nm 내지 0.3365 nm인 것인 음극 활물질.The natural graphite primary particles have a surface spacing (d 002 ) of the (002) plane by powder state X-ray diffraction analysis of 0.3355 nm to 0.3365 nm.
- 청구항 1에 있어서,The method according to claim 1,상기 천연흑연 1차 입자는 전극 상태 X선 회절 분석에 의한 (002)면과 (110)면의 피크강도비(I002/I110)가 550 내지 650이고, (004)면과 (110)면의 피크강도비(I004/I110)가 25 내지 35인 것인 음극 활물질.The natural graphite primary particles have a peak intensity ratio (I 002 / I 110 ) of (550) to (650) and (110) plane of (002) plane and (110) plane by electrode state X-ray diffraction analysis. The negative electrode active material having a peak intensity ratio (I 004 / I 110 ) of 25 to 35.
- 청구항 1에 있어서,The method according to claim 1,상기 천연흑연 1차 입자는 평균입경이 2 ㎛ 내지 10 ㎛인 것인 음극 활물질.The natural graphite primary particles are negative active material having an average particle diameter of 2 ㎛ to 10 ㎛.
- 청구항 1에 있어서,The method according to claim 1,상기 인조흑연은 니들 코크스계 인조흑연, 모자익 코크스계 인조흑연 및 MCMB(meso-carbon microbeads)형 인조흑연으로 이루어진 군으로부터 선택된 1종 이상인 것인 음극 활물질.The artificial graphite is at least one selected from the group consisting of needle coke-based artificial graphite, mosaic coke-based artificial graphite and MCMB (meso-carbon microbeads) artificial graphite.
- 청구항 1에 있어서,The method according to claim 1,상기 인조흑연은 모자익 코크스계 인조흑연 및 MCMB형 인조흑연으로 이루어진 군으로부터 선택된 1종 이상인 것인 음극 활물질.The artificial graphite is at least one selected from the group consisting of mosaic coke-based artificial graphite and MCMB artificial graphite.
- 청구항 1에 있어서,The method according to claim 1,상기 인조흑연 1차 입자의 용량은 320 mAh/g 내지 340 mAh/g인 것인 음극 활물질.The capacity of the artificial graphite primary particles is 320 mAh / g to 340 mAh / g of the negative electrode active material.
- 청구항 1에 있어서,The method according to claim 1,상기 인조흑연 1차 입자는 분체 상태 X선 회절 분석에 의한 (002)면의 면간격(d002)이 0.3365 nm 내지 0.3380 nm인 것인 음극 활물질.The artificial graphite primary particles have a surface spacing (d 002 ) of the (002) plane by powder state X-ray diffraction analysis of 0.3365 nm to 0.3380 nm.
- 청구항 1에 있어서,The method according to claim 1,상기 인조흑연 1차 입자는 전극 상태 X선 회절 분석에 의한 (002)면과 (110)면의 피크강도비(I002/I110)가 50 내지 150이고, (004)면과 (110)면의 피크강도비(I004/I110)가 5 내지 15인 것인 음극 활물질.The artificial graphite primary particles have a peak intensity ratio (I 002 / I 110 ) of 50 to 150 between (002) plane and (110) plane by electrode state X-ray diffraction analysis, and (004) plane and (110) plane. The negative electrode active material having a peak intensity ratio (I 004 / I 110 ) of 5 to 15.
- 청구항 1에 있어서,The method according to claim 1,상기 인조흑연 1차 입자는 평균입경이 2 ㎛ 내지 10 ㎛인 것인 음극 활물질.The artificial graphite primary particles have an average particle diameter of 2 ㎛ to 10 ㎛.
- 청구항 1에 있어서,The method according to claim 1,상기 흑연 2차 입자의 평균입경은 10 ㎛ 내지 30 ㎛인 것인 음극 활물질.The average particle diameter of the graphite secondary particles is 10 ㎛ to 30 ㎛ negative active material.
- 청구항 1에 있어서,The method according to claim 1,상기 흑연 2차 입자의 어스팩트비는 1 내지 1.5인 것인 음극 활물질.An aspect ratio of the graphite secondary particles is 1 to 1.5 negative electrode active material.
- 청구항 1에 있어서,The method according to claim 1,상기 흑연 2차 입자는 전극 상태 X선 회절 분석에 의한 (002)면과 (110)면의 피크강도비(I002/I110)가 200 내지 400이고, (004)면과 (110)면의 피크강도비(I004/I110)가 10 내지 25인 것인 음극 활물질.The graphite secondary particles have a peak intensity ratio (I 002 / I 110 ) between (002) and (110) planes of 200 to 400, and (004) and (110) planes by electrode state X-ray diffraction analysis. The peak active material ratio (I 004 / I 110 ) is 10 to 25 negative electrode active material.
- 비정질계 탄소재 전구체 물질과 천연흑연 1차 입자를 혼합하고 열처리하여 비정질계 탄소재가 코팅된 천연흑연 1차 입자를 제조하는 단계;Mixing the amorphous carbon material precursor material with the natural graphite primary particles and heat-treating them to prepare natural graphite primary particles coated with the amorphous carbon material;석탄계 중질유, 섬유계 중질유, 타르류, 피치류 및 코크스류로 이루어진 군에서 선택된 1 종 이상을 500 내지 3000℃의 열처리로 분체 흑연화하여 인조흑연 1차 입자를 제조하는 단계;Preparing artificial graphite primary particles by powder-graphitizing one or more selected from the group consisting of coal-based heavy oil, fibrous heavy oil, tars, pitches, and coke by heat treatment at 500 to 3000 ° C;비정질계 탄소재가 코팅된 천연흑연 1차 입자, 인조흑연 1차 입자, 바인더 및 촉매를 혼합하는 단계; 및Mixing the natural graphite primary particles, artificial graphite primary particles, a binder, and a catalyst coated with an amorphous carbon material; And1000 내지 2800℃로 열처리하여 흑연 2차 입자를 제조하는 단계;를 포함하는 음극 활물질의 제조방법.Method of manufacturing a negative electrode active material comprising a; step of producing a graphite secondary particles by heat treatment at 1000 to 2800 ℃.
- 청구항 17에 있어서,The method according to claim 17,상기 비정질계 탄소재는 석유계 중질유 및 피치오일유로 이루어진 군으로부터 선택된 1종 이상으로 제조되는 것인 음극 활물질의 제조방법.The amorphous carbon material is a method for producing a negative electrode active material is prepared from at least one selected from the group consisting of petroleum-based heavy oil and pitch oil oil.
- 청구항 17에 있어서,The method according to claim 17,상기 천연흑연 1차 입자에 코팅되는 비정질계 탄소재의 코팅량은 0% 초과 및 30% 이하인 것인 음극 활물질의 제조방법.The coating amount of the amorphous carbon material coated on the natural graphite primary particles is greater than 0% and 30% or less.
- 청구항 17에 있어서,The method according to claim 17,상기 흑연 2차 입자는 비정질계 탄소재로 코팅된 천연흑연 1차 입자와 인조흑연 1차 입자가 3:7 내지 7:3의 중량비를 갖도록 포함하는 것인 음극 활물질의 제조방법.The graphite secondary particles are a method for producing a negative electrode active material comprising a natural graphite primary particles and an artificial graphite primary particles coated with an amorphous carbon material to have a weight ratio of 3: 7 to 7: 3.
- 천연흑연 1차 입자 및 이흑연화 탄소(soft carbon) 입자를 혼합하여 2차 입자로 조립하는 단계;Mixing the natural graphite primary particles and soft carbon particles into granulated secondary particles;상기 조립된 2차 입자를 3000 내지 3200℃의 열처리로 분체 흑연화 하여 흑연 2차 입자를 제조하는 단계;를 포함하는 음극 활물질의 제조방법.Preparing graphite secondary particles by powder graphitizing the assembled secondary particles by heat treatment at 3000 to 3200 ° C .;
- 청구항 1에 기재된 음극 활물질을 포함하는 음극 슬러리가 집전체 상에 도포된 이차전지용 음극.The negative electrode for secondary batteries which the negative electrode slurry containing the negative electrode active material of Claim 1 apply | coated on the electrical power collector.
- 청구항 22에 기재된 이차전지용 음극과 양극, 상기 음극과 양극 사이에 개재된 분리막 및 전해질을 포함하는 리튬 이차전지.A lithium secondary battery comprising a separator and an electrolyte interposed between the negative electrode and the positive electrode for a secondary battery according to claim 22, the negative electrode and the positive electrode.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201580002768.5A CN105794027B (en) | 2014-07-29 | 2015-07-27 | Graphite secondary and the lithium secondary battery for including it |
JP2017500385A JP6464252B2 (en) | 2014-07-29 | 2015-07-27 | Graphite secondary particles and lithium secondary battery containing the same |
EP15827495.1A EP3054509B1 (en) | 2014-07-29 | 2015-07-27 | Graphite secondary particle, and lithium secondary battery comprising same |
US15/035,635 US10361426B2 (en) | 2014-07-29 | 2015-07-27 | Secondary graphite particle and secondary lithium battery comprising the same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2014-0096737 | 2014-07-29 | ||
KR20140096737 | 2014-07-29 | ||
KR1020150105325A KR101685832B1 (en) | 2014-07-29 | 2015-07-24 | Graphite secondary particles and lithium secondary battery comprising thereof |
KR10-2015-0105325 | 2015-07-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016018023A1 true WO2016018023A1 (en) | 2016-02-04 |
Family
ID=55217831
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2015/007820 WO2016018023A1 (en) | 2014-07-29 | 2015-07-27 | Graphite secondary particle, and lithium secondary battery comprising same |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2016018023A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017135794A1 (en) * | 2016-02-05 | 2017-08-10 | 주식회사 엘지화학 | Negative electrode active material and secondary battery comprising same |
WO2018008955A1 (en) * | 2016-07-04 | 2018-01-11 | 주식회사 엘지화학 | Negative electrode and secondary battery including same negative electrode |
KR20180004678A (en) * | 2016-07-04 | 2018-01-12 | 주식회사 엘지화학 | Negative electrode and lithium secondarty battery comprising the negative electrode |
WO2018012821A1 (en) * | 2016-07-13 | 2018-01-18 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and rechargeable lithium battery including same |
CN110400906A (en) * | 2018-04-24 | 2019-11-01 | 三星Sdi株式会社 | Negative electrode for lithium rechargeable battery and the lithium rechargeable battery including it |
CN111682177A (en) * | 2020-06-18 | 2020-09-18 | 贝特瑞新材料集团股份有限公司 | Graphite composite material, preparation method and application thereof |
CN111684627A (en) * | 2018-03-15 | 2020-09-18 | 株式会社Lg化学 | Negative electrode active material for lithium secondary battery and negative electrode for lithium secondary battery comprising same |
JP2021048142A (en) * | 2016-07-04 | 2021-03-25 | エルジー・ケム・リミテッド | Negative electrode for secondary battery |
US11217783B2 (en) | 2017-12-22 | 2022-01-04 | Samsung Sdi Co., Ltd. | Negative electrode active material for lithium secondary battery, negative electrode including the same, and lithium secondary battery including the negative electrode |
WO2023043081A1 (en) * | 2021-09-16 | 2023-03-23 | 주식회사 엘지에너지솔루션 | Anode and secondary battery comprising same |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20010072967A (en) * | 1998-08-27 | 2001-07-31 | 가네꼬 히사시 | Nonaqueous Electrolyte Secondary Cell, Method for Manufacturing the Same, and Carbonaceous Material Composition |
KR20070040853A (en) * | 2003-01-22 | 2007-04-17 | 히다치 막셀 가부시키가이샤 | Negative electrode for lithtum secondary battery, method for producing same, and lithtum secondary battery using same |
KR20100072160A (en) * | 2010-06-17 | 2010-06-30 | 엘에스엠트론 주식회사 | Anode active material for lithium secondary battery and lithium secondary battery containing the same for anode |
US20120074610A1 (en) * | 2010-09-27 | 2012-03-29 | Long Time Technology Corp., LTD. | Anode material of lithium-ion secondary battery and preparation method thereof |
KR101249349B1 (en) * | 2009-10-20 | 2013-04-01 | 주식회사 엘지화학 | Negative active material for lithium secondary battery and lithium secondary battery using same |
-
2015
- 2015-07-27 WO PCT/KR2015/007820 patent/WO2016018023A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20010072967A (en) * | 1998-08-27 | 2001-07-31 | 가네꼬 히사시 | Nonaqueous Electrolyte Secondary Cell, Method for Manufacturing the Same, and Carbonaceous Material Composition |
KR20070040853A (en) * | 2003-01-22 | 2007-04-17 | 히다치 막셀 가부시키가이샤 | Negative electrode for lithtum secondary battery, method for producing same, and lithtum secondary battery using same |
KR101249349B1 (en) * | 2009-10-20 | 2013-04-01 | 주식회사 엘지화학 | Negative active material for lithium secondary battery and lithium secondary battery using same |
KR20100072160A (en) * | 2010-06-17 | 2010-06-30 | 엘에스엠트론 주식회사 | Anode active material for lithium secondary battery and lithium secondary battery containing the same for anode |
US20120074610A1 (en) * | 2010-09-27 | 2012-03-29 | Long Time Technology Corp., LTD. | Anode material of lithium-ion secondary battery and preparation method thereof |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021101434A (en) * | 2016-02-05 | 2021-07-08 | エルジー・ケム・リミテッド | Negative-electrode active material and secondary cell including the same |
JP2018530887A (en) * | 2016-02-05 | 2018-10-18 | エルジー・ケム・リミテッド | Negative electrode active material and secondary battery including the same |
WO2017135794A1 (en) * | 2016-02-05 | 2017-08-10 | 주식회사 엘지화학 | Negative electrode active material and secondary battery comprising same |
US10938033B2 (en) | 2016-02-05 | 2021-03-02 | Lg Chem, Ltd. | Negative electrode active material and secondary battery comprising same |
CN107925083A (en) * | 2016-02-05 | 2018-04-17 | 株式会社Lg化学 | Negative active core-shell material and the secondary cell for including it |
CN107925083B (en) * | 2016-02-05 | 2021-06-18 | 株式会社Lg化学 | Negative active material and secondary battery comprising same |
KR20180004678A (en) * | 2016-07-04 | 2018-01-12 | 주식회사 엘지화학 | Negative electrode and lithium secondarty battery comprising the negative electrode |
JP2019507460A (en) * | 2016-07-04 | 2019-03-14 | エルジー・ケム・リミテッド | A negative electrode and a secondary battery including the negative electrode |
KR102005281B1 (en) * | 2016-07-04 | 2019-07-31 | 주식회사 엘지화학 | Negative electrode and lithium secondarty battery comprising the negative electrode |
JP7246810B2 (en) | 2016-07-04 | 2023-03-28 | エルジー エナジー ソリューション リミテッド | Anode for secondary battery |
US11777080B2 (en) | 2016-07-04 | 2023-10-03 | Lg Energy Solution, Ltd. | Negative electrode for secondary battery |
WO2018008955A1 (en) * | 2016-07-04 | 2018-01-11 | 주식회사 엘지화학 | Negative electrode and secondary battery including same negative electrode |
JP2021048142A (en) * | 2016-07-04 | 2021-03-25 | エルジー・ケム・リミテッド | Negative electrode for secondary battery |
CN108352505A (en) * | 2016-07-04 | 2018-07-31 | 株式会社Lg化学 | Cathode and secondary cell comprising it |
US11043692B2 (en) | 2016-07-04 | 2021-06-22 | Lg Chem, Ltd. | Negative electrode and secondary battery including the same |
CN109478647A (en) * | 2016-07-13 | 2019-03-15 | 三星Sdi株式会社 | Negative electrode active material for lithium rechargeable battery and the lithium rechargeable battery including it |
US11705552B2 (en) | 2016-07-13 | 2023-07-18 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and rechargeable lithium battery including same |
WO2018012821A1 (en) * | 2016-07-13 | 2018-01-18 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and rechargeable lithium battery including same |
US11217783B2 (en) | 2017-12-22 | 2022-01-04 | Samsung Sdi Co., Ltd. | Negative electrode active material for lithium secondary battery, negative electrode including the same, and lithium secondary battery including the negative electrode |
US20200365875A1 (en) * | 2018-03-15 | 2020-11-19 | Lg Chem, Ltd. | Negative electrode active material for lithium secondary battery and negative electrode for lithium secondary battery including the same |
CN111684627B (en) * | 2018-03-15 | 2023-07-04 | 株式会社Lg新能源 | Negative electrode active material for lithium secondary battery and negative electrode for lithium secondary battery comprising same |
US11764349B2 (en) * | 2018-03-15 | 2023-09-19 | Lg Energy Solution, Ltd. | Negative electrode active material for lithium secondary battery and negative electrode for lithium secondary battery including the same |
CN111684627A (en) * | 2018-03-15 | 2020-09-18 | 株式会社Lg化学 | Negative electrode active material for lithium secondary battery and negative electrode for lithium secondary battery comprising same |
CN110400906A (en) * | 2018-04-24 | 2019-11-01 | 三星Sdi株式会社 | Negative electrode for lithium rechargeable battery and the lithium rechargeable battery including it |
CN111682177A (en) * | 2020-06-18 | 2020-09-18 | 贝特瑞新材料集团股份有限公司 | Graphite composite material, preparation method and application thereof |
WO2023043081A1 (en) * | 2021-09-16 | 2023-03-23 | 주식회사 엘지에너지솔루션 | Anode and secondary battery comprising same |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2016018023A1 (en) | Graphite secondary particle, and lithium secondary battery comprising same | |
WO2019107936A1 (en) | Negative electrode active material, negative electrode and lithium secondary battery comprising same | |
WO2019235885A1 (en) | Cathode active material for secondary battery, manufacturing method therefor, and lithium secondary battery comprising same | |
WO2016032240A1 (en) | Negative electrode active material having double coating layers, method for preparing same, and lithium secondary battery comprising same | |
WO2015130106A1 (en) | Lithium-nickel based cathode active material, method for preparing same, and lithium secondary battery including same | |
WO2017099456A1 (en) | Negative electrode active material for lithium secondary battery comprising core composed of carbon, manufacturing method therefor, and lithium secondary battery including same | |
WO2019035669A2 (en) | Negative electrode for lithium secondary battery and lithium secondary battery comprising same | |
WO2019194510A1 (en) | Cathode active material for lithium secondary battery, method for manufacturing same, cathode comprising same for lithium secondary battery, and lithium secondary battery | |
WO2020116858A1 (en) | Positive electrode active material for rechargeable battery, production method therefor and rechargeable battery positive electrode comprising same | |
WO2021154021A1 (en) | Positive electrode active material precursor for secondary battery, positive electrode active material, and lithium secondary battery comprising same | |
WO2019168352A1 (en) | Anode active material, preparation method therefor, and anode and lithium secondary battery, which include anode active material | |
WO2021015511A1 (en) | Method for preparing cathode active material for lithium secondary battery, and cathode active material prepared by preparation method | |
WO2021049918A1 (en) | Positive electrode material for secondary battery and lithium secondary battery comprising same | |
WO2018221827A1 (en) | Negative electrode active material, negative electrode comprising negative electrode active material, and secondary battery comprising negative electrode | |
WO2022060138A1 (en) | Negative electrode and secondary battery comprising same | |
WO2022039576A1 (en) | Cathode active material preparation method | |
WO2019078626A1 (en) | Method for preparing cathode active material for secondary battery and secondary battery using same | |
WO2021112606A1 (en) | Cathode active material for lithium secondary battery and method for preparing cathode active material | |
WO2017074109A1 (en) | Cathode for secondary battery, method for preparing same, and lithium secondary battery comprising same | |
WO2021066580A1 (en) | Anode active material, method for preparing anode active material, anode comprising same, and lithium secondary battery | |
WO2018124593A1 (en) | Cathode active material for secondary battery, method for manufacturing same, and lithium secondary battery comprising same | |
WO2022149951A1 (en) | Method for preparing cathode active material and cathode active material | |
WO2022092906A1 (en) | Cathode active material and preparation method therefor | |
WO2021154024A1 (en) | Positive electrode active material precursor for secondary battery, positive electrode active material, method for producing same, and lithium secondary battery including same | |
WO2020180125A1 (en) | Lithium secondary battery |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15827495 Country of ref document: EP Kind code of ref document: A1 |
|
REEP | Request for entry into the european phase |
Ref document number: 2015827495 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015827495 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15035635 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2017500385 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |