WO2019177338A1 - Composite silicium-carbone amorphe, son procédé de préparation et batterie secondaire au lithium le comprenant - Google Patents

Composite silicium-carbone amorphe, son procédé de préparation et batterie secondaire au lithium le comprenant Download PDF

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WO2019177338A1
WO2019177338A1 PCT/KR2019/002843 KR2019002843W WO2019177338A1 WO 2019177338 A1 WO2019177338 A1 WO 2019177338A1 KR 2019002843 W KR2019002843 W KR 2019002843W WO 2019177338 A1 WO2019177338 A1 WO 2019177338A1
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amorphous silicon
carbon composite
carbon
silicon
composite
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PCT/KR2019/002843
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English (en)
Korean (ko)
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김장배
박수진
채종현
양지혜
복태수
홍동기
류재건
유석근
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주식회사 엘지화학
울산과학기술원
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Priority claimed from KR1020190026971A external-priority patent/KR102207529B1/ko
Application filed by 주식회사 엘지화학, 울산과학기술원 filed Critical 주식회사 엘지화학
Priority to CN201980006152.3A priority Critical patent/CN111433154B/zh
Priority to JP2020531992A priority patent/JP7062212B2/ja
Priority to EP19767922.8A priority patent/EP3718969A4/fr
Priority to US16/769,909 priority patent/US11616233B2/en
Publication of WO2019177338A1 publication Critical patent/WO2019177338A1/fr
Priority to US18/110,153 priority patent/US20230197957A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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 relates to an amorphous silicon-carbon composite, a method of manufacturing the same, and a negative electrode and a lithium secondary battery for a lithium secondary battery comprising the same.
  • Lithium secondary batteries for example, lithium ion batteries
  • nickel hydride batteries and other secondary batteries are becoming increasingly important as power supplies for on-board power supplies or portable terminals such as notebook computers.
  • a lithium secondary battery capable of obtaining high energy density at a light weight can be used as a high output power source for mounting a vehicle, and thus it is expected to continuously increase demand in the future.
  • the lithium secondary battery is manufactured by using a material capable of inserting and detaching lithium ions as an active material of a negative electrode, installing a porous separator between the positive electrode and the negative electrode, and then injecting a liquid electrolyte. Electricity is generated or consumed by redox reactions following insertion and desorption.
  • the lithium secondary battery various types of carbon-based materials including artificial graphite, natural graphite, hard carbon, and soft carbon capable of inserting and detaching lithium have been applied as a negative electrode active material.
  • the carbon-based graphites the graphite not only exhibits a high discharge voltage of 3.6 V, but also provides an advantage in terms of energy density of the lithium secondary battery, and guarantees the long life of the lithium secondary battery with excellent reversibility. It is widely used.
  • the graphite active material has a low graphite density (theoretical density of 2.2 g / cc) in the production of the electrode plate, which has a low capacity in terms of energy density per unit volume of the electrode plate, and easily generates side reactions with the organic electrolyte used at high voltages. There was a problem of capacity reduction.
  • the carbon-based negative electrode active material In order to solve such a problem of the carbon-based negative electrode active material, a Si-based negative electrode active material having a much higher capacity than graphite has been developed and studied.
  • the high-capacity Si-based negative electrode material is accompanied by a severe volume change during charging and discharging, which causes a breakdown of particles and thus has a disadvantage of poor life characteristics.
  • the silicon or silicon oxide (SiO x , 0 ⁇ x ⁇ 2) -based negative electrode active material capable of alloying and dealloying lithium ions has a volume expansion of up to 300%. During such volume expansion and contraction, the SiO x -based negative active material is subjected to severe physical stress and collapses.
  • the result is a breakdown of the existing SEI layer and the creation of a new interface, forming a new SEI layer.
  • This causes continuous electrolyte decomposition and consumption of lithium ions, thereby degrading the cycle characteristics of the battery.
  • the conductive structure is destroyed by the volume expansion and contraction of the SiO x -based negative electrode active material, and durability of the electrode decreases, thereby deteriorating battery life.
  • SiO x in the form of nanotubes has been developed.
  • An object of the present invention is to provide an amorphous silicon-carbon composite having a small volume change and no fragmentation during charging and discharging of a lithium secondary battery.
  • an object of the present invention is to provide a method for producing an amorphous silicon-carbon composite having a simple manufacturing process using a pyrolysis method.
  • an object of the present invention is to provide a negative electrode and a lithium secondary battery of a lithium secondary battery including the amorphous silicon-carbon composite to improve the electrical conductivity and life characteristics of the battery.
  • the present invention is an amorphous silicon-carbon composite in which silicon (Si) and carbon (C) are mixed at the molecular level,
  • the composite provides a composite having a diameter of 10 nm to 1 ⁇ m.
  • the present invention comprises the steps of a) preparing a mixed solution by mixing a silane compound containing a hydrocarbon with an organic solvent;
  • the present invention is an active material; Conductive material; In the negative electrode for a lithium secondary battery comprising a binder,
  • the active material provides a negative electrode for a lithium secondary battery comprising the amorphous silicon-carbon composite of the present invention.
  • the present invention is an anode; cathode; A separator interposed between the anode and the cathode; And lithium secondary battery comprising an electrolyte,
  • the negative electrode provides a lithium secondary battery, characterized in that the negative electrode of the present invention.
  • silicon and carbon are mixed in a molecular unit, and thus have a small volume change and no fragmentation during charging and discharging of a battery.
  • the method of manufacturing the amorphous silicon-carbon composite of the present invention has the advantage of a simple process.
  • the lithium secondary battery including the amorphous silicon-carbon composite of the present invention has an excellent electrical conductivity and life characteristics.
  • FIG. 1 is a schematic diagram of an amorphous silicon-carbon composite of the present invention.
  • Example 2 is a transmission electron microscope (TEM) image of the amorphous silicon-carbon composite prepared in Example 1-1.
  • TEM transmission electron microscope
  • Example 3 is a photograph measured using a transmission electron microscope (TEM) energy dispersive spectroscopy of the amorphous silicon-carbon composite (Si-C) prepared in Example 1-1.
  • TEM transmission electron microscope
  • TEM 7 is a transmission electron microscope (TEM) photograph of the amorphous silicon-carbon composite prepared in Comparative Example 3-1.
  • FIG. 8 is an X-ray diffraction graph of Experimental Example 1.
  • Example 10 is an initial charge and discharge graph of Example 1-3, Comparative Example 1-3, and Comparative Example 2-3.
  • Example 11 is an initial charge and discharge graph of Example 1-3 and Comparative Example 3-3.
  • Silicon has a capacity of about 10 times that of graphite, but there is a problem in that the lifespan characteristics of the battery are deteriorated due to volume change and fragmentation occurring during charging and discharging of the battery.
  • the present invention has been made to provide an amorphous silicon-carbon composite in which silicon (Si) and carbon (C) are mixed on a molecular basis.
  • silicon and carbon are mixed in a molecular unit, thereby solving the above problems.
  • the present invention relates to an amorphous silicon-carbon composite in which silicon (Si) and carbon (C) are mixed at the molecular level, and the diameter of the composite is 10 nm to 1 ⁇ m.
  • the amorphous silicon-carbon composite is formed by a pyrolytic deposition process for a silicon source and a carbon source, and the composite includes silicon-carbon covalent bonds, silicon-silicon covalent bonds, and carbon-carbon covalent bonds. Is irregularly present in the complex.
  • the amorphous silicon-carbon composite may further include a hetero atom, in which case the complex may further include one or more bonds among hetero atom-carbon covalent bonds and hetero atom-silicone covalent bonds, and the covalent Bonds are irregularly present in the complex.
  • the hetero atom may be at least one selected from the group consisting of boron (B), phosphorus (P), nitrogen (N) and sulfur (S).
  • the amorphous silicon-carbon composite is formed by a pyrolytic deposition process of a silane compound including a hydrocarbon, and when the compound is pyrolyzed, a part or the entire bond of the compound is broken to form an amorphous silicon-carbon composite.
  • the silicon source and carbon source may be a silane compound comprising a hydrocarbon. Therefore, the composite of the present invention is a silicon and carbon is distributed without a concentration gradient it can minimize the volume expansion problem when applied to a lithium secondary battery, it is possible to improve the life characteristics of the battery.
  • the amorphous silicon-carbon composite includes silicon and carbon in a weight ratio of 3: 7 to 7: 3.
  • the silicon is included below the range may reduce the capacity of the battery, if included beyond the range may reduce the life of the battery.
  • the life of the battery may be reduced, and when the above range is exceeded, the capacity of the battery may be reduced.
  • the amorphous silicon-carbon composite may include trace amounts of hydrogen and oxygen.
  • the amorphous silicon-carbon composite is in the form of particles, the diameter of the composite may be 10nm to 1 ⁇ m, preferably 100 to 500nm. If the diameter of the composite is less than 10nm, not only the density of the composite is significantly lowered, but also difficult to manufacture the electrode. If the diameter exceeds 1 ⁇ m, the electrical conductivity of the composite is greatly reduced, thereby deteriorating battery life and rate characteristics.
  • the density of the amorphous silicon-carbon composite is 0.2 to 0.6 g / cc, preferably 0.3 to 0.5 g / cc. If the density is less than 0.2g / cc, the electrode density is low, that is, the thickness of the electrode becomes thicker compared to the same loading amount, so that the energy density of the battery is lowered. If the density exceeds 0.6g / cc, the resistance of the electrode is increased, thereby decreasing the rate characteristic. do.
  • the amorphous silicon-carbon composite of the present invention is a mixture of silicon and carbon at a molecular level, and consists of a plurality of silicon atoms, a plurality of carbon atoms, and covalent bonds thereof, and may be used as a negative electrode active material of a lithium secondary battery.
  • the amorphous silicon-carbon composite of the present invention When the amorphous silicon-carbon composite of the present invention is used in a lithium secondary battery, problems such as volume change and fragmentation of silicon generated during battery charging and discharging may be solved, and the battery may exhibit excellent electrical conductivity and lifespan characteristics.
  • the present invention comprises the steps of a) preparing a mixed solution by mixing a silane compound containing a hydrocarbon with an organic solvent;
  • Step a) is a step of preparing a mixed solution by mixing a silane compound containing a hydrocarbon with an organic solvent.
  • the silane compound containing the hydrocarbon is a compound containing a hydrocarbon as a functional group in the silane structure, and the kind thereof is not particularly limited, but in the present invention, tetramethylsilane, dimethylsilane, methylsilane, triethylsilane, and phenylsilane are preferred. And it may include one or more selected from the group consisting of diphenylsilane.
  • silane compound including the hydrocarbon may be a compound further comprising a hetero atom.
  • the kind of the compound is not particularly limited as long as the hetero atom can form a covalent bond with silicon and carbon.
  • the hetero atom may be at least one selected from the group consisting of boron (B), phosphorus (P), nitrogen (N) and sulfur (S).
  • the organic solvent may be used without particular limitation as long as it can dissolve the silane compound containing hydrocarbon, preferably, the boiling point is about 100 ° C. or higher, the viscosity is not high, and carbonization is performed at a temperature of 600 ° C. or higher.
  • Organic solvents that do not occur may be used, and in the present invention may specifically include one or more selected from the group consisting of, for example, toluene, benzene, ethylbenzene, xylene, mesitylene, heptane and octane.
  • the organic solvent is used as a dilution to compensate for the boiling point of the silane compound including a hydrocarbon having a relatively low boiling point, and when the pyrolysis temperature is 800 ° C. or higher, thermal decomposition of the organic solvent may occur together. It can serve to control the ratio of silicon and carbon by providing additional carbon within.
  • Mixing of the compound and the organic solvent is preferably performed for about 10 to 30 minutes at room temperature.
  • step b) the mixed solution is thermally decomposed in an inert atmosphere and deposited on a substrate.
  • the pyrolysis is performed by a process of bubbling by supplying an inert gas to the mixed solution, and the inert atmosphere is preferably an argon (Ar) gas atmosphere.
  • the inert atmosphere is preferably an argon (Ar) gas atmosphere.
  • the pyrolysis temperature is 600 to 900 °C, if the pyrolysis temperature is less than 600 °C can not produce an amorphous silicon-carbon composite due to the thermal decomposition of the silane compound containing a hydrocarbon, Above 900 ° C., direct decomposition of the organic solvent may occur to escape the desired mixing ratio of silicon and carbon, as well as to control its content.
  • the pyrolysis temperature is within the above temperature range, the higher the temperature, the lower the content of hydrogen in the amorphous silicon-carbon composite, so the pyrolysis temperature is preferably 700 to 800 ° C.
  • the pyrolysis is made for 10 minutes to 1 hour, preferably 30 minutes to 1 hour.
  • the amorphous silicon-carbon composite produced by the pyrolysis is deposited on a substrate, and further comprising the step of separating the deposited composite can finally produce an amorphous silicon-carbon composite in the form of particles.
  • the method for separating the deposited composite is not particularly limited in the present invention, but preferably, a ball-mill process may be used.
  • the diameter of the deposited composite has a size of more than 1 ⁇ m, the diameter of the amorphous silicon-carbon composite having a particle form separated from the substrate is 10nm to 1 ⁇ m, preferably 100 to 500nm. If the diameter of the composite is less than 10nm, not only the density of the composite is significantly lowered, but also difficult to manufacture the electrode. If the diameter exceeds 1 ⁇ m, the electrical conductivity of the composite is greatly reduced, thereby deteriorating battery life and rate characteristics.
  • the kind of the substrate is not particularly limited in the present invention, and preferably, a silicon or alumina substrate can be used.
  • a mixed solution of the compound and the organic solvent at room temperature is prepared.
  • an inert gas is flowed into the furnace to make it inert atmosphere and heated to adjust the temperature inside the furnace at a constant temperature.
  • the mixture is poured into a furnace to pyrolyze a silane compound including a hydrocarbon to prepare an amorphous silicon-carbon composite, and the composite is deposited on a substrate.
  • the composite deposited on the substrate may be obtained through a process such as a ball mill to obtain an amorphous silicon-carbon composite in the form of particles.
  • the amorphous silicon-carbon composite is manufactured in the form of particles through a process of separating a complex such as a ball mill after substrate deposition, the amorphous silicon-carbon composite is in the form of particles, the diameter of the amorphous silicon-carbon composite in the form of particles Is 10 nm to 1 ⁇ m, and preferably 100 nm to 500 nm.
  • the production method of the present invention is to prepare an amorphous silicon-carbon composite through a simple pyrolysis method, the manufacturing process has a simple advantage.
  • the present invention is an active material; Conductive material; And it relates to a negative electrode for a lithium secondary battery comprising a binder, the active material comprises the amorphous silicon-carbon composite of the present invention.
  • the negative electrode includes a negative electrode active material formed on the negative electrode current collector, the negative electrode active material uses an amorphous silicon-carbon composite prepared according to the present invention.
  • the negative electrode current collector may be specifically selected from the group consisting of copper, stainless steel, titanium, silver, palladium, nickel, alloys thereof, and combinations thereof.
  • the stainless steel may be surface treated with carbon, nickel, titanium, or silver, and an aluminum-cadmium alloy may be used as the alloy.
  • calcined carbon, a nonconductive polymer surface-treated with a conductive material, or a conductive polymer may be used.
  • the said conductive material is used in order to improve the electroconductivity of an electrode active material further.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, 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; Polyphenylene derivatives and the like can be used.
  • the binder is used for bonding the electrode active material and the conductive material to the current collector.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polymethacrylic acid (PMA), polymethyl methacrylate (PMMA) polyacrylamide (PAM), polymethacrylamide, polyacrylonitrile (PAN), polymethacrylonitrile, polyimide (PI), alginic acid, alginate, chitosan, carboxymethylcellulose (CMC) ), Starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber (SBR) , Fluororubbers, various copolymers thereof, and the like.
  • PVDF polyvinyliden
  • the negative electrode may further include a filler and other additives.
  • the present invention is an anode; cathode; A separator interposed between the anode and the cathode; And a lithium secondary battery comprising an electrolyte, the negative electrode relates to a lithium secondary battery characterized in that the negative electrode of the present invention described above.
  • the configuration of the positive electrode, the negative electrode, the separator and the electrolyte of the lithium secondary battery is not particularly limited in the present invention, and is known in the art.
  • the positive electrode includes a positive electrode active material formed on a positive electrode current collector.
  • the positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery, and for example, carbon, nickel on the surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel Surface treated with titanium, silver, or the like can be used.
  • the positive electrode current collector may use various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric having fine irregularities formed on a surface thereof so as to increase the adhesion with the positive electrode active material.
  • cathode active material any cathode active material available in the art may be used.
  • the electrode layer may further include a binder, a conductive material, a filler, and other additives in addition to the positive electrode active material, and the binder and the conductive material are the same as described above for the negative electrode for the lithium secondary battery.
  • the separator may be made of a porous substrate, and the porous substrate may be used as long as it is a porous substrate that is typically used in an electrochemical device.
  • a porous substrate that is typically used in an electrochemical device.
  • a polyolefin-based porous membrane or a nonwoven fabric may be used. It is not.
  • the separator is polyethylene, polypropylene, polybutylene, polypentene, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polycarbonate, polyimide, polyether ether ketone, polyether sulfone, It may be a porous substrate composed of any one selected from the group consisting of polyphenylene oxide, polyphenylene sulfide, and polyethylene naphthalate or a mixture of two or more thereof.
  • the electrolyte of the lithium secondary battery is a non-aqueous electrolyte containing lithium salt and is composed of a lithium salt and a solvent, and a non-aqueous organic solvent, an organic solid electrolyte and an inorganic solid electrolyte are used as the solvent.
  • the lithium salt is a material that is easy to dissolve in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiSCN, LiC 4 BO 8 , LiCF 3 CO 2 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiC 4 F 9 SO 3 , LiC (CF 3 SO 2 ) 3 , (CF 3 SO 2 ) .2NLi, lithium chloroborane, lower aliphatic lithium carbonate, lithium tetraphenyl borate imide and the like can be used.
  • the non-aqueous organic solvent is, for example, N-methyl-2-pyrrolidone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, gamma-butyrolactone, 1,2 Dimethoxy ethane, 1,2-diethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, 4-methyl-1,3-dioxene, Diethyl ether, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxolane derivatives, sulfolane, methylsulforane, 1,3- Aprotic organic solvents such as dimethyl-2-imidazolidinone, propylene carbonate
  • organic solid electrolytes examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyagitation lysine, polyester sulfides, polyvinyl alcohol, polyvinylidene fluoride, Polymers including secondary dissociation groups and the like can be used.
  • Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates and the like of Li, such as Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 S-SiS 2 , and the like, may be used.
  • the non-aqueous electrolyte may further include other additives for the purpose of improving charge / discharge characteristics, flame retardancy, and the like.
  • the additives include pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexa phosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazoli Dinon, N, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol, aluminum trichloride, fluoroethylene carbonate (FEC), propene sultone (PRS), vinylene carbonate ( VC) etc. are mentioned.
  • FEC fluoroethylene carbonate
  • PRS propene sultone
  • VC vinylene carbonate
  • Lithium secondary battery according to the present invention in addition to the winding (winding) which is a general process, it is possible to lamination (stacking) and folding (folding) of the separator and the electrode.
  • the battery case may be cylindrical, square, pouch type, or coin type.
  • TMS tetramethylsilane
  • argon (Ar) gas purity 99.999%) was flowed at a rate of 500 cc / min to make the inside of the furnace in an inert atmosphere. Thereafter, the furnace was heated at a temperature rising rate of 10 ° C./min and heated up to 750 ° C. After the furnace temperature reached 750 ° C., the temperature was maintained for 10 to 30 minutes to keep the temperature inside the furnace constant.
  • the mixed solution was injected into the furnace at a rate of 100 cc / min, and argon gas was flowed and bubbled to thermally decompose the mixed solution.
  • the furnace temperature is lowered to room temperature to obtain an amorphous silicon-carbon composite decomposed on the substrate inside the furnace, and the composite is passed through a ball mill to form silicon (Si) and carbon (C) in the form of particles.
  • Amorphous silicon-carbon composites (Si-C) mixed at the molecular level were prepared (FIGS. 2 and 3).
  • the silicon-carbon composite had a diameter of about 200 nm and a density of 0.42 g / cc.
  • the amorphous silicon-carbon composite prepared in Example 1-1 was used as a negative electrode active material.
  • 80 wt% of the negative electrode active material, 10 wt% of the binder (PAA / CMC, 1: 1 weight ratio), and 10 wt% of the conductive material (super-P) were dispersed in water to form a negative electrode slurry, and the electrode plate was manufactured by coating on a copper electrode.
  • the electrode plate prepared in Example 1-2 was used as the negative electrode.
  • Lithium metal was used as a counter electrode and a polyethylene separator was interposed between the cathode and the counter electrode, and then a mixed solvent of ethylene carbonate and dimethyl carbonate (EC / DEC, 3: 7, volume ratio) using 1.3 M LiPF 6 was used as an electrolyte.
  • Coin cells were prepared using 10% by weight of FEC as an additive.
  • the silicon-carbon composites (Si) were simply mixed by inducing about 15wt% of Si (about 3500mAh / g) and about 85wt% of graphite (about 372mAh / g) to meet 600mAh / g of discharge capacity.
  • -Graphite was prepared (FIG. 4).
  • a coin cell was manufactured in the same manner as in Example 1-3, except that the cathode plate prepared in Comparative Example 1-2 was used as a cathode.
  • silicone oil silicone oil
  • SiOC silicon-oxygen-carbon composite
  • a coin cell was manufactured in the same manner as in Example 1-3, except that the cathode plate prepared in Comparative Example 2-2 was used as the cathode.
  • Si-C amorphous silicon-carbon composite
  • a coin cell was manufactured in the same manner as in Example 1-3, except that the cathode plate prepared in Comparative Example 3-2 was used as a cathode.
  • the silicon-carbon composite (Si-C) of Example 1-1 showed a wide area peak at 32 degrees and 60 degrees. Since the silicon of the silicon-carbon composite (Si-Graphite) of Comparative Example 1-1 is not amorphous, the six silicon peaks (approximately 28 degrees, 47 degrees, 56 degrees, 69 degrees, 76 degrees, and 88 degrees) are clear. The peaks of Graphite appeared at about 26 degrees, 35 degrees, and 44 degrees. In addition, the silicon-oxygen-carbon composite (SiOC) of Comparative Example 2-1 showed a wide area peak at 30 degrees and 42 degrees.
  • Example 1-2 The electrode plates prepared in Example 1-2, Comparative Example 1-2, and Comparative Example 2-2 were measured for electrical conductivity using a four-point probe (Four-point probe) (Fig. 9).
  • the electrode plate of Example 1-2 had excellent electrical conductivity and showed low resistance value.
  • the electrode plate of Comparative Example 1-2 had a low resistance value due to its excellent electrical conductivity because Graphite had a very good electrical conductivity in the form of stacked carbon layers.
  • the electrode plate of Comparative Example 2-3 contained a silicon-oxygen-carbon composite (SiOC), which is a ceramic material, and thus exhibited low electrical conductivity, thereby showing a very high resistance.
  • SiOC silicon-oxygen-carbon composite
  • the charge and discharge rate of the coin cells prepared in Example 1-3, Comparative Example 1-3 and Comparative Example 2-3 is fixed to 0.05 C-rate And, the operating voltage was set to 0.005 ⁇ 2.5V to measure the charge and discharge characteristics of the coin cell (Fig. 10).
  • Example 1-3 having a smaller diameter of the silicone composite has superior charge and discharge characteristics than Comparative Example 3-3, which has a diameter of the silicone composite exceeding 1 ⁇ m.
  • the coin cell of Example 1-3 showed excellent life characteristics because the capacity of the battery hardly decreased even after the cycle progressed.
  • the coin cell of Comparative Examples 1-3 is a very unstable connection because silicon is in contact with the graphite particles with dots, and as the cycle progresses, the volume expansion of the silicon causes the capacity of the battery to decrease, resulting in poor life characteristics. I could not.
  • the coin cell of Comparative Example 2-3 also had a poor battery life as the capacity of the battery decreased as the cycle progressed.
  • Example 1-3 showed a saturation capacity and stable life characteristics before 50cylce, while Comparative Example 3-3 did not saturate for 100 cycles and showed a low capacity.
  • the charge and discharge rates of the coin cells prepared in Examples 1-3, Comparative Examples 1-3 and Comparative Examples 2-3 were 20 cycles at 0.2 C-rate, 10 cycles at 0.5 C-rate, and then 5 Each cycle, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 C-rate was adjusted to charge and discharge rate, and finally returned to 0.2-rate to check whether it is restored normally (Fig. 14).

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Abstract

La présente invention concerne un composite silicium-carbone amorphe, un procédé de préparation d'un composite silicium-carbone amorphe à l'aide d'un procédé de pyrolyse, et une anode de batterie secondaire au lithium et une batterie secondaire au lithium, les deux le comprenant.
PCT/KR2019/002843 2018-03-14 2019-03-12 Composite silicium-carbone amorphe, son procédé de préparation et batterie secondaire au lithium le comprenant WO2019177338A1 (fr)

Priority Applications (5)

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CN201980006152.3A CN111433154B (zh) 2018-03-14 2019-03-12 无定形硅-碳复合物、其制备方法和包含其的锂二次电池
JP2020531992A JP7062212B2 (ja) 2018-03-14 2019-03-12 非晶質シリコン－炭素複合体、この製造方法及びこれを含むリチウム二次電池
EP19767922.8A EP3718969A4 (fr) 2018-03-14 2019-03-12 Composite silicium-carbone amorphe, son procédé de préparation et batterie secondaire au lithium le comprenant
US16/769,909 US11616233B2 (en) 2018-03-14 2019-03-12 Amorphous silicon-carbon composite, preparation method therefor, and lithium secondary battery comprising same
US18/110,153 US20230197957A1 (en) 2018-03-14 2023-02-15 Amorphous silicon-carbon composite, preparation method therefor, and lithium secondary battery comprising same

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KR10-2018-0029924 2018-03-14
KR20180029924 2018-03-14
KR1020190026971A KR102207529B1 (ko) 2018-03-14 2019-03-08 비정질 실리콘-탄소 복합체, 이의 제조방법 및 이를 포함하는 리튬 이차전지
KR10-2019-0026971 2019-03-08

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US18/110,153 Division US20230197957A1 (en) 2018-03-14 2023-02-15 Amorphous silicon-carbon composite, preparation method therefor, and lithium secondary battery comprising same

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JP2013065496A (ja) * 2011-09-20 2013-04-11 Yoshiaki Nagaura シリコン二次電池アモルファス電極の高周波大気圧プラズマｃｖｄによる製造方法
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KR101612603B1 (ko) 2014-03-19 2016-04-14 오씨아이 주식회사 탄소-실리콘 복합체, 이를 포함하는 이차전지용 음극활물질 및 탄소-실리콘 복합체를 제조하는 방법
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KR20170069163A (ko) * 2015-12-10 2017-06-20 주식회사 엘지화학 리튬 이차전지용 음극활물질의 제조 방법 및 이를 적용한 리튬 이차전지
KR20180029924A (ko) 2016-09-12 2018-03-21 윤원준 피더세포 없이 줄기세포 배양이 가능한 배양 조성물 및 방법
KR20190026971A (ko) 2014-08-04 2019-03-13 토요 세이칸 가부시키가이샤 패리슨 공급 장치 및 공급 방법, 이들을 이용한 블로우 성형기 및 블로우 성형 방법

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JPH06263423A (ja) * 1993-03-12 1994-09-20 Minoru Matsuda シリコン材料の製造方法
JP2013065496A (ja) * 2011-09-20 2013-04-11 Yoshiaki Nagaura シリコン二次電池アモルファス電極の高周波大気圧プラズマｃｖｄによる製造方法
KR101583216B1 (ko) * 2013-02-05 2016-01-07 주식회사 케이씨씨 실리콘 나노 입자의 연속 제조 방법 및 이를 포함하는 리튬이차전지용 음극활물질
KR101612603B1 (ko) 2014-03-19 2016-04-14 오씨아이 주식회사 탄소-실리콘 복합체, 이를 포함하는 이차전지용 음극활물질 및 탄소-실리콘 복합체를 제조하는 방법
KR20190026971A (ko) 2014-08-04 2019-03-13 토요 세이칸 가부시키가이샤 패리슨 공급 장치 및 공급 방법, 이들을 이용한 블로우 성형기 및 블로우 성형 방법
JP2016091915A (ja) * 2014-11-10 2016-05-23 信越化学工業株式会社 非水電解質二次電池用負極材及びその製造方法並びに非水電解質二次電池
KR20170069163A (ko) * 2015-12-10 2017-06-20 주식회사 엘지화학 리튬 이차전지용 음극활물질의 제조 방법 및 이를 적용한 리튬 이차전지
KR20180029924A (ko) 2016-09-12 2018-03-21 윤원준 피더세포 없이 줄기세포 배양이 가능한 배양 조성물 및 방법

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