[go: up one dir, main page]

WO2025116625A1 - Matériau actif d'électrode négative pour batterie secondaire, son procédé de fabrication et électrode négative le comprenant pour batterie secondaire - Google Patents

Matériau actif d'électrode négative pour batterie secondaire, son procédé de fabrication et électrode négative le comprenant pour batterie secondaire Download PDF

Info

Publication number
WO2025116625A1
WO2025116625A1 PCT/KR2024/019320 KR2024019320W WO2025116625A1 WO 2025116625 A1 WO2025116625 A1 WO 2025116625A1 KR 2024019320 W KR2024019320 W KR 2024019320W WO 2025116625 A1 WO2025116625 A1 WO 2025116625A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative electrode
active material
electrode active
secondary battery
graphene
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/KR2024/019320
Other languages
English (en)
Korean (ko)
Inventor
김영준
심준명
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corenergy Solution Co Ltd
Sungkyunkwan University
Original Assignee
Corenergy Solution Co Ltd
Sungkyunkwan University
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
Priority claimed from KR1020240167611A external-priority patent/KR20250083125A/ko
Application filed by Corenergy Solution Co Ltd, Sungkyunkwan University filed Critical Corenergy Solution Co Ltd
Publication of WO2025116625A1 publication Critical patent/WO2025116625A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • 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
    • 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
    • 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
    • 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 for a secondary battery, a method for producing the same, and a negative electrode for a secondary battery comprising the same.
  • Lithium-ion secondary batteries are in increasing demand for energy storage devices such as portable electronic devices, electric vehicles, and energy storage systems, and their market has also grown significantly. Accordingly, the need for improving the power density and energy density of lithium-ion secondary batteries is increasing.
  • Silicon has been highlighted as a high-capacity anode material due to its high theoretical capacity (4200 mAh/g).
  • the large expansion (approximately 400%) when reacting with lithium ions, material pulverization during repeated charge/discharge, and unstable solid-electrolyte interface reduce the life of secondary batteries, so improvement is needed for practical use.
  • low electrical conductivity and initial Coulombic efficiency of silicon are factors that hinder the implementation of high energy density of the cell, so these also need to be improved.
  • silicon-based materials silicon oxide (SiO x ) is in the spotlight due to its improved volume expansion and lifespan compared to pure silicon materials, but it has the disadvantages of reduced electrical conductivity and initial Coulombic efficiency.
  • the purpose of the present invention is to provide a negative electrode active material for a secondary battery having improved long-term cycle characteristics during a charge/discharge process, a method for producing the same, and a negative electrode for a secondary battery comprising the same.
  • another object of the present invention is to provide a negative electrode active material for a secondary battery having improved electrochemical performance, a method for producing the same, and a negative electrode for a secondary battery including the same by overcoming the problems of a secondary battery using a silicon compound as an negative electrode.
  • One embodiment of the present invention provides a negative electrode active material for a secondary battery, a method for manufacturing the same, and a secondary battery including the same.
  • the negative electrode active material for the secondary battery includes a silicon compound; and a surface layer provided to cover at least a portion of a surface of the silicon compound; wherein the surface layer includes graphene and carbon, and the carbon can be formed by carbonizing an organic compound that forms a catechol bond with the silicon compound.
  • the silicon compound may include at least one of SiO x (0 ⁇ x ⁇ 2), SiO x including a lithium compound (0 ⁇ x ⁇ 2), SiO x including a magnesium compound (0 ⁇ x ⁇ 2), a silicon alloy, and a silicon-carbon composite (Si-C composite).
  • the average thickness of the surface layer may be 10 nm to 10 ⁇ m.
  • the thickness of the surface layer may be 0.05% to 10% with respect to the average radius of the negative electrode active material.
  • the carbon in the silicon compound may be from 0.2 wt% to 20 wt%.
  • the weight ratio of the organic compound to the silicon compound may be 1:0.1 to 0.8.
  • the organic compound may include at least one selected from the group consisting of polydopamine, cellulose, polyphenylene, polypropylene, resin, tannic acid, lignan, catechin, flavonoid, phenolic acid, and stilbene.
  • the organic compound comprises a polymer formed by polymerizing a monomer, wherein the monomer may include one or more of catechol, dopamine, dopamine hydrochloride, norepinephrine, L-dihydroxyphenylalanine, hydroxyphenolic acid, adrenaline, lignin monomer, ellagitannin, and pyrogall (1,2,3-benzenetriol).
  • the monomer may include one or more of catechol, dopamine, dopamine hydrochloride, norepinephrine, L-dihydroxyphenylalanine, hydroxyphenolic acid, adrenaline, lignin monomer, ellagitannin, and pyrogall (1,2,3-benzenetriol).
  • the temperature for carbonizing the organic compound may be from 300° C. to 1500° C.
  • the electrical conductivity of the silicon negative electrode material using the negative electrode active material may be 0.001 S/cm to 30 S/cm.
  • the method for producing the negative active material for a secondary battery may include a step of dispersing a monomer in a first solvent, adding a silicon compound to the first solvent, and stirring a first dispersion solution to produce a silicon compound coated with an organic compound; a step of preparing a graphene dispersion solution in which graphene and a cationic surfactant are dispersed, and mixing the silicon compound coated with the organic compound with the graphene dispersion solution to produce a second dispersion solution; and a step of centrifuging the second dispersion solution to select a solid material.
  • the monomer may include at least one of catechol, dopamine, dopamine hydrochloride, norepinephrine, L-dihydroxyphenylalanine, hydroxyphenolic acid, adrenaline, a lignin monomer, ellagitannin, and pyrogall (1,2,3-benzenetriol), and the silicon compound may include at least one of SiO x (0 ⁇ x ⁇ 2), SiO x including a lithium compound (0 ⁇ x ⁇ 2), SiO x including a magnesium compound (0 ⁇ x ⁇ 2), a silicon alloy, and a silicon-carbon composite (Si-C composite).
  • the silicon compound may include at least one of SiO x (0 ⁇ x ⁇ 2), SiO x including a lithium compound (0 ⁇ x ⁇ 2), SiO x including a magnesium compound (0 ⁇ x ⁇ 2), a silicon alloy, and a silicon-carbon composite (Si-C composite).
  • the monomer in the first solvent may be 0.05 wt% to 5 wt%, and the weight ratio of the monomer to the silicon compound may be 1:0.1 to 0.8.
  • the organic compound may include at least one selected from the group consisting of polydopamine, cellulose, polyphenylene, polypropylene, resin, and tannic acid, lignan, catechin, flavonoid, phenolic acid, and stilbene.
  • the graphene dispersion solution is prepared by dispersing graphene in a second solvent, adding the cationic surfactant, and physically stirring the cationic surfactant, wherein the surfactant is 0.05 wt% to 100 wt% with respect to the graphene, and the surfactant is cetyltrimethylammonium bromide (CTAB), alkyltrimethylammonium chlorides, dialkyl dimethyl ammonium chlorides, benzalkonium chloride, didecyldimethylammonium chloride, 1,2-distearoyl-sn-glycero-3-phosphorylethanolamine-N-[methoxy(polyethylene glycol)].
  • CTAB cetyltrimethylammonium bromide
  • alkyltrimethylammonium chlorides dialkyl dimethyl ammonium chlorides
  • benzalkonium chloride didecyldimethylammonium chloride, 1,2-distearoyl-sn-glycero-3-phosphorylethanolamine
  • It may include at least one of poly(ethylene glycol)-1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)] (DSPE-mPEG), polyvinylpyrrolidone (PVP), polyacrylonitrile (PAN), polyethylene glycol tert-octylphenyl ether (Triton X-100), and sodium dodecyl sulfate (SDS).
  • DSPE-mPEG poly(ethylene glycol)-1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)]
  • PVP polyvinylpyrrolidone
  • PAN polyacrylonitrile
  • PAN polyethylene glycol tert-octylphenyl ether
  • SDS sodium dodecyl sulfate
  • the silicon compound coated with the organic compound is dispersed in a third solvent, and then the second dispersion solution is prepared by physical stirring with the graphene dispersion solution, and the concentration of graphene in the graphene dispersion solution is 0.1 wt% to 3 wt%, and the weight ratio of graphene with respect to 100 wt% of the silicon compound may be 1 wt% to 10 wt%.
  • the negative electrode active material for the secondary battery includes silicon oxide and a surface layer formed on the surface of the silicon oxide, and the surface layer includes graphene and carbon, and the step of preparing the second dispersion solution and the step of selecting the solid material are repeated at least once to increase the thickness of the surface layer.
  • the step of selecting the solid material may further include a step of heat treating the solid material in an inert gas atmosphere at a temperature of 300° C. to 1500° C. for 0.5 hour to 24 hours.
  • a secondary battery negative electrode which includes the negative electrode active material; graphite; a binder; and a conductive material, wherein, based on 100 parts by weight of the total of the negative electrode active material, the graphite, the binder, and the conductive material, the graphite is included in an amount of 30 to 95 parts by weight, the binder is included in an amount of 2 to 10 parts by weight, and the conductive material is included in an amount of 0 to 10 parts by weight.
  • a negative electrode active material for a secondary battery which can reduce the content of a conductive material and a binder, and has reduced volume expansion occurring during a charge/discharge process, a method for producing the same, and a negative electrode for a secondary battery including the same.
  • the conductivity between silicon compounds can be improved and the life characteristics of a secondary battery can be improved.
  • FIG. 1 is a drawing schematically illustrating a negative electrode active material for a secondary battery according to one embodiment of the present invention.
  • Figure 2 is a flow chart of a method for manufacturing a negative electrode active material for a secondary battery according to one embodiment of the present invention.
  • FIG. 3 is a drawing schematically illustrating a method for manufacturing a negative electrode active material according to one embodiment of the present invention.
  • Figure 4 is a SEM image of graphene-coated SiO x .
  • Figure 5 is a SEM image of a negative electrode material in which polydopamine (PDA) and graphene (Gr) are sequentially coated on SiO x .
  • PDA polydopamine
  • Gr graphene
  • Figure 6 is a diagram showing the FT-IR results of SiO x , dopamine-coated SiO x , and polydopamine-coated SiO x .
  • Figure 7 is a graph showing the FT-IR results of the negative electrode material before and after carbonization.
  • Figure 8 is a graph showing the Raman peak changes of the negative electrode active material before and after carbonization.
  • Figure 9 shows SiO x, graphene coated SiO x (SiO x +Gr) And the results of measuring the electrical conductivity of carbonized SiO x (SiO x +Gr+PAD) coated with polydopamine and graphene.
  • Figure 10 shows the results of evaluating the electrochemical performance of a half-cell using SiO x and a negative electrode active material according to an embodiment of the present invention as a negative electrode.
  • Figure 11 shows the results of evaluating the electrochemical performance of a half-cell using artificial graphite as a negative electrode by mixing SiO x and an negative electrode active material according to an embodiment of the present invention.
  • Figure 12 shows the TGA confirmation results for SiO x and a negative electrode active material according to an embodiment of the present invention.
  • variable includes all values within the described range including the described endpoints of the range.
  • a range of "5 to 10" will be understood to include the values 5, 6, 7, 8, 9, and 10, as well as any subranges of 6 to 10, 7 to 10, 6 to 9, 7 to 9, etc., and also any value between the integers that fall within the described range, such as 5.5, 6.5, 7.5, 5.5 to 8.5, and 6.5 to 9.
  • a range of "10% to 30%” would be understood to include not only the values 10%, 11%, 12%, 13%, etc., and all integers up to and including 30%, but also any subranges such as 10% to 15%, 12% to 18%, 20% to 30%, and also any value between reasonable integers within the stated range, such as 10.5%, 15.5%, 25.5%, etc.
  • FIG. 1 is a drawing schematically illustrating a negative electrode active material for a secondary battery according to one embodiment of the present invention.
  • the negative electrode active material (100) for a secondary battery according to the present invention may include a silicon compound (110); and a surface layer (120) provided to cover at least a portion of the surface of the silicon compound.
  • the surface layer (120) may include graphene and carbon, and the carbon may be provided by carbonizing an organic compound that forms a catechol bond with the silicon compound (110).
  • the present invention is to improve a problem caused by volume expansion of a silicon compound material used as an anode active material (100) for a secondary battery.
  • the surface layer (120) By providing the surface layer (120) on the silicon compound (110), the conductivity of the silicon compound (110) can be improved, and the deterioration of long-term cycle characteristics of a secondary battery due to volume expansion can be solved.
  • the surface layer (120) can improve the structural stability of the anode active material (100) for a secondary battery, and can be implemented by stably coating carbon and graphene on the silicon compound (110) using a novel method.
  • the above silicon compound (110) may include at least one of SiO x (0 ⁇ x ⁇ 2), SiO x containing a lithium compound (0 ⁇ x ⁇ 2), SiO x containing a magnesium compound (0 ⁇ x ⁇ 2), a silicon alloy, and a silicon-carbon composite (Si-C composite).
  • the silicon compound (110) containing the lithium compound, SiO x (0 ⁇ x ⁇ 2) can include lithium through a prelithiation method of Si or silicon oxide.
  • the prelithiation method includes a method of manufacturing a negative electrode after lithiating the silicon compound (110) through a physicochemical method or an electrochemical charging method.
  • the SiO x (0 ⁇ x ⁇ 2) containing the above magnesium compound may include MgSiO 3 crystals and Mg 2 SiO 4 crystals in silicon oxide.
  • the above silicon alloy may be represented as Si-M, where M may be Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.
  • the silicon alloy may be one selected from SiTiNi, SiAlMn, SiAlFe, SiFeCu, SiCuMn, SiMgAl, SiMgCu, and a combination thereof.
  • the above silicon-carbon composite may be a material formed by silicon and carbon through heat treatment or the like, wherein the carbon may be at least one of carbon, carbon nanotubes, and graphene.
  • the average thickness (t) of the surface layer (120) may be 10 nm to 10 ⁇ m. If the thickness (t) of the surface layer (120) is less than 10 nm, the effect of improving the volume expansion problem of the silicon compound (110) due to the surface layer is minimal, and if it exceeds 10 ⁇ m, the ion conductivity of the secondary battery may deteriorate. Specifically, the average thickness (t) of the surface layer (120) may be 10 nm to 5 ⁇ m, or 50 nm to 5 ⁇ m, or 100 nm to 5 ⁇ m, or 100 nm to 1 ⁇ m.
  • the average thickness (t) of the surface layer (120) may be provided as a length of 0.05% to 10% with respect to the average radius of the negative electrode active material (100).
  • the negative electrode active material (100) may have a silicon compound (110) provided therein, and the surface layer (120) may be provided on the surface of the silicon compound (110). If the average thickness (t) of the surface layer (120) is less than 0.05% with respect to the average radius of the negative electrode active material (100), the surface layer (120) is difficult to be uniformly formed on the surface of the silicon compound (110), and if it exceeds 10%, the electrolyte is difficult to be uniformly impregnated into the silicon compound (110), and an unreacted region may be formed during the formation process by charge and discharge.
  • the average thickness (t) of the surface layer (120) may be 0.05% to 8%, or 0.1% to 8%, or 0.5% to 8%, or 1% to 8%, or 5% to 8% with respect to the average radius of the negative electrode active material (100).
  • the content of the carbon in the silicon compound (110) may be included in a weight ratio of 0.2 wt% to 20 wt%, as evaluated by TGA.
  • the surface layer (120) includes the graphene and carbon, and the carbon may be formed by carbonizing the organic compound. If the weight ratio of the carbon in the silicon compound (110) is less than 0.2 wt%, the effect of improving the conductivity of the negative electrode active material is insignificant, and if it exceeds 20 wt%, the surface layer is not stably fixed, which is problematic.
  • the carbon in the silicon compound (110) may be 0.2 wt% to 15 wt%, or 0.2 wt% to 10 wt%, or 1 wt% to 10 wt%, or 1 wt% to 7 wt%.
  • the weight ratio of the organic compound to the silicon compound (110) may be 1:0.1 to 0.8.
  • the silicon compound (110) is provided in a particle form, and the organic compound may be coated on the silicon compound (110) in the particle form by a catechol bond.
  • the weight ratio of the organic compound to the silicon compound is less than 0.1, it is difficult to stably fix the graphene to the silicon compound (110), and when it exceeds 0.8, a part where the organic compound clumps is formed may be formed, which may lower the electrical conductivity of the secondary battery.
  • the silicon compound (110) is 1, the weight ratio of the organic compound may be 0.1 to 0.7, or 0.3 to 0.7, or 0.4 to 0.6.
  • the above organic compound may be selected from the group consisting of polydopamine, cellulose, polyphenylene, polypropylene, resin, tannic acid, lignan, catechin, flavonoid, phenolic acid and stilbene.
  • the organic compound may include a polymer formed by polymerizing a monomer.
  • the monomer may include at least one of dopamine, dopamine hydrochloride, norepinephrine, L-dihydroxyphenylalanine, hydroxyphenolic acid, adrenaline, lignin monomer, ellagitannin, and pyrogall (1,2,3-benzenetriol).
  • the silicon compound (110) can be manufactured into an organic compound by coating the monomer and polymerizing the coated monomer.
  • the amine functional group of the organic compound and the silicon compound (110) can form a catechol bond through a covalent bond. Since the catechol bond forms a high bonding strength, graphene or the like can be stably fixed to the silicon compound (110).
  • the above organic compound may include at least one catechol functional group and an amine functional group that perform the catechol bond.
  • the catechol functional group may be provided with a structure in which two hydroxyl groups (-OH) are adjacent to each other at the terminal of a benzene ring.
  • the two hydroxyl groups of the organic compound may be bonded to the surface of the silicon compound and then oxidized to change into a quinone.
  • the quinone may form a catechol bond through a chain network formation reaction with an amine group.
  • the monomer may include dopamine
  • the organic compound may include polydopamine formed by polymerization of the dopamine.
  • the dopamine is a substance having a molecular weight of approximately 153 Da and having catechol and amine functional groups, and after being provided on the surface of the silicon compound (110), a coating layer of polydopamine may be formed by oxidation of the catechol amine included in the dopamine.
  • the polydopamine includes a catechol functional group, and the catechol functional group has redox ability, and thus can stably fix the graphene to the surface of the silicon compound (110) through the reduction ability of metal ions and specific adhesiveness at the same time.
  • the silicon compound (110) coated with the organic compound can be added to the graphene dispersion solution so that the graphene can be provided on the surface of the organic compound.
  • the silicon compound provided with both the graphene and the organic compound can be heat-treated, and the organic compound can be carbonized and converted into carbon through the heat treatment.
  • the temperature for carbonizing the organic compound may be 300° C. to 1500° C. If the temperature for carbonizing the organic compound is less than 300° C., the organic compound may not be carbonized uniformly, which may be problematic, and if it is more than 1500° C., crystallization of silicon nanodomains may occur on the surface of the silicon compound, thereby deteriorating the structure and crystallinity of the silicon compound or forming silicon carbide.
  • the temperature for carbonizing the organic compound may be 300° C. to 1200° C., or 300° C. to 1000° C., or 500° C. to 1500° C., or 500° C. to 1200° C., or 700° C. to 1500° C., or 700° C. to 1100° C., or 700° C. to 1000° C.
  • the negative electrode active material (100) for a secondary battery uses a silicon compound (110) as a main material, and may include a surface layer (120) provided on the surface of the silicon compound (110).
  • the surface layer (120) can prevent problems such as the negative electrode active materials (100) colliding with each other by inducing slippage between the negative electrode active materials (100) when adjacent negative electrode active materials (100) collide with each other.
  • the volume of the silicon compound repeatedly shrinks and expands reversibly and irreversibly, causing the position of the silicon compound in the negative electrode to change, and the negative electrode as a whole to expand, resulting in a problem of reduced conductivity.
  • the negative electrode layer coated on the negative electrode plate may peel off, resulting in a problem of reduced electrical conductivity.
  • the negative electrode active material (100) according to the present embodiment is provided with a surface layer (120), when the silicon compound (110) expands and contracts as charge and discharge are performed, slip is induced by the surface layer (120), thereby preventing the negative electrode active material (100) from being damaged.
  • the graphene provided in the surface layer (120) is provided by being directly or closely bonded to the negative electrode active material (100), it can act as a path for electron transfer, thereby effectively maintaining high ionic conductivity between neighboring negative electrode active materials (100).
  • the negative electrode active material (100) according to the present embodiment can improve the electrochemical performance of a secondary battery by alleviating the widening of the particle spacing, the decrease in electrical conductivity, etc. caused by the volume expansion of the silicon compound.
  • the electrical conductivity of a secondary battery using the above negative electrode active material (100) may be 0.01 S/cm to 30 S/cm.
  • Figure 2 is a flow chart of a method for manufacturing a negative electrode active material for a secondary battery according to one embodiment of the present invention.
  • the method for producing a negative electrode active material for a secondary battery may include: a step of dispersing a monomer of the method in a first solvent, adding a silicon compound to the first solvent, and stirring a first dispersion solution to produce a silicon compound coated with an organic compound; a step of preparing a graphene dispersion solution in which graphene and a cationic surfactant are dispersed, and mixing the silicon compound coated with the organic compound with the graphene dispersion solution to produce a second dispersion solution; and a step of centrifuging the second dispersion solution to select a solid material.
  • the above solid material may include a silicon compound in the center and graphene and carbon in the surface portion.
  • the surface portion may be stably fixed to the silicon compound with a predetermined thickness.
  • the surface layer may be formed by providing an organic compound and graphene to the silicon compound and then carbonizing the organic compound.
  • the above monomer may include at least one of dopamine, dopamine hydrochloride, norepinephrine, L-dihydroxyphenylalanine, hydroxyphenolic acid, adrenaline, lignin monomer, ellagitannin, and pyrogall (1,2,3-benzenetriol).
  • the silicon compound (110) may include at least one of SiO x (0 ⁇ x ⁇ 2), SiO x including a lithium compound (0 ⁇ x ⁇ 2), SiO x including a magnesium compound (0 ⁇ x ⁇ 2), a silicon alloy, and a silicon-carbon composite (Si-C composite).
  • the first solvent may include at least one of ultrapure water, N-methyl-2-pyrrolidone (NMP), methanol, ethanol, polypyrrolidone, isopropanol, acetone, petroleum ether, tetrahydrofuran, ethyl acetate, N,N-dimethylacetamide, N,N-dimethylformamide, n-hexane, and a halogenated hydrocarbon.
  • NMP N-methyl-2-pyrrolidone
  • methanol ethanol
  • polypyrrolidone polypyrrolidone
  • isopropanol acetone
  • petroleum ether tetrahydrofuran
  • ethyl acetate N,N-dimethylacetamide
  • N,N-dimethylformamide N,N-dimethylformamide
  • n-hexane n-hexane
  • the monomer in the first solvent may be 0.05 wt% to 5 wt%, and the weight ratio of the monomer to the silicon compound may be 1:0.1 to 0.8.
  • the monomer in the first solvent may be 0.1 wt% to 5 wt%, or 0.1 wt% to 3 wt%, or 0.5 wt% to 5 wt%, or 0.5 wt% to 3 wt%.
  • the monomer for the silicon compound is provided in an amount less than 0.1, the effect of the monomer is insignificant, and if it exceeds 0.8, the dispersibility of the monomer deteriorates, so that the surface layer may not be formed uniformly.
  • the monomer is provided in the above-described weight ratio for the silicon compound, so that the monomer does not deteriorate the electrical characteristics of the silicon compound and can be uniformly coated.
  • the monomer for the silicon compound may be in a weight ratio of 1:0.1 to 0.7, or in a weight ratio of 1:0.3 to 0.7, or in a weight ratio of 1:0.3 to 0.6.
  • the first dispersion solution can be stirred for 0.5 to 24 hours to produce a silicon compound coated with an organic compound. If the time for stirring the first dispersion solution is less than 0.5 hours, the organic compound is not stably coated on the surface of the silicon compound, which is problematic, and since 24 hours is sufficient, if the stirring is performed for longer than this, the process efficiency may be reduced, which is problematic.
  • the monomer By stirring the first dispersion solution for the aforementioned time, the monomer can be manufactured into an organic compound, and at the same time, the organic compound can be stably coated on the surface of the silicon compound.
  • the above graphene dispersion solution can be prepared by dispersing graphene in a second solvent, adding the cationic surfactant, and physically stirring.
  • the above surfactants are cetyltrimethylammonium bromide (CTAB), alkyltrimethylammonium chlorides, dialkyl dimethyl ammonium chloride, benzalkonium chloride, didecyldimethylammonium chloride, 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)] (DSPE-mPEG), polyvinylpyrrolidone (PVP), polyacrylonitrile (PAN), polyethylene glycol-tert-octylphenyl ether. (polyethylene glycol tert-octylphenyl ether, Triton X-100), and sodium dodecyl sulfate (Sodium Dodecyl Sulfate, SDS).
  • CTAB cetyltrimethylammonium bromide
  • alkyltrimethylammonium chlorides dialkyl dimethyl ammonium chloride
  • benzalkonium chloride dide
  • the second solvent may include at least one of ultrapure water, N-methyl-2-pyrrolidone (NMP), methanol, ethanol, polypyrrolidone, isopropanol, acetone, petroleum ether, tetrahydrofuran, ethyl acetate, N,N-dimethylacetamide, N,N-dimethylformamide, n-hexane, and a halogenated hydrocarbon.
  • NMP N-methyl-2-pyrrolidone
  • methanol ethanol
  • ethanol polypyrrolidone
  • isopropanol acetone
  • petroleum ether tetrahydrofuran
  • ethyl acetate N,N-dimethylacetamide
  • N,N-dimethylformamide N,N-dimethylformamide
  • n-hexane n-hexane
  • the above graphene dispersion solution can be prepared by stirring graphene in the second solvent and then adding the cationic surfactant thereto. By sequentially adding graphene and the cationic surfactant to the second solvent, the graphene can be uniformly dispersed without clumping within the second solvent.
  • the surfactant for the graphene may be 0.05 wt% to 100 wt%. If the surfactant for the graphene is less than 0.05 wt%, a problem of the surface layer being detached from the silicon compound during the process of manufacturing a slurry may occur. In addition, the surface layer formation becomes easier as the surfactant is added in a large amount, and the surfactant is carbonized by subsequent heat treatment, so that a problem of side reactions does not occur. By providing the surfactant in the above-described range, the graphene can be stably dispersed in the second solvent. Specifically, the surfactant for the graphene may be 0.05 wt% to 80 wt%, or 0.1 wt% to 80 wt%, or 0.1 wt% to 50 wt%.
  • the silicon compound coated with the organic compound is dispersed in a third solvent, and then the graphene dispersion solution is added thereto and physically stirred to prepare the second dispersion solution.
  • the concentration of graphene in the graphene dispersion solution may be 0.8 wt% to 2 wt%. If the concentration of graphene in the graphene dispersion solution is less than 0.8 wt%, it is difficult for the graphene to be uniformly coated on the surface of the silicon compound, and if it exceeds 2 wt%, problems such as graphene clumping in the graphene dispersion solution may occur.
  • the content of graphene with respect to 100 wt% of the silicon compound may be 1 wt% to 10 wt%. If the content of the graphene is less than 1 wt%, the effect by the graphene is insignificant, and if it exceeds 10 wt%, the capacity of the secondary battery may be reduced.
  • the graphene with respect to the silicon compound is provided in the above-described weight ratio, thereby improving the conductivity of the silicon compound by the graphene, and effectively improving the life characteristics of the secondary battery.
  • the graphene may be 1 wt% to 8 wt%, or 3 wt% to 8 wt%, or 4 wt% to 6 wt%.
  • the above physical agitation may include one or more of ultrasonic mixing, mechanical mixing, and mixing using shear force.
  • the above ultrasonic mixing can be performed at 10 kHz to 80 kHz.
  • the graphene raw material can be pulverized and its size can be reduced.
  • the graphene raw material can be pulverized during the ultrasonic mixing process, and can be controlled to a predetermined size by performing the process at a time and frequency within the above-described range. If the frequency is less than 10 kHz, the graphene raw material is not pulverized to a desired size, and if it exceeds 80 kHz, the size of the pulverized graphene is too small to be attached in a scale-like form on the surface of the silicon compound, which is problematic.
  • the above mechanical mixing can be accomplished by spinning at high speed, by applying pressure into the fluid, by spraying the fluid through small holes or gaps, or by dispersing the fluid by colliding with the walls of the container.
  • the dispersion utilizing the above shear force can be achieved by applying a shear force to the liquid while rotating two cylindrical rotating bodies and passing the fluid between the two rotating bodies.
  • the above secondary battery negative electrode active material includes silicon oxide and a surface layer formed on the surface of the silicon oxide, and the surface layer includes graphene and carbon, and the carbon can be formed by carbonizing an organic compound that forms a catechol bond with the silicon compound.
  • the step of preparing the second dispersion solution and the step of selecting the solid material can be repeated at least once to increase the thickness of the surface layer.
  • the thickness of the surface layer can be easily controlled by controlling the number of repetitions of the step of manufacturing the second dispersion solution and the step of selecting the solid material.
  • the method may further include a step of heat treating in an inert gas atmosphere at a temperature of 300° C. to 1500° C. for 0.5 to 24 hours after the step of selecting the solid material.
  • the organic compound of the surface layer is carbonized, whereby the surface layer can be stably fixed to the surface of the silicon compound.
  • electrical conductivity can be improved.
  • the first to third solvents may each include at least one of ethanol, ultrapure water, N-methyl-2-pyrrolidone (NMP), methanol, ethanol, polypyrrolidone, isopropanol, acetone, petroleum ether, tetrahydrofuran, ethyl acetate, N,N-dimethylacetamide, N,N-dimethylformamide, n-hexane, and halogenated hydrocarbons.
  • NMP N-methyl-2-pyrrolidone
  • methanol ethanol
  • polypyrrolidone polypyrrolidone
  • isopropanol acetone
  • petroleum ether tetrahydrofuran
  • ethyl acetate N,N-dimethylacetamide
  • N,N-dimethylformamide N-hexane
  • halogenated hydrocarbons halogenated hydrocarbons
  • FIG. 3 is a drawing schematically illustrating a method for manufacturing a negative electrode active material according to one embodiment of the present invention.
  • the negative electrode active material can be manufactured by coating an organic compound and graphene on a silicon compound, and carbonizing the organic compound through heat treatment to form a surface layer.
  • the organic compound can be polydopamine, and the polydopamine can be formed by polymerizing dopamine as a monomer.
  • the silicon compound (Si) can be coated with dopamine (DA) and polymerized to manufacture a silicon compound coated with polydopamine (PDA).
  • the polydopamine can be stably fixed to the silicon compound by catechol bonding.
  • the silicon compound coated with polydopamine is added to a graphene dispersion solution and physically stirred, and graphene included in the graphene dispersion solution can be attached to the polydopamine.
  • the polydopamine is carbonized to form carbon, and a surface layer made of graphene and carbon can be formed on the surface of the silicon compound.
  • the above surface layer provides a sliding effect to adjacent negative active materials, so that even if the negative active materials reversibly change in volume during the charge and discharge process, they slide against each other without being destroyed by applying a physical force to the surrounding negative active materials, thereby improving the life characteristics of the secondary battery.
  • the graphene provided in the surface layer greatly improves the conductivity between adjacent negative active materials due to increased electrical conductivity, and can provide a path for charge movement by connecting like a bridge in empty spaces formed by displacement due to volume change of the negative active materials.
  • the present invention includes the negative electrode active material; graphite; a binder; and a conductive material, and based on 100 parts by weight of the total of the negative electrode active material, graphite, binder, and conductive material, the graphite may be included in an amount of 30 to 95 parts by weight, the binder in an amount of 2 to 10 parts by weight, and the conductive material in an amount of 0 to 10 parts by weight.
  • the negative electrode for the secondary battery may be used by mixing the negative electrode active material having the silicon compound and the surface layer and graphite.
  • the binder and the conductive agent may be included in a lower content than in the case of using graphite alone or in the case of using a mixture of the silicon compound and graphite, and the conductive agent may not be included.
  • the above graphite may include natural graphite or artificial graphite.
  • the above natural graphite may be flake graphite, vein graphite, or amorphous graphite, and specifically, may be flake graphite or vein graphite.
  • the natural graphite may have a high tap density or bulk density because the contact area between particles increases, the bonding area increases, and thus the bonding strength is improved.
  • the above artificial graphite may be in the form of powder, flake, block, plate, or rod, and specifically, in order to exhibit the best output characteristics, the shorter the movement distance of lithium ions, the better, and in order to shorten the movement distance in the electrode direction, the crystal grain orientation of the artificial graphite may be isotropic.
  • the graphite is included in the above-described range and mixed with the negative electrode active material, thereby further improving the capacity characteristics and life characteristics of the secondary battery through electrochemical, particle shape, and particle surface interactions with the negative electrode active material.
  • the negative electrode essentially contains a binder for binding particles together and a conductive agent for improving electrical conductivity.
  • the binder and the conductive agent relatively reduce the specific capacity of the negative electrode, and increase the production cost in order to uniformly mix the binder and the conductive agent with the negative electrode active material, graphite, etc.
  • the conductive agent exists as separate particles from the negative electrode active material, graphite, etc., the negative electrode active material, graphite, etc., which undergo volume expansion during the cycle, and the conductive agent do not come into close contact, which causes a problem that electrical conductivity is reduced. In particular, this has been an even greater problem in the case of a silicon compound that undergoes large volume expansion during the charge and discharge process.
  • the above binder may be provided in an amount of 2 to 10 parts by weight.
  • the binder physically binds between the negative electrode active material and graphite, and between the negative electrode active material, graphite, and current collector. If it is less than 2 parts by weight, the function of the binder is not sufficient, and if it exceeds 10 parts by weight, unnecessary use of binder may reduce the specific capacity of the secondary battery and improve the production cost.
  • the above binder may include at least one of styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), nitrile butadiene rubber (NBR), polyacrylamide (PAM), polyacrylonitrile (PAN), polyimide (PI), and polyamideimide (PAI).
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • PAA polyacrylic acid
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • NBR nitrile butadiene rubber
  • PAM polyacrylamide
  • PAN polyacrylonitrile
  • PI polyimide
  • PAI polyamideimide
  • the conductive material may be 0 to 10 parts by weight. That is, in the present embodiment, the conductive material may be omitted altogether, and even when the conductive material is used, the electrochemical characteristics and cycle characteristics of the secondary battery may be improved even when used in a lower amount than conventional amounts, such as 10 parts by weight or less.
  • the conductive material may include carbon nanotubes, graphene, graphite, carbon black, and carbon fibers.
  • the conductive material may include carbon nanotubes, graphene, graphite such as natural graphite and artificial graphite, carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, summer black, superp, toka black, and denka black, carbon fibers, and the like. More specifically, the conductive material may be carbon nanotubes or graphene.
  • the present invention can improve the problem of volume change of SiO x material, and specifically, it can solve the problem by providing conductivity to the surface of a silicon-based negative electrode active material and forming a surface layer for volume improvement, thereby ensuring structural stability within the electrode.
  • a carbonization process to the surface of a silicon-based negative electrode active material through the introduction of a carbon layer and graphene coating, the performance can be improved.
  • the negative electrode active material for a secondary battery according to the present invention can improve the conductivity of the negative electrode for a secondary battery by increasing the interlayer adhesion between the surface of the silicon compound and graphene, and forming a surface layer including graphene and carbon through final carbonization.
  • the method for manufacturing the negative electrode active material for a secondary battery according to the present invention can improve process efficiency and productivity by using an aqueous graphene solution and a water-soluble polymer in consideration of the negative electrode aqueous process, thereby enabling an aqueous process rather than an organic solvent.
  • an aqueous process is possible, the use of organic solvents is reduced, so that the negative electrode active material for a secondary battery can be manufactured in an environmentally friendly manner.
  • DA dopamine hydrochloride
  • silicon material SiO x
  • the dopamine-silicon dispersion solution after stirring, was physically stirred for 12 h to form a polydopamine (PDA) layer on the surface of the silicon material. After stirring, the solution was filtered and distilled water was used to wash away the remaining impurities.
  • PDA polydopamine
  • Graphene (11 mg) was dispersed in 1000 mL of DI water to prepare a 1.1 wt% (11 mg/mL-water) dispersion.
  • 1 wt% of a cationic surfactant was added to the 1.1 wt% graphene dispersion solution, and the dispersion was performed using a tip sonicator (BANDELIN, SONOPLUS HD 4200, pulse time 3/2 s, 20 kHz model amp 60%) for 1.5 h to reduce the size of the graphene and ensure uniform dispersion with the surfactant.
  • CTAB Cetyltrimethylammonium bromide
  • Centrifugation (Hanil fleta 40p) was performed at 3000 rpm for 3 min to obtain the graphene-coated silicone material. At this time, the rotation speed of the centrifugation was set to 500 ⁇ 4000 rpm. The solid material obtained by centrifugation was dried in a vacuum oven using each manufactured cathode and at 80°C for 4 h. The graphene repeat coating process was performed by repeating the above processes three times.
  • Polydopamine (PDA) coated between the silicon material surface and the graphene layer was carbonized, and heat treatment was performed to remove the surfactant remaining after coating.
  • the heat treatment was performed at a temperature increase rate of 5 °C/min from room temperature to 800 °C, and then for 2 h in an argon atmosphere to manufacture a negative electrode active material of SiO x coated with graphene and carbon.
  • the dopamine content was 0.5 g per 1 g of silicon material (SiO x ), and the graphene dispersion solution prepared by the aforementioned method was added so that the silicon material and the graphene dispersion solution were 1:2 to prepare a mixed solution.
  • the process was carried out at room temperature, and the mixed solution was mixed at 3000 rpm for 1 min using a vortex (Vortex, genie2) to perform coating.
  • ethanol was additionally added to the conical tube in an amount of at least 0 g and up to approximately 30 g, and centrifugation (Hanil fleta 40p) was performed at 3000 rpm for 3 min.
  • the solid material obtained by centrifugation was dried in a vacuum oven at 80 °C for 4 h, thereby preparing a negative electrode active material of SiO x coated with graphene.
  • a negative electrode slurry was prepared using the negative electrode active material manufactured according to the method described above.
  • the composition ratio of silicon material, conductive material (carbon black), and binder was 80:10:10 wt%, and DI water was added to prepare a negative electrode slurry.
  • the composition ratio of the anode active material which is a mixture of silicon material and graphite, the conductive material (carbon black) and the binder (a mixture of SBR:CMC in a weight ratio of 1:1) was 94:3:3 wt%, and DI water was added to adjust the solid content to 45% to prepare a cathode slurry.
  • the anode active material was used by mixing 20 wt% of silicon material and 80 wt% of graphite.
  • each negative electrode having a negative electrode density of 1.6 g/cm 3 was used.
  • the CR2032 coin cell was subjected to 3 cycles at 0.1 C before performing charge and discharge cycles.
  • 1 C is 1600 mAh/g
  • an anode mixed of a silicon material and artificial graphite it is 580 mAh/g.
  • Figure 4 is a SEM image of SiO x coated with graphene.
  • Figure 5 is a SEM image of a negative electrode material sequentially coated with polydopamine (PDA) and graphene (Gr) on SiO x .
  • PDA polydopamine
  • Gr graphene
  • Figure 4 is a negative electrode active material in which only graphene (Gr) is coated on SiOx
  • Figure 5 is a negative electrode active material in which both polydopamine (PDA) and graphene (Gr) are coated on SiOx and then carbonized.
  • FIG. 4 it was confirmed that graphene was attached to SiO x while maintaining a sheet shape, and that FIG. 4 shows that graphene was uniformly coated on the entire SiO x by polydopamine. It was confirmed that the coating had a similar shape regardless of before and after the carbonization process of polydopamine by heat treatment. That is, even when polydopamine was included, there was no significant difference in surface morphology, and it was confirmed that there was no significant change before and after performing carbonization.
  • Figure 6 is a diagram showing the FT-IR results of SiO x , dopamine-coated SiO x , and polydopamine-coated SiO x .
  • Figure 7 is a graph showing the FT-IR results of the negative electrode active material before and after carbonization.
  • Figure 8 is a graph showing the Raman peak changes of the negative electrode active material before and after carbonization.
  • Figure 9 shows SiO x, graphene coated SiO x (SiO x +Gr) And the results of measuring the electrical conductivity of carbonized SiO x (SiO x +Gr+PAD) coated with polydopamine and graphene.
  • Polydopamine itself does not affect electrical conductivity, but by fixing the graphene more firmly with polydopamine and performing carbonization here, it was confirmed that the electrical conductivity improvement by the graphene greatly increases. It was confirmed that the carbon material formed as a result of the carbonization of polydopamine alone electrically connects neighboring graphene and, at the same time, is stably fixed to SiO x to increase electrical conductivity.
  • Figure 10 shows the results of evaluating the electrochemical performance of a half-cell using SiO x and a negative electrode active material according to an embodiment of the present invention as a negative electrode.
  • Fig. 10 SiO x alone and SiO x coated with polydopamine and graphene, which are negative active materials according to an embodiment of the present invention, and carbonized were used as negative active materials, respectively.
  • the composition of the negative electrode in the half-cell of Fig. 10 was 80 wt% of the negative active material, 10 wt% of the conductive agent (carbon black), and 10 wt% of the binder (SBR/CMC). After each went through a formation process at room temperature, 3 cycles were performed with 0.005-1.5 V charge and 0.1 C discharge to confirm.
  • the capacity was found to decrease as charge and discharge were performed, whereas the negative electrode active material according to an embodiment of the present invention stably maintained the same capacity during three charge and discharge cycles.
  • the negative electrode active material according to an embodiment of the present invention stably maintained the capacity during the cycle, whereas the negative electrode active material of SiO x alone showed a relatively low capacity and it was confirmed that the capacity gradually decreased during the cycle.
  • Figure 11 shows the results of evaluating the electrochemical performance of a half-cell using artificial graphite as a negative electrode by mixing SiO x and an negative electrode active material according to an embodiment of the present invention.
  • the composition of the cathode was composed of 94 wt% of the cathode active material (20 wt% of silicon material, 80 wt% of artificial graphite), 3 wt% of the conductive agent (carbon black), and 3 wt% of the binder (SBR/CMC).
  • the ratio of silicon and graphite was determined based on a capacity of 600 mAh/g.
  • the electrode density of the cathode electrode was 1.6 g/cc. After each formation process at room temperature, 3 cycles were performed with 0.005-1.5 V charge and 0.1 C discharge to confirm.
  • the cathode manufactured according to this example stably exhibited high capacity and improved cycle characteristics. In addition, it was confirmed that the characteristics were effectively exhibited even when used in combination with graphite.
  • Figure 12 shows the TGA confirmation results for SiO x and a negative electrode active material according to an embodiment of the present invention.
  • SiO x and the negative electrode active material according to the embodiment of the present invention were each measured twice using TGA (STA7300, Hitachi).
  • the amount of graphene coating per 1 g of the active material in the negative electrode active material according to the embodiment of the present invention was found to be about 5 wt%.

Landscapes

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

Abstract

La présente invention concerne un matériau actif d'électrode négative pour une batterie secondaire, comprenant un composé de silicium et une couche de surface disposée pour recouvrir au moins une partie de la surface du composé de silicium, la couche de surface contenant du graphène et un composé organique, et le composé organique formant une liaison catéchol conjointement avec le composé de silicium.
PCT/KR2024/019320 2023-11-30 2024-11-29 Matériau actif d'électrode négative pour batterie secondaire, son procédé de fabrication et électrode négative le comprenant pour batterie secondaire Pending WO2025116625A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20230170449 2023-11-30
KR10-2023-0170449 2023-11-30
KR1020240167611A KR20250083125A (ko) 2023-11-30 2024-11-21 이차전지용 음극활물질, 이의 제조방법 및 이를 포함하는 이차전지용 음극
KR10-2024-0167611 2024-11-21

Publications (1)

Publication Number Publication Date
WO2025116625A1 true WO2025116625A1 (fr) 2025-06-05

Family

ID=95897371

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2024/019320 Pending WO2025116625A1 (fr) 2023-11-30 2024-11-29 Matériau actif d'électrode négative pour batterie secondaire, son procédé de fabrication et électrode négative le comprenant pour batterie secondaire

Country Status (1)

Country Link
WO (1) WO2025116625A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101767393B1 (ko) * 2017-02-09 2017-08-11 한국지질자원연구원 실리콘-탄소-그래핀 복합체 제조방법, 이에 따라 제조되는 복합체 및 이를 적용한 이차전지
KR20200027787A (ko) * 2018-09-05 2020-03-13 주식회사 엘지화학 음극 및 이를 포함하는 이차전지

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101767393B1 (ko) * 2017-02-09 2017-08-11 한국지질자원연구원 실리콘-탄소-그래핀 복합체 제조방법, 이에 따라 제조되는 복합체 및 이를 적용한 이차전지
KR20200027787A (ko) * 2018-09-05 2020-03-13 주식회사 엘지화학 음극 및 이를 포함하는 이차전지

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DE GUZMAN RHET C.; YANG JINHO; CHENG MARK MING-CHENG; SALLEY STEVEN O.; SIMON NG K.Y.: "Effects of graphene and carbon coating modifications on electrochemical performance of silicon nanoparticle/graphene composite anode", JOURNAL OF POWER SOURCES, ELSEVIER, AMSTERDAM, NL, vol. 246, 3 August 2013 (2013-08-03), AMSTERDAM, NL, pages 335 - 345, XP028739896, ISSN: 0378-7753, DOI: 10.1016/j.jpowsour.2013.07.100 *
LEE LANLEE, TO A RAN WEERAWAT, LEE JUNG-HUN, HWANG SOO MIN, KIM YOUNG-JUN: "Self-adaptive anode design with graphene-coated SiOx/graphite for high-energy Li-ion batteries", CHEMICAL ENGENEERING JOURNAL, ELSEVIER, AMSTERDAM, NL, vol. 442, 1 August 2022 (2022-08-01), AMSTERDAM, NL , pages 136166, XP093320072, ISSN: 1385-8947, DOI: 10.1016/j.cej.2022.136166 *
LI NINGNING; LIU YI; JI XIAOYU; FENG JIAXIN; WANG KAI; XIE JIAYUE; LEI GUANGLU; LIU XIANGHONG; GUO XIANGXIN; ZHANG JUN: "Polydopamine-mediated synthesis of Si@carbon@graphene aerogels for enhanced lithium storage with long cycle life", CHINESE CHEMICAL LETTERS, ELSEVIER, AMSTERDAM, NL, vol. 32, no. 12, 26 April 2021 (2021-04-26), AMSTERDAM, NL , pages 3787 - 3792, XP086945401, ISSN: 1001-8417, DOI: 10.1016/j.cclet.2021.04.029 *

Similar Documents

Publication Publication Date Title
WO2019151774A1 (fr) Matériau actif d'anode, procédé de préparation de matériau actif d'anode, anode comprenant un matériau actif d'anode et batterie secondaire comprenant l'anode
WO2016204565A1 (fr) Composite d'oxyde de silicium-carbone-polymère et matériau actif d'anode comprenant ce dernier
WO2018030616A1 (fr) Composite soufre-carbone, son procédé de préparation et batterie au lithium-soufre comprenant celui-ci
WO2017099456A1 (fr) Matériau actif d'électrode négative pour batterie secondaire au lithium comprenant un cœur composé de carbone, son procédé de fabrication et batterie secondaire au lithium comprenant celui-ci
WO2020149622A1 (fr) Anode et batterie rechargeable comprenant ladite anode
WO2014185730A1 (fr) Particules creuses à base de silicium, leur procédé de préparation, et matériau actif d'anode pour une batterie secondaire au lithium les contenant
WO2020040613A1 (fr) Matériau actif d'anode, anode le comprenant, et batterie secondaire au lithium
WO2018084449A2 (fr) Composite de soufre-carbone et batterie au lithium-soufre le comprenant
WO2019088475A1 (fr) Composite soufre-carbone et batterie lithium-soufre le comprenant
CN111406334A (zh) 负极活性物质及其制造方法
WO2019013525A2 (fr) Matériau actif d'électrode négative pour batterie secondaire au lithium, son procédé de fabrication, et batterie secondaire au lithium le comprenant
WO2019093820A1 (fr) Matériau actif d'électrode négative, électrode négative comprenant ledit matériau actif d'électrode négative, et accumulateur comprenant ladite électrode négative
WO2020101301A1 (fr) Matériau actif d'anode et son procédé de fabrication
WO2020009333A1 (fr) Composite soufre-carbone et son procédé de production, et électrode positive de batterie au lithium-soufre et batterie au lithium-soufre comprenant ledit composite
WO2019093830A1 (fr) Matériau actif d'électrode négative, électrode négative comprenant ledit matériau actif d'électrode négative, et batterie secondaire comprenant ladite électrode négative
WO2020091345A1 (fr) Matériau actif d'anode et batterie secondaire au lithium le comprenant
WO2018174619A1 (fr) Procédé de production d'une composition de barbotine pour électrode positive de batterie secondaire, électrode positive pour batterie secondaire produite à l'aide de celui-ci, et batterie secondaire au lithium la comprenant
WO2020153728A1 (fr) Matériau actif d'anode pour batterie secondaire au lithium, et anode et batterie secondaire au lithium le comprenant
WO2022055309A1 (fr) Matériau actif d'électrode négative, électrode négative renfermant un matériau actif d'électrode négative, et batterie secondaire comprenant une électrode négative
WO2012141503A2 (fr) Matière active d'électrode positive, son procédé de préparation et électrode positive et batterie au lithium l'utilisant
WO2017052246A1 (fr) Matériau actif de cathode et cathode comprenant des nanoparticules métalliques, ainsi que batterie au soufre et lithium en étant équipée
WO2020242257A1 (fr) Électrode négative et batterie secondaire comprenant une électrode négative
WO2021080066A1 (fr) Matériau actif d'anode comprenant un composite de silicium formé par réseau de fibres conductrices, son procédé de préparation et batterie secondaire au lithium le comprenant
WO2022045852A1 (fr) Électrode négative et batterie secondaire la comprenant
WO2022124716A1 (fr) Électrode négative et batterie au lithium la comprenant

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: 24898219

Country of ref document: EP

Kind code of ref document: A1