WO2018203731A1 - Matériau actif d'électrode négative, électrode négative comprenant un matériau actif d'électrode négative, batterie secondaire comprenant une électrode négative, et procédé de préparation de matériau actif d'électrode négative - Google Patents

Matériau actif d'électrode négative, électrode négative comprenant un matériau actif d'électrode négative, batterie secondaire comprenant une électrode négative, et procédé de préparation de matériau actif d'électrode négative Download PDF

Info

Publication number
WO2018203731A1
WO2018203731A1 PCT/KR2018/005228 KR2018005228W WO2018203731A1 WO 2018203731 A1 WO2018203731 A1 WO 2018203731A1 KR 2018005228 W KR2018005228 W KR 2018005228W WO 2018203731 A1 WO2018203731 A1 WO 2018203731A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative electrode
layer
active material
resin
electrode active
Prior art date
Application number
PCT/KR2018/005228
Other languages
English (en)
Korean (ko)
Inventor
김동혁
김은경
이용주
조래환
최정현
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN202211141716.4A priority Critical patent/CN115440956A/zh
Priority to EP18795093.6A priority patent/EP3611784B1/fr
Priority to PL18795093T priority patent/PL3611784T3/pl
Priority to CN201880028840.5A priority patent/CN110622343B/zh
Priority to JP2019560141A priority patent/JP7027643B2/ja
Priority claimed from KR1020180051920A external-priority patent/KR102227809B1/ko
Publication of WO2018203731A1 publication Critical patent/WO2018203731A1/fr
Priority to US16/671,487 priority patent/US11929497B2/en

Links

Classifications

    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode active material, a negative electrode including the negative electrode active material, a secondary battery including the negative electrode and a method of manufacturing the negative electrode active material, specifically, the method of manufacturing the negative electrode active material is SiO x (0.5 ⁇ x ⁇ 1.3)
  • the method of manufacturing the negative electrode active material is SiO x (0.5 ⁇ x ⁇ 1.3)
  • Preparing a silicon-based compound comprising a; Disposing a polymer layer including a polymer compound on the silicon compound; Disposing a metal catalyst layer on the polymer layer; And heat treating the silicon-based compound having the polymer layer and the metal catalyst layer disposed thereon.
  • a representative example of an electrochemical device using such electrochemical energy is a secondary battery, and its use area is gradually increasing.
  • portable devices such as portable computers, portable telephones, cameras, and the like
  • secondary batteries high energy density, that is, high capacity lithium secondary batteries
  • a secondary battery is composed of a positive electrode, a negative electrode, an electrolyte, and a separator.
  • the negative electrode includes a negative electrode active material for inserting and detaching lithium ions from the positive electrode, and a silicon-based active material having a large discharge capacity may be used as the negative electrode active material.
  • the silicon-based active material is accompanied with excessive shrinkage and expansion during charging and discharging of the battery, the conductive path in the active material is blocked, thereby deteriorating cycle characteristics of the battery.
  • a carbon coating layer was formed on the surface of the silicon-based active material (see Korean Patent Publication No. 10-2016-0149862). Further, there is an attempt to further improve conductivity by allowing the carbon coating layer to include graphene.
  • conventional chemical vapor deposition (CVD) is mainly used, but this process cannot be simplified because a separate hydrocarbon source must be used.
  • One problem to be solved by the present invention is to provide a method of manufacturing a negative electrode active material that can simplify the process of forming a carbon coating layer containing graphene on the surface of the silicon-based active material.
  • Another object of the present invention is to provide a negative electrode active material, a negative electrode, and a secondary battery capable of controlling excessive volume change of the negative electrode active material during charge and discharge of the battery.
  • preparing a silicon-based compound comprising SiO x (0.5 ⁇ x ⁇ 1.3); Disposing a polymer layer including a polymer compound on the silicon compound; Disposing a metal catalyst layer on the polymer layer; Heat-treating the silicon compound on which the polymer layer and the metal catalyst layer are disposed; And removing the metal catalyst layer, wherein the polymer compound is glucose, fructose, galactose, maltose, lactose, sucrose, phenolic resin, naphthalene resin, polyvinyl alcohol resin, urethane resin, polyimide, furan resin , Cellulose resin, epoxy resin, polystyrene resin, resorcinol-based resin, phloroglucinol-based resin, coal-based pitch, petroleum-based pitch and tar, any one selected from the group consisting of or a mixture of two or more thereof This is provided.
  • the polymer compound is glucose, fructose, galactose, maltose, lacto
  • a silicon-based compound including SiO x (0.5 ⁇ x ⁇ 1.3); An amorphous carbon layer disposed on the silicon compound; A graphene layer disposed on the amorphous carbon layer; And a negative electrode active material including a pore layer corresponding to a spaced space between the amorphous carbon layer and the graphene layer, a negative electrode including the negative electrode active material, and a secondary battery including the negative electrode.
  • the manufacturing method of the negative electrode active material according to an embodiment of the present invention does not require a separate CVD process for supplying a carbon raw material when manufacturing the graphene layer.
  • the amorphous carbon layer and the graphene layer may be formed while the polymer layer and the metal catalyst layer are heat treated, the process may be simplified.
  • the internal stress may be alleviated when the battery is charged and discharged by the pore layer in the negative electrode active material. Accordingly, structure collapse of the negative electrode is suppressed, and the conductive path in the negative electrode active material can be maintained, so that the cycle characteristics of the battery can be improved.
  • the terms “comprise”, “comprise” or “have” are intended to indicate that there is a feature, number, step, component, or combination thereof, that is, one or more other features, It should be understood that it does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.
  • the thickness of the amorphous carbon layer, the graphene layer, the polymer layer, the metal catalyst layer, etc. may be confirmed through a transmission electron microscope (TEM).
  • Method of manufacturing a negative electrode active material comprises the steps of preparing a silicon-based compound comprising SiO x (0.5 ⁇ x ⁇ 1.3); Disposing a polymer layer including a polymer compound on the silicon compound; Disposing a metal catalyst layer on the polymer layer; Heat-treating the silicon compound on which the polymer layer and the metal catalyst layer are disposed; And removing the metal catalyst layer, wherein the polymer compound is glucose, fructose, galactose, maltose, lactose, sucrose, phenolic resin, naphthalene resin, polyvinyl alcohol resin, urethane resin, polyimide, furan resin , Cellulose resin, epoxy resin, polystyrene resin, resorcinol-based resin, phloroglucinol-based resin, coal-based pitch, petroleum-based pitch and tar, any one selected from the group consisting of or a mixture of two or more thereof.
  • the polymer compound is glucose, fructose, galacto
  • the silicon-based compound may include SiO x (0.5 ⁇ x ⁇ 1.3). Preparing the silicon-based compound may include reacting the SiO x1 (0 ⁇ x1 ⁇ 2) with a metal.
  • the SiO x1 (0 ⁇ x1 ⁇ 2 ) may be in the form containing the Si and SiO 2. That is, x and x1 correspond to the number ratio of O to Si contained in the SiO x (0.5 ⁇ x ⁇ 1.3) or the SiO x1 (0 ⁇ x1 ⁇ 2), respectively.
  • the silicon-based compound may further include a metal silicate.
  • the metal silicate may be doped into the SiO x (0.5 ⁇ x ⁇ 1.3) through reacting the SiO x1 (0 ⁇ x1 ⁇ 2) with a metal.
  • the metal silicate may be located inside the silicon-based compound.
  • the metal silicate may be present in a doped state in the SiO x (0.5 ⁇ x ⁇ 1.3).
  • the metal silicate includes at least one selected from the group consisting of Li 2 Si 2 O 5 , Li 3 SiO 3 , Li 4 SiO 4 , Mg 2 SiO 4 , MgSiO 3 , Ca 2 SiO 4 , CaSiO 3 , and TiSiO 4 . It may include.
  • the metal of the metal silicate may be included in an amount of 1 to 30 parts by weight, and specifically 2 to 20 parts by weight, based on 100 parts by weight of SiO x (0.5 ⁇ x ⁇ 1.3). When the above range is satisfied, the growth of Si grains can be suppressed and the initial efficiency can be improved.
  • the SiO x1 (0 ⁇ x1 ⁇ 2 ) with reaction with the metal may be one of a metallic powder or a metallic gas and a reaction containing the metal to SiO x1 (0 ⁇ x1 ⁇ 2 ).
  • the metal may be at least one selected from the group consisting of Li, Mg, Ti, and Ca, and specifically, Li and Mg.
  • the reaction may be performed at 300 ° C. to 1000 ° C. for 1 hour to 24 hours.
  • the reaction may be performed while flowing an inert gas.
  • the inert gas may be at least one selected from the group consisting of Ar, N 2 , Ne, He, and Kr.
  • the preparing of the silicon-based compound may further include removing a part of the metal silicate generated during the reaction with the metal.
  • preparing the silicon-based compound may include removing metal silicates disposed on a surface of the silicon-based compound of the metal silicates generated during the reaction with the metal.
  • the metal silicate can be removed using an aqueous HCl solution.
  • the average particle diameter (D 50 ) of the silicon compound may be 0.1 ⁇ m to 20 ⁇ m, and specifically 0.5 ⁇ m to 10 ⁇ m. When the average particle diameter of the silicon compound satisfies the above range, the rate rate of the battery may be improved.
  • disposing a polymer layer including a polymer compound on the silicon-based compound may include a general method.
  • the polymer layer may be thermally cured after applying the polymer compound on the silicon-based compound, or heat-treated after the carbon-containing material is applied on the silicon-based compound to form the polymer layer.
  • the polymer layer includes polyimide
  • polyacrylic acid (PAA) may be coated on the silicon compound, followed by heat treatment to form the polymer layer.
  • the polymer compound is glucose, fructose, galactose, maltose, lactose, sucrose, phenolic resin, naphthalene resin, polyvinyl alcohol resin, urethane resin, polyimide, furan resin, cellulose resin, epoxy resin, polystyrene resin, resorcy It may be any one selected from the group consisting of nol resin, phloroglucinol resin, coal-based pitch, petroleum-based pitch and tar, or a mixture of two or more thereof, and specifically, may be polyimide.
  • the polymer layer may have a thickness of 0.001 ⁇ m to 10 ⁇ m, and specifically 0.01 ⁇ m to 5 ⁇ m. If the thickness range is satisfied, a sufficient carbon source can be supplied, so that the graphene layer can be formed continuously and uniformly.
  • the disposing a metal catalyst layer on the polymer layer may include the following method.
  • the silicon-based compound on which the polymer layer is formed may be added to a solution containing a metal salt, and then a metal catalyst layer may be disposed on the polymer layer by using an electroless plating method of adding and stirring a reducing agent.
  • the metal catalyst layer may include at least one selected from the group consisting of Ni, Cu, Fe, Cu, and Co, and specifically, may include Ni.
  • the metal catalyst layer may have a thickness of 0.001 ⁇ m to 10 ⁇ m, and specifically 0.01 ⁇ m to 5 ⁇ m. When the thickness range is satisfied, the graphene layer having high crystallinity may be continuously and uniformly formed.
  • the weight ratio of the polymer layer and the metal catalyst layer may be 1: 1 to 20: 1, and specifically 2: 1 to 10: 1.
  • the graphene layer may be formed continuously and uniformly.
  • the polymer layer may be carbonized through the heat treatment of the silicon-based compound in which the polymer layer and the metal catalyst layer are disposed. Accordingly, an amorphous carbon layer may be formed on the silicon compound.
  • a carbon source generated from a polymer layer may be supplied to the metal catalyst layer to form a graphene layer.
  • the heat treatment may be carried out at 300 °C to 1000 °C, specifically 450 °C to 900 °C. When the heat treatment range is satisfied, the graphene layer having high crystallinity may be formed while silicon grain growth is suppressed.
  • the heat treatment may be performed for 0.5 minutes to 1 hour.
  • the removing of the metal catalyst layer may include the following method.
  • the silicon-based compound having the metal catalyst layer formed in the acidic solution may be added, and then etched and dried for a predetermined time to remove the metal catalyst layer.
  • a pore layer corresponding to a spaced space between the amorphous carbon layer and the metal catalyst layer may be formed. Accordingly, since the volume of the negative electrode active material may be prevented from being excessively changed during charging and discharging of the battery, a conductive path in the negative electrode active material may be secured, thereby improving cycle characteristics.
  • a negative active material a silicon-based compound containing SiO x (0.5 ⁇ x ⁇ 1.3); An amorphous carbon layer disposed on the silicon compound; A graphene layer disposed on the amorphous carbon layer; And a pore layer corresponding to a spaced space between the amorphous carbon layer and the graphene layer.
  • the silicon-based compound including SiO x (0.5 ⁇ x ⁇ 1.3) is the same as described above, and thus description thereof is omitted.
  • the amorphous carbon layer may be disposed on the silicon compound.
  • the amorphous carbon layer may include amorphous carbon, and specifically, may be made of amorphous carbon. By the amorphous carbon layer, the rate (rate) characteristics of the battery can be improved.
  • the amorphous carbon layer may have a thickness of 0.001 ⁇ m to 10 ⁇ m, and specifically 0.01 ⁇ m to 5 ⁇ m. When the thickness range is satisfied, it is possible to manufacture a battery having excellent rate characteristics without reducing the initial efficiency.
  • the graphene layer may be disposed on the amorphous carbon layer.
  • the graphene layer may include graphene, and specifically, may be made of graphene.
  • graphene means a carbonaceous structure having a thickness of 0.2 nm or less, including carbon atoms constituting a hexagonal lattice, having flexibility, and having a thin film form.
  • the graphene layer may have a thickness of 0.5 nm to 200 nm, and specifically 1 nm to 100 nm. If the thickness range is satisfied, the cycle characteristics of the battery may be improved.
  • the amorphous carbon layer and the graphene layer may be formed by carbonizing the above-described polymer layer.
  • the pore layer may be located between the amorphous carbon layer and the graphene layer. Specifically, the pore layer corresponds to a spaced space between the amorphous carbon layer and the graphene layer.
  • the void layer may be one spaced space or two or more spaced spaces. That is, the pore layer may exist on at least a portion of the surface of the amorphous carbon layer, and in the case of two or more spaced spaces, they may be scattered on the surface of the amorphous carbon layer.
  • the pore layer is not formed only by removing the metal catalyst layer. Specifically, the pore layer may be implemented because the polymer layer is contracted while being carbonized (pyrolyzed) by the heat treatment.
  • the heat treatment proceeds, so that the pore layer may be formed.
  • the pore layer may play a role of alleviating internal stress caused by a change in volume of the silicon-based compound during charge and discharge of the battery, thereby maintaining a conductive path of the negative electrode active material.
  • the average thickness of the pore layer may be 0.5nm to 200nm, specifically, may be 100nm to 200nm. When the thickness is satisfied, a sufficient area for alleviating the internal stress caused by the volume change of the silicon-based compound during charge and discharge of the battery is secured, so that the conductive path of the negative electrode active material can be more smoothly maintained.
  • the negative electrode according to another embodiment of the present invention may include a negative electrode active material, wherein the negative electrode active material is the same as the negative electrode active material described above.
  • the negative electrode may include a current collector and a negative electrode active material layer disposed on the current collector.
  • the negative electrode active material layer may include the negative electrode active material.
  • the negative electrode active material layer may further include a binder and / or a conductive material.
  • the negative electrode may further include graphite particles, and the graphite particles may be included in the negative electrode active material layer.
  • the binder is polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (polyvinylidene fluoride (PVDF)), polyacrylonitrile, polymethylmethacrylate (polymethylmethacrylate) , Polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM) , Sulfonated EPDM, styrene butadiene rubber (SBR), fluorine rubber, poly acrylic acid (poly acrylic acid) and hydrogen may be included at least one selected from the group consisting of substances substituted with Li, Na or Ca and the like. And also various copolymers thereof.
  • PVDF-co-HFP polyvinylid
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • Examples of the conductive material include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, farnes black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Conductive tubes such as carbon nanotubes; Metal powders such as fluorocarbon, aluminum and nickel powders; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the graphite-based active material particles may be at least one selected from the group consisting of artificial graphite, natural graphite, graphitized carbon fiber, and graphitized mesocarbon microbeads.
  • a secondary battery according to another embodiment of the present invention may include a negative electrode, a positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, and the negative electrode is the same as the negative electrode described above. Since the cathode has been described above, a detailed description thereof will be omitted.
  • the positive electrode may include a positive electrode active material.
  • the cathode active material may be a cathode active material that is commonly used.
  • the cathode active material may be a layered compound such as lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), or a compound substituted with one or more transition metals; Lithium manganese oxides such as Li 1 + y 1 Mn 2-y 1 O 4 (0 ⁇ y 1 ⁇ 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 ; Lithium copper oxide (Li 2 CuO 2 ); Vanadium oxides such as LiV 3 O 8 , V 2 O 5 , Cu 2 V 2 O 7, and the like; Ni-site type lithium nickel oxide represented by the formula LiNi 1-y2 M y2 O 2 , wherein M is Co, Mn, Al, Cu, Fe, Mg, B, or Ga, and satisfies 0.01 ⁇ y
  • the separator separates the negative electrode from the positive electrode and provides a passage for lithium ions, and can be used without particular limitation as long as the separator is used as a separator in a secondary battery. In particular, it has a low resistance to ion migration of the electrolyte and an excellent ability to hydrate the electrolyte. It is preferable.
  • a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer or the like Laminate structures of two or more layers may be used.
  • porous nonwoven fabrics such as nonwoven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers and the like may be used.
  • a coated separator including a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be optionally used as a single layer or a multilayer structure.
  • the electrolyte may include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like, which can be used in manufacturing a lithium secondary battery, but are not limited thereto.
  • the electrolyte may include a non-aqueous organic solvent and a metal salt.
  • non-aqueous organic solvent for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butylo lactone, 1,2-dime Methoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolon, formamide, dimethylformamide, dioxoron, acetonitrile, nitromethane, methyl formate, Methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, pyrion
  • An aprotic organic solvent such as methyl acid or ethyl
  • ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, may be preferably used as high-viscosity organic solvents because they have high dielectric constants to dissociate lithium salts well, such as dimethyl carbonate and diethyl carbonate.
  • high-viscosity organic solvents because they have high dielectric constants to dissociate lithium salts well, such as dimethyl carbonate and diethyl carbonate.
  • an electrolyte having a high electrical conductivity can be made, and thus it can be more preferably used.
  • the metal salt may be a lithium salt
  • the lithium salt is a material that is readily soluble in the non-aqueous electrolyte, for example, is in the lithium salt anion 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 SO 2 ) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -
  • the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc. for the purpose of improving battery life characteristics, reducing battery capacity, and improving discharge capacity of the battery.
  • haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc.
  • Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N-substituted imida
  • One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be included.
  • a battery module including the secondary battery as a unit cell and a battery pack including the same are provided. Since the battery module and the battery pack include the secondary battery having high capacity, high rate characteristics, and cycle characteristics, a medium-large device selected from the group consisting of an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system It can be used as a power source.
  • the temperature of the chamber was then raised to 800 ° C.
  • Ar was used as the inert gas.
  • the chamber temperature was reduced to room temperature to collect the product in the reaction vessel.
  • the collected product was acid treated with HCl.
  • the acid-treated product was milled to have an average particle diameter (D 50 ) of 5 ⁇ m to prepare a silicon compound.
  • the silicon-based compound includes Li 2 Si 2 O 5 and Li 2 SiO 3 , which are metal silicates, and lithium of Li 2 Si 2 O 5 and Li 2 SiO 3 is 100 weight of the silicon-based compound. It was confirmed that the total amount included 5 parts by weight.
  • the silicon compound of Preparation Example 1 was added to a dimethylacetamide (DMAC) solution containing poly acrylic acid (PAA), and stirred for 1 hour in a reducing atmosphere. At this time, Ar gas was used for formation of a reducing atmosphere. Thereafter, the silicon-based compound was extracted through centrifugation, and then PAA-coated silicon-based compound was obtained by vacuum drying.
  • the PAA-coated silicon-based compound was imidized by heat treatment at 300 ° C. for 60 minutes in a reducing atmosphere to form a polyimide layer having a thickness of 1 ⁇ m on the silicon-based compound.
  • the silicon compound on which the polyimide layer was formed was introduced into an aqueous potassium hydroxide (KOH) solution at 50 ° C., followed by stirring for 10 minutes. Thereafter, the silicon compound was extracted by centrifugation. The extracted silicon compound was added to a nickel sulfate (Ni 2 SO 4 ) aqueous solution, stirred for 10 minutes, and then rinsed. Thereafter, the silicon compound was added to an aqueous borohydride solution at 50 ° C., and stirred for 30 minutes to prepare particles having a nickel catalyst layer having a thickness of 100 nm formed on the polyimide layer.
  • KOH potassium hydroxide
  • the particles were introduced into a tube furnace and heat-treated at 600 ° C. for 10 minutes in a reducing atmosphere to form an amorphous carbon layer from the polyimide layer; And a graphene layer disposed on the nickel catalyst layer and including a plurality of graphenes. At this time, Ar gas was used for the reducing atmosphere.
  • the amorphous carbon layer had a thickness of 300 nm and the graphene layer had a thickness of 50 nm.
  • the silicon-based compound having the amorphous carbon layer and the graphene layer formed on the surface of the 1M FeCl 3 aqueous solution was etched for 2 hours, and then dried with ethanol to remove the nickel catalyst layer. As the nickel catalyst layer was removed, a gap layer corresponding to a space in which the amorphous carbon layer and the graphene layer were spaced apart from each other was formed between the amorphous carbon layer and the graphene layer.
  • the thickness of the pore layer was 100 nm to 200 nm.
  • a negative electrode active material of Example 2 was prepared in the same manner as in Example 1, except that the nickel catalyst layer was formed to have a thickness of 50 nm.
  • the thickness of the amorphous carbon layer in the prepared negative active material was 150nm, the thickness of the graphene layer was 25nm.
  • the thickness of the said void layer was 50 nm or more and less than 100 nm.
  • the silicon compound in which the amorphous carbon layer is disposed was placed in a reaction vessel of a chamber, and the temperature of the chamber was raised to 950 ° C. At this time, the atmospheric pressure of the chamber was maintained at 10 mTorr using a rotary pump. Thereafter, after injecting methane gas for 5 minutes, the temperature of the chamber was reduced to room temperature. Thereafter, the product in the reaction vessel was collected to form a crystalline carbon layer having a thickness of 50 nm on the amorphous carbon layer. There was no spaced space between the amorphous carbon layer and the crystalline carbon layer.
  • the silicon compound on which the amorphous carbon layer was formed was added to an aqueous potassium hydroxide (KOH) solution at 50 ° C., followed by stirring for 10 minutes. Thereafter, the silicon compound was extracted by centrifugation. The extracted silicon compound was added to a nickel sulfate (Ni 2 SO 4 ) aqueous solution, stirred for 10 minutes, and then rinsed. Thereafter, the silicon-based compound was added to an aqueous solution of borohydride at 50 ° C., and stirred for 30 minutes to prepare particles having a nickel catalyst layer having a thickness of 100 nm formed on the amorphous carbon layer.
  • KOH potassium hydroxide
  • the silicon-based compound having the nickel catalyst layer and the amorphous carbon layer disposed on the surface thereof was placed in the reaction vessel of the chamber, and the temperature of the chamber was raised to 950 ° C.
  • the atmospheric pressure of the chamber was maintained at 10 mTorr using a rotary pump.
  • the temperature of the chamber was reduced to room temperature.
  • the product in the reaction vessel was collected to form a graphene layer having a thickness of 50 nm on the amorphous carbon layer. There is no spaced space between the amorphous carbon layer and the graphene layer.
  • Examples 1, 2 and Comparative Examples 1, 2, and 3 each of the negative electrode active material, natural graphite, and carbon black, CMC, and styrene butadiene rubber (SBR) having an average particle diameter (D 50 ) of 65 nm were 9.6: 86.2: A negative electrode slurry with a mixture solid content of 45% was prepared by adding and mixing the solvent with distilled water at 1.0: 1.7: 1.5.
  • SBR styrene butadiene rubber
  • Each of the negative electrode slurry was applied to a copper (Cu) metal thin film which is a negative electrode current collector having a thickness of 20 ⁇ m at a loading of 160 mg / 25 cm 2 and dried. At this time, the temperature of the air circulated was 70 °C. Subsequently, a negative electrode was prepared by rolling and applying the slurry to which the slurry was applied and dried, and drying in a vacuum oven at 130 ° C. for 8 hours.
  • Cu copper
  • a negative electrode current collector having a thickness of 20 ⁇ m at a loading of 160 mg / 25 cm 2
  • Each of the negative electrodes was cut into 1.4875 cm 2 circles to form a negative electrode, and a positive electrode was used for Li-metal.
  • An electrolyte solution containing LiPF 6 dissolved in a concentration of 1 M was injected into a mixed solution having a mixing volume of 7: 3 of ethyl methyl carbonate (EMC) and ethylene carbonate (EC) through a separator of porous polyethylene between the positive electrode and the negative electrode.
  • EMC ethyl methyl carbonate
  • EC ethylene carbonate
  • One cycle was charged at 0.1 C and discharged at 0.1 C.
  • the charge was charged at 0.5 C and discharged at 0.5 C from two cycles to 50 cycles.
  • Capacity retention rate (%) (50 discharge capacity / 1 1.0V discharge capacity) ⁇ 100
  • Example 3 Example 4 Comparative Example 4 Comparative Example 5 Comparative Example 6 Capacity retention 96 91 75 85 87
  • the capacity retention rate is significantly higher than that of the battery of Comparative Example 4 using the negative electrode active material containing no graphene High.
  • the batteries of Examples 3 and 4 have a higher capacity retention rate than the batteries of Comparative Examples 5 and 6 including the negative electrode active material prepared by a general method of sequentially forming an amorphous carbon layer and a crystalline carbon layer (or graphene layer). You can see that. This is because, in the case of the negative electrode active materials of Examples 1 and 2, the pore layer plays a role of suppressing structural collapse of the negative electrode active material and maintaining a conductive path.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un matériau actif d'électrode négative, le procédé comprenant les étapes consistant à : préparer un composé à base de silicium contenant du SiOx (0,5<x<1,3); disposer une couche de polymère contenant un composé polymère sur le composé à base de silicium; disposer une couche de catalyseur métallique sur la couche de polymère; traiter thermiquement le composé à base de silicium sur lequel la couche de polymère et la couche de catalyseur métallique ont été disposées; et retirer la couche de catalyseur métallique, le composé polymère étant l'un quelconque choisi dans le groupe constitué par le glucose, le fructose, le galactose, le maltose, le lactose, le saccharose, une résine à base de phénol, une résine de naphtalène, une résine d'alcool polyvinylique, une résine d'uréthane, un polyimide, une résine furannique, une résine de cellulose, une résine époxy, une résine de polystyrène, une résine à base de résorcinol, une résine à base de phloroglucinol, un brai de houille, un brai de pétrole et du goudron, ou un mélange de deux ou plusieurs de ceux-ci.
PCT/KR2018/005228 2017-05-04 2018-05-04 Matériau actif d'électrode négative, électrode négative comprenant un matériau actif d'électrode négative, batterie secondaire comprenant une électrode négative, et procédé de préparation de matériau actif d'électrode négative WO2018203731A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN202211141716.4A CN115440956A (zh) 2017-05-04 2018-05-04 负极活性材料、包含所述负极活性材料的负极以及包含所述负极的二次电池
EP18795093.6A EP3611784B1 (fr) 2017-05-04 2018-05-04 Matériau actif d'électrode négative, électrode négative comprenant un matériau actif d'électrode négative, batterie secondaire comprenant une électrode négative, et procédé de préparation de matériau actif d'électrode négative
PL18795093T PL3611784T3 (pl) 2017-05-04 2018-05-04 Materiał czynny elektrody ujemnej, elektroda ujemna zawierająca materiał czynny elektrody ujemnej, akumulator zawierający elektrodę ujemną i sposób wytwarzania materiału czynnego elektrody ujemnej
CN201880028840.5A CN110622343B (zh) 2017-05-04 2018-05-04 制备负极活性材料的方法
JP2019560141A JP7027643B2 (ja) 2017-05-04 2018-05-04 負極活物質、前記負極活物質を含む負極、前記負極を含む二次電池及び前記負極活物質の製造方法
US16/671,487 US11929497B2 (en) 2017-05-04 2019-11-01 Negative electrode active material, negative electrode including the negative electrode active material, secondary battery including the negative electrode, and method of preparing the negative electrode active material

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2017-0057050 2017-05-04
KR20170057050 2017-05-04
KR1020180051920A KR102227809B1 (ko) 2017-05-04 2018-05-04 음극 활물질, 상기 음극 활물질을 포함하는 음극, 상기 음극을 포함하는 이차 전지 및 상기 음극 활물질의 제조 방법
KR10-2018-0051920 2018-05-04

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US16/671,487 Continuation US11929497B2 (en) 2017-05-04 2019-11-01 Negative electrode active material, negative electrode including the negative electrode active material, secondary battery including the negative electrode, and method of preparing the negative electrode active material

Publications (1)

Publication Number Publication Date
WO2018203731A1 true WO2018203731A1 (fr) 2018-11-08

Family

ID=64016167

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/005228 WO2018203731A1 (fr) 2017-05-04 2018-05-04 Matériau actif d'électrode négative, électrode négative comprenant un matériau actif d'électrode négative, batterie secondaire comprenant une électrode négative, et procédé de préparation de matériau actif d'électrode négative

Country Status (1)

Country Link
WO (1) WO2018203731A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112490419A (zh) * 2020-11-05 2021-03-12 浙江大学 一种麦芽糖衍生碳/钛铌氧复合材料及其制备方法和应用
CN114122339A (zh) * 2020-08-31 2022-03-01 贝特瑞新材料集团股份有限公司 硅基复合材料、其制备方法和锂离子电池

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080166474A1 (en) * 2006-02-17 2008-07-10 Masahiro Deguchi Conductive composite particle, method of manufacturing the same, electrode using the same, lithium ion secondary battery
KR20100043060A (ko) * 2007-07-12 2010-04-27 스미또모 가가꾸 가부시끼가이샤 전기 화학적 축전 디바이스용 전극
KR101042009B1 (ko) * 2008-09-30 2011-06-16 한국전기연구원 음극 활물질의 제조방법, 그 음극 활물질 및 이를 구비한 리튬이차전지
KR20160001481A (ko) * 2014-06-27 2016-01-06 주식회사 엘지화학 표면 코팅된 다공성 실리콘계 음극 활물질 및 이의 제조방법
KR20160103272A (ko) * 2015-02-24 2016-09-01 주식회사 포스코이에스엠 리튬폴리실리케이트가 코팅된 리튬 망간 복합 산화물의 제조방법, 상기 제조방법에 의하여 제조된 리튬 이차 전지용 리튬 망간 복합 산화물, 및 이를 포함하는 리튬 이차 전지
KR20160149862A (ko) 2015-06-19 2016-12-28 주식회사 엘지화학 실리콘 산화물-탄소-고분자 복합체, 및 이를 포함하는 음극 활물질

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080166474A1 (en) * 2006-02-17 2008-07-10 Masahiro Deguchi Conductive composite particle, method of manufacturing the same, electrode using the same, lithium ion secondary battery
KR20100043060A (ko) * 2007-07-12 2010-04-27 스미또모 가가꾸 가부시끼가이샤 전기 화학적 축전 디바이스용 전극
KR101042009B1 (ko) * 2008-09-30 2011-06-16 한국전기연구원 음극 활물질의 제조방법, 그 음극 활물질 및 이를 구비한 리튬이차전지
KR20160001481A (ko) * 2014-06-27 2016-01-06 주식회사 엘지화학 표면 코팅된 다공성 실리콘계 음극 활물질 및 이의 제조방법
KR20160103272A (ko) * 2015-02-24 2016-09-01 주식회사 포스코이에스엠 리튬폴리실리케이트가 코팅된 리튬 망간 복합 산화물의 제조방법, 상기 제조방법에 의하여 제조된 리튬 이차 전지용 리튬 망간 복합 산화물, 및 이를 포함하는 리튬 이차 전지
KR20160149862A (ko) 2015-06-19 2016-12-28 주식회사 엘지화학 실리콘 산화물-탄소-고분자 복합체, 및 이를 포함하는 음극 활물질

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3611784A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114122339A (zh) * 2020-08-31 2022-03-01 贝特瑞新材料集团股份有限公司 硅基复合材料、其制备方法和锂离子电池
CN112490419A (zh) * 2020-11-05 2021-03-12 浙江大学 一种麦芽糖衍生碳/钛铌氧复合材料及其制备方法和应用
CN112490419B (zh) * 2020-11-05 2022-04-12 浙江大学 一种麦芽糖衍生碳/钛铌氧复合材料及其制备方法和应用

Similar Documents

Publication Publication Date Title
WO2019151774A1 (fr) Matériau actif d&#39;anode, procédé de préparation de matériau actif d&#39;anode, anode comprenant un matériau actif d&#39;anode et batterie secondaire comprenant l&#39;anode
WO2020149622A1 (fr) Anode et batterie rechargeable comprenant ladite anode
WO2017164702A1 (fr) Électrode négative et son procédé de fabrication
WO2019172661A1 (fr) Procédé de fabrication d&#39;une électrode négative
WO2018164405A1 (fr) Matériau actif d&#39;anode, anode comprenant le matériau actif d&#39;anode et batterie secondaire comprenant l&#39;anode
WO2019078690A2 (fr) Matériau actif négatif, électrode négative renfermant un matériau actif négatif, et batterie secondaire comprenant une électrode négative
WO2018203599A1 (fr) Matériau actif d&#39;anode, anode comprenant le matériau actif d&#39;anode, batterie rechargeable comprenant l&#39;anode, et procédé de préparation du matériau actif d&#39;anode
WO2019156461A1 (fr) Électrode positive et batterie rechargeable comprenant une électrode positive
WO2018088735A1 (fr) Anode et son procédé de fabrication
WO2018217071A1 (fr) Procédé de fabrication de cathode pour une batterie rechargeable, cathode pour une batterie rechargeable fabriquée par ce procédé, et batterie rechargeable au lithium comprenant la même cathode
WO2021187961A1 (fr) Matériau actif d&#39;électrode positive pour batterie secondaire et batterie secondaire au lithium le comprenant
US11929497B2 (en) Negative electrode active material, negative electrode including the negative electrode active material, secondary battery including the negative electrode, and method of preparing the negative electrode active material
WO2019093830A1 (fr) Matériau actif d&#39;électrode négative, électrode négative comprenant ledit matériau actif d&#39;électrode négative, et batterie secondaire comprenant ladite électrode négative
WO2020101301A1 (fr) Matériau actif d&#39;anode et son procédé de fabrication
WO2022010121A1 (fr) Anode ayant une propriété de charge rapide améliorée et batterie secondaire au lithium
WO2019156462A1 (fr) Nouveau matériau conducteur, électrode comprenant ledit matériau conducteur, batterie secondaire comprenant ladite électrode, et procédé de fabrication dudit matériau conducteur
WO2019093820A1 (fr) Matériau actif d&#39;électrode négative, électrode négative comprenant ledit matériau actif d&#39;électrode négative, et accumulateur comprenant ladite électrode négative
WO2019164343A1 (fr) Batterie secondaire
WO2018174616A1 (fr) Composition de pré-dispersion de matériau actif d&#39;électrode positive, électrode positive pour batterie secondaire, et batterie secondaire au lithium la comprenant
WO2022055309A1 (fr) Matériau actif d&#39;électrode négative, électrode négative renfermant un matériau actif d&#39;électrode négative, et batterie secondaire comprenant une électrode négative
WO2020149681A1 (fr) Anode, et batterie auxiliaire comprenant l&#39;anode
WO2022045852A1 (fr) Électrode négative et batterie secondaire la comprenant
WO2019050216A2 (fr) Matériau actif d&#39;anode, anode comprenant ledit matériau actif d&#39;anode et batterie secondaire comprenant ladite anode
WO2021112607A1 (fr) Procédé permettant de produire un matériau d&#39;électrode positive pour une batterie rechargeable
WO2018226070A1 (fr) Électrode négative, batterie secondaire comprenant ladite électrode négative, et procédé de fabrication de ladite électrode négative

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: 18795093

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019560141

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018795093

Country of ref document: EP

Effective date: 20191111