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WO2025193043A1 - Matériau d'électrode négative comprenant un composite mg(o)/c, électrode négative, batterie secondaire au lithium-ion et procédé de fabrication de composite mg(o)/c - Google Patents

Matériau d'électrode négative comprenant un composite mg(o)/c, électrode négative, batterie secondaire au lithium-ion et procédé de fabrication de composite mg(o)/c

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Publication number
WO2025193043A1
WO2025193043A1 PCT/KR2025/099657 KR2025099657W WO2025193043A1 WO 2025193043 A1 WO2025193043 A1 WO 2025193043A1 KR 2025099657 W KR2025099657 W KR 2025099657W WO 2025193043 A1 WO2025193043 A1 WO 2025193043A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative electrode
ion secondary
lithium
complex
secondary battery
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/KR2025/099657
Other languages
English (en)
Korean (ko)
Inventor
정이진
정윤채
송민상
유지상
황치현
전상진
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.)
LG Energy Solution Ltd
Original Assignee
LG Energy Solution Ltd
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Filing date
Publication date
Application filed by LG Energy Solution Ltd filed Critical LG Energy Solution Ltd
Priority claimed from KR1020250031510A external-priority patent/KR20250138670A/ko
Publication of WO2025193043A1 publication Critical patent/WO2025193043A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—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
    • H01M4/36—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
    • 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 material comprising a Mg(O)/C composite, a negative electrode comprising the negative electrode material, a lithium ion secondary battery comprising the negative electrode, and a method for producing the Mg(O)/C composite.
  • Lithium-ion secondary batteries utilizing solid electrolytes have recently attracted attention. To improve the energy density of these batteries, the use of lithium as an anode active material has been proposed.
  • the capacity density (capacity per unit weight) of lithium is approximately ten times that of graphite, a commonly used anode material. Therefore, using lithium as an anode active material allows for thinner lithium-ion secondary batteries while increasing their output.
  • an anodeless lithium-ion secondary battery including a negative electrode active material layer including a metal that forms an alloy with lithium and a carbon material is known.
  • the above anode-less lithium-ion secondary battery is driven by a mechanism in which metallic lithium is deposited between the negative electrode active material layer and the current collector during charging, and the metallic lithium is ionized and moves toward the positive electrode during discharge.
  • the purpose of the present invention is to provide a negative electrode material, a negative electrode, and a lithium ion secondary battery capable of improving the operating characteristics and life characteristics of the battery.
  • the purpose is to provide an efficient method for manufacturing a Mg(O)/C composite having excellent performance as a cathode material.
  • a cathode material comprising a Mg(O)/C complex, which is a carbide of Mg-MOF-74 (metal-organic framework-74(magnesium)), wherein O is present or absent in the Mg(O)/C complex.
  • Mg-MOF-74 metal-organic framework-74(magnesium)
  • a negative electrode which includes a negative electrode active material layer comprising 35 to 60 wt% of the above negative electrode material, 35 to 60 wt% of the conductive material, and 3 to 15 wt% of the binder.
  • a lithium ion secondary battery comprising the above negative electrode; the positive electrode; and an electrolyte disposed between the negative electrode and the positive electrode.
  • a method for producing a Mg(O)/C composite including a step of carbonizing the above Mg-MOF-74 at a temperature of 500 to 1000°C.
  • the negative electrode material, negative electrode, and lithium ion secondary battery of the present invention provide an effect of improving the operating characteristics and life characteristics of the battery by including a Mg(O)/C complex.
  • the method for producing a Mg(O)/C composite of the present invention provides an efficient method for producing a Mg(O)/C composite having excellent performance as a negative electrode material.
  • Figure 1 is a cross-sectional view schematically showing the structure of a lithium ion secondary battery of the present invention.
  • Figure 2 is a scanning electron microscope image (a) and an EDS (Energy-dispersive X-ray spectroscopy) image (b) of the Mg(O)/C composite of the present invention.
  • Figure 3 is a transmission electron microscope image of the Mg(O)/C complex of the present invention.
  • Figure 4 is a graph showing the results of X-ray diffraction analysis of Mg(O)/C composites manufactured by examples and comparative examples.
  • Figure 5 is a graph showing the results of measuring the discharge capacity retention rate and charge/discharge efficiency of the lithium ion secondary battery of Example 1 in Experimental Example 2.
  • Figure 6 is a graph showing the results of confirming the activity of the Mg(O)/C complex in Experimental Example 3.
  • Figure 7 is an SEM image showing the morphology of the Mg(O)/C complex according to pH control during the preparation of the Mg(O)/C complex.
  • Figures 8 and 9 are cross-sectional views schematically showing the structure of a lithium ion secondary battery of the present invention.
  • the negative electrode material of the present invention has the characteristic of including a Mg(O)/C complex, which is a carbide of Mg-MOF-74 (metal-organic framework-74 (magnesium)).
  • Mg-MOF-74 metal-organic framework-74 (magnesium)
  • O oxygen
  • the above Mg(O)/C complex has a structure that is a mixture of crystalline and amorphous.
  • the above Mg(O)/C composite has the characteristics of improving the dispersibility between carbon and metal and securing structural stability through the carbon matrix. In addition, it has the characteristic of stabilizing the interface between the solid electrolyte layer and the negative electrode active material layer through the decomposition of MgO during battery operation.
  • the weight ratio of Mg and C may be 1:0.5 to 10, and more preferably 1:1 to 4.
  • the weight ratio of MgO and C may be 1:0.25 to 5, and more preferably 1:0.5 to 2.
  • Mg and MgO When Mg and MgO are included together in the above Mg(O)/C complex, their weight ratio may be 1:0.25 to 8, and more preferably 1:0.5 to 3.
  • the weight ratio between atoms or between atoms and molecules in the above Mg(O)/C complex was measured by thermogravimetric analysis.
  • the particle size of the Mg(O)/C complex described above may be 10 nm to 10 ⁇ m, preferably 50 nm to 1 ⁇ m, and more preferably 50 nm to 500 nm.
  • the particle size can be measured using a particle size analyzer (manufacturer: Malvern).
  • the above Mg-MOF-74 (metal-organic framework-74 (magnesium)) may have, for example, the following structure.
  • the present invention is a.
  • an anode comprising a anode active material layer comprising 40 to 89 wt% of the above-described anode material, 10 to 50 wt% of a conductive material, and 1 to 10 wt% of a binder.
  • the anode material may be composed of 100 wt% of a Mg(O)/C composite, or may be composed of 80 to 99 wt% of the Mg(O)/C composite and 1 to 20 wt% of another material such as a metal.
  • the other material such as a metal, materials known in the art may be used without limitation.
  • the above negative electrode may include a negative electrode active material layer and a negative electrode current collector.
  • the negative electrode active material layer may also be called a protective layer in that it protects the battery from dendrites.
  • a lithium ion secondary battery comprising the above negative electrode; the positive electrode; and an electrolyte disposed between the negative electrode and the positive electrode.
  • the above electrolyte may preferably include a sulfide-based solid electrolyte, but is not limited thereto.
  • the above lithium ion secondary battery may be an anodeless battery.
  • magnesium precursor at least one selected from the group consisting of magnesium nitrate hexahydrate (Mg(NO 3 ) 2 ⁇ 6H 2 O), magnesium nitrate dihydrate (Mg(NO 3 ) 2 ⁇ 2H 2 O), magnesium nitrate (Mg(NO 3 ) 2 ), and magnesium hydroxide (Mg(OH) 2 ) may be used.
  • the above 2,5-dihydroxyterephthalate acid may be used in an amount of 200 to 300 parts by weight based on 100 parts by weight of magnesium contained in the magnesium precursor. If the above 2,5-dihydroxyterephthalate acid is used in an amount less than 200 parts by weight, a problem may arise in which the magnesium does not react sufficiently, and if it is used in an amount exceeding 300 parts by weight, the amount of unreacted residue increases, which may cause side reactions, and thus is not preferable.
  • a solvent mixed with dimethylformamide, ethanol, and water in a volume ratio of 10 to 25:0.5 to 2:1 can be used, and more preferably, a solvent mixed with a volume ratio of 15 to 20:0.7 to 1.5:1 can be used.
  • the volume ratio of the above dimethylformamide is mixed at less than 10
  • the problem of rapid increase in the size of Mg-MOF-74 may occur, and if it is mixed at more than 25, the problem of failure to develop the structure of Mg-MOF-74 may occur, which is not preferable.
  • the weight ratio of the above ethanol is mixed at less than 0.5, the problem of failure to develop the structure of Mg-MOF-74 may occur, and if it is mixed at more than 2, the problem of rapid increase in the size of Mg-MOF-74 may occur, which is not preferable.
  • the pH of the solution can be adjusted to 9 to 11, preferably 9 to 10.5, more preferably 9.5 to 10. If the pH of the solution is less than 9 or more than 11, the problem of Mg-MOF-74 not being synthesized occurs, which is not preferred.
  • the above pH adjustment can be performed by adding a basic substance such as NaOH, for example.
  • the particle size of the Mg(O)/C complex decreases, showing a tendency to become similar to that of non-graphite carbon materials (see Fig. 7).
  • the heat treatment in step c) may be performed at 110 to 140°C, preferably 120 to 130°C. If the heat treatment is performed at a temperature lower than 110°C, a problem may arise in which the reaction does not occur, and if it is performed at a temperature higher than 140°C, a problem may arise in which the composite is not uniformly formed due to concentration changes caused by solvent evaporation, etc., which is not preferable.
  • the heat treatment in step c) above is performed for 18 to 30 hours, and more preferably for 23 to 30 hours.
  • the above solvent can be used in an amount of 30 to 300 times the weight of the combined weight of the magnesium precursor and 2,5-dihydroxyterephthalic acid, preferably 50 to 200 times, and more preferably 70 to 150 times.
  • the size of Mg-MOF-74 may increase, and if it exceeds 300 times, it is not desirable because it is unfavorable in terms of reaction kinetics.
  • the solid in step d), can be obtained by a process of adding the heat-treated reactant to a solvent to obtain a precipitate.
  • the solid can be obtained by adding the reactant to methanol to produce a precipitate and drying the precipitate.
  • the drying can be performed using a vacuum drying method.
  • the carbonization in step e) above can be performed at a temperature of 500 to 1000°C, preferably 600 to 700°C. If the carbonization temperature is less than 500°C or more than 1000°C, the shape of the particles may be deformed, which is not preferable.
  • the above carbonization can be performed under an inert atmosphere.
  • Figure 8 is a cross-sectional view showing a schematic configuration of a lithium ion secondary battery according to one embodiment of the present invention.
  • a lithium ion secondary battery (100) is a so-called lithium ion secondary battery that performs charging and discharging by moving lithium ions between a positive electrode (10) and a negative electrode (20).
  • this lithium ion secondary battery (100) is composed of a positive electrode (10), a negative electrode (20), and a solid electrolyte layer (30) disposed between the positive electrode (10) and the negative electrode (20).
  • the positive electrode (10) includes a positive electrode current collector (12) and a positive electrode active material layer (14) arranged sequentially toward the negative electrode (20).
  • the positive electrode current collector (12) may be plate-shaped or foil-shaped.
  • the positive electrode current collector (12) may be, for example, one type of metal selected from indium, copper, magnesium, stainless steel, titanium, iron, cobalt, nickel, zinc, aluminum, germanium, and lithium, or an alloy of two or more types of metals.
  • the cathode active material layer (14) can reversibly store and release lithium ions.
  • the cathode active material layer (14) can include a cathode active material and a solid electrolyte.
  • the above cathode active material may be a compound capable of insertion/de-insertion of lithium.
  • the compound capable of insertion/de-insertion of lithium include Li a A 1-b B' b D' 2 (wherein, 0.90 ⁇ a ⁇ 1.8, and 0 ⁇ b ⁇ 0.5); Li a E 1 - b B' b O 2-c D' c (wherein, 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); LiE 2-b B' b O 4-c D' c (wherein, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); Li a Ni 1-bc Co b B' c D' ⁇ (wherein, 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2); Li a Ni 1-bc Co b B' c O 2- ⁇ F' ⁇ (In the above formula, 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, 0 ⁇ 2); Li
  • A is Ni, Co, Mn, or a combination thereof
  • B' is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof
  • D' is O, F, S, P, or a combination thereof
  • E is Co, Mn, or a combination thereof
  • F' is F, S, P, or a combination thereof
  • G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof
  • Q is Ti, Mo, Mn, or a combination thereof
  • I' is Cr, V, Fe, Sc, Y, or a combination thereof
  • J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.
  • positive electrode active material examples include lithium cobaltate (hereinafter referred to as LCO), lithium nickelate, lithium nickel cobaltate, lithium nickel cobalt aluminumate (hereinafter referred to as NCA), lithium nickel cobalt manganese (hereinafter referred to as NCM), lithium manganese acid, lithium iron phosphate, and lithium salts, and lithium sulfide.
  • LCO lithium cobaltate
  • NCA lithium nickelate
  • NCM lithium nickel cobalt aluminumate
  • NCM lithium nickel cobalt manganese
  • the positive electrode active material layer (14) may include only one type selected from these compounds as the positive electrode active material, or may include two or more types.
  • the above-described positive electrode active material may include a lithium salt of a transition metal oxide having a layered rock salt structure among the lithium salts described above.
  • the “layered rock salt structure” refers to a structure in which oxygen atomic layers and metal atomic layers are alternately and regularly arranged in the direction of the cubic rock salt structure, and as a result, each atomic layer forms a two-dimensional plane.
  • the “cubic rock salt structure” refers to a sodium chloride structure, which is a type of crystal structure.
  • the “cubic rock salt structure” refers to a structure in which face-centered cubic lattices in which cations and anions are respectively formed are arranged with a displacement of half of the corners of the unit cell.
  • the cathode active material layer (14) includes the lithium salt of the ternary transition metal oxide having such a layered rock salt structure as a cathode active material, thereby improving the energy density and thermal stability of the lithium ion secondary battery (100).
  • examples of the shape of the positive electrode active material include spherical, elliptical, and spherical particle shapes.
  • the particle size of the positive electrode active material is not particularly limited, and may be within the range applicable to positive electrode materials for typical lithium-ion secondary batteries.
  • the content of the positive electrode active material in the positive electrode active material layer (14) is not particularly limited, and may be within the range applicable to positive electrodes for typical lithium-ion secondary batteries.
  • the coating layer may include a coating element compound of an oxide, a hydroxide, an oxyhydroxide of the coating element, an oxycarbonate of the coating element, or a hydroxycarbonate of the coating element.
  • the compounds forming these coating layers may be amorphous or crystalline.
  • the coating elements included in the coating layer may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or mixtures thereof.
  • the coating layer forming process may use any coating method as long as it can coat the compound with these elements and does not adversely affect the properties of the positive electrode active material (e.g., spray coating, dipping, etc.). Since this is well understood by those working in this field, a detailed description thereof will be omitted.
  • the above coating layer includes Li 2 O-ZrO 2 , etc.
  • the solid electrolyte included in the positive electrode active material layer (14) may be the same as or different from the solid electrolyte included in the solid electrolyte layer (30) described later.
  • the cathode active material layer (14) may be a material in which not only the cathode active material and solid electrolyte described above, but also additives such as a conductive agent, a binder, a filler, a dispersant, or an ion conductive auxiliary agent are appropriately mixed.
  • Examples of the above-mentioned conductive agent include graphite, carbon black, acetylene black, Ketjen black, carbon fiber, or metal powder.
  • Examples of the above-mentioned binder include styrene-butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, or polyethylene.
  • SBR styrene-butadiene rubber
  • known materials commonly used in electrodes of lithium-ion secondary batteries can be used as the above-mentioned filler, dispersant, or ion-conductive auxiliary agent.
  • the negative electrode (20) may include a negative electrode current collector (22) and a negative electrode active material layer (24) arranged sequentially toward the positive electrode (10).
  • the negative electrode current collector (22) may be plate-shaped or foil-shaped.
  • the negative electrode current collector (22) may include a material that does not react with lithium, i.e., does not form any alloys or compounds with lithium. Examples of materials constituting the negative electrode current collector (22) include copper, stainless steel, titanium, iron, cobalt, and nickel.
  • the negative electrode current collector (22) may be composed of one type of these metals, or may be composed of an alloy of two or more types of metals or a clad material.
  • the negative electrode active material layer (24) may not contain lithium between the negative electrode current collector (22), the negative electrode active material layer (24), or the negative electrode active material layer (24) and the solid electrolyte layer (30) in the initial state or the state after complete discharge.
  • the active material contained in the negative electrode active material layer (24) and the lithium ions moved from the positive electrode (10) form an alloy or compound, and a metal layer (26) mainly composed of lithium may be formed (deposited) on the negative electrode (20) as shown in FIG. 9.
  • the metal layer (26) may be deposited and disposed between the negative electrode current collector (22) and the negative electrode active material layer (24), inside the negative electrode active material layer (24), or both. Between the negative electrode current collector (22) and the negative electrode active material layer (24), the metal layer (26) containing lithium as a main component may be arranged closer to the negative electrode current collector layer (22) than to the negative electrode active material layer (24).
  • the above-described negative electrode active material layer (24) may include carbon particles, metal particles, metal oxide particles, and a binder in addition to the Mg(O)/C composite described above.
  • the binder binder
  • the negative electrode active material layer (24) can be stabilized on the negative electrode current collector (22).
  • materials constituting the binder (binding agent) include resin materials such as styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride (PVDF), and polyethylene.
  • the binder (binding agent) may be composed of one or more types selected from these resin materials.
  • the negative electrode active material layer (24) may be appropriately mixed with additives used in conventional lithium ion secondary batteries, such as fillers, dispersants, and ionic conductive agents. Specific examples of the additives are the same as those described for the positive electrode described above.
  • the overall thickness of the negative electrode active material layer (24) is not particularly limited, but may be 1 ⁇ m to 100 ⁇ m, or 10 ⁇ m to 60 ⁇ m. If the thickness of the negative electrode active material layer (24) is less than 1 ⁇ m, the performance of the lithium ion secondary battery may not be sufficiently improved. If the thickness of the negative electrode active material layer (24) exceeds 100 ⁇ m, the resistance of the negative electrode active material layer (24) is high, and as a result, the performance of the lithium ion secondary battery may not be sufficiently improved. By using the above-described binder, the thickness of the negative electrode active material layer (24) can be easily secured at an appropriate level.
  • a film including a material capable of forming an alloy or compound with lithium may be further included on the negative electrode current collector (22), and the film may be disposed between the negative electrode current collector (22) and the negative electrode active material layer.
  • the thickness of the film may be from 1 nm to 500 nm.
  • the thickness of the film may be, for example, from 2 nm to 400 nm.
  • the thickness of the film may be, for example, from 3 nm to 300 nm.
  • the thickness of the film may be, for example, from 4 nm to 200 nm.
  • the thickness of the film may be, for example, from 5 nm to 100 nm.
  • a solid electrolyte layer (30) is disposed between the positive electrode (10) and the negative electrode (20) (e.g., between the positive electrode active material layer (14) and the negative electrode active material layer (24)).
  • the solid electrolyte layer (30) includes a solid electrolyte capable of moving ions.
  • the solid electrolyte layer (30) may include a sulfide-based solid electrolyte.
  • the above sulfide-based solid electrolytes are Li 2 SP 2 S 5 , Li 2 SP 2 S 5 -LiX (X is a halogen element), Li 2 SP 2 S 5 -Li 2 O, Li 2 SP 2 S 5 -Li 2 O-LiI, Li 2 S-SiS 2 , Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -LiBr, Li 2 S-SiS 2 -LiCl, Li 2 S-SiS 2 -B 2 S 3 -LiI, Li 2 S-SiS 2 -P 2 S 5 -LiI, Li 2 SB 2 S 3 , Li 2 SP 2 S 5 -Z m S n (m and n are positive numbers, Z is one of Ge, Zn or Ga), Li 2 S-GeS 2 , Li 2 S-SiS 2 -Li 3 PO 4 , Li 2 S-SiS 2 -Li p MO q (
  • the above sulfide-based solid electrolyte may include a solid electrolyte represented by the following chemical formula 1:
  • x, y, z, w are independently 0 to 6;
  • M' is one or more of As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb, or Ta;
  • A is one or more of F, Cl, Br, or I.
  • one of the sulfide solid electrolyte materials containing sulfur (S), phosphorus (P), and lithium (Li) as constituent elements can be used.
  • one containing Li 2 SP 2 S 5 can be used.
  • solid electrolytes can be amorphous or crystalline, or a mixture of amorphous and crystalline states.
  • the lithium ion secondary battery (100) of the present invention may be a lithium ion secondary battery (100) including a positive electrode (10), a solid electrolyte layer (30), and a negative electrode (20) in this order, as illustrated in FIG. 8.
  • a lithium ion secondary battery (100) can be obtained by manufacturing a positive electrode (10), a negative electrode (20), and a solid electrolyte layer (30), respectively, and then laminating each of the above layers.
  • the positive electrode manufacturing process is explained as follows, for example. First, materials constituting the positive electrode active material layer (14) (positive electrode active material, binder, etc.) are added to a non-polar solvent to produce a slurry (or paste). Next, the obtained slurry is applied onto the prepared positive electrode current collector (12). This is dried to obtain a laminate. Next, the obtained laminate is pressed using, for example, hydrostatic pressure to obtain a positive electrode (10). In this case, the pressing process is omitted.
  • the negative electrode can be manufactured by preparing a slurry for forming each layer and sequentially stacking each layer according to the stacking order using the method described above.
  • the solid electrolyte layer (30) can be manufactured using a solid electrolyte including, for example, a sulfide-based solid electrolyte material.
  • the starting materials e.g., Li2S, P2S5, etc.
  • the starting materials are processed by a melt-quenching method or a mechanical milling method to obtain a sulfide-based solid electrolyte material.
  • the starting materials are mixed in a predetermined amount, made into pellets, reacted in a vacuum at a predetermined reaction temperature, and then rapidly cooled to produce a sulfide-based solid electrolyte material.
  • the reaction temperature of the mixture of Li2S and P2S5 may be 400°C to 1000°C, for example, 800°C to 900°C.
  • the reaction time may be 0.1 hour to 12 hours, for example, 1 hour to 12 hours.
  • the quenching temperature of the reactants may be 10°C or lower, for example, 0°C or lower, and the quenching rate may be typically 1°C/sec to 10,000°C/sec, for example, 1°C/sec to 1000°C/sec.
  • a sulfide-based solid electrolyte material when using a mechanical milling method, can be manufactured by stirring and reacting the starting raw materials using a ball mill, etc.
  • the stirring speed and stirring time of the mechanical milling method are not particularly limited, but the faster the stirring speed, the faster the production speed of the sulfide-based solid electrolyte material can be, and the longer the stirring time, the higher the conversion rate of the raw materials into the sulfide-based solid electrolyte material can be.
  • the obtained mixed raw material (sulfide-based solid electrolyte material) is heat-treated at a predetermined temperature and then pulverized to produce a solid electrolyte in particle form.
  • the solid electrolyte may change from an amorphous state to a crystalline state through heat treatment.
  • the solid electrolyte obtained by the above method can be formed into a film using a known film forming method such as an aerosol position method, a cold spray method, or a sputtering method, thereby manufacturing a solid electrolyte layer (30).
  • the solid electrolyte layer (30) can be manufactured by pressurizing solid electrolyte particles.
  • the solid electrolyte layer (30) can be manufactured by mixing a solid electrolyte, a solvent, and a binder, applying, drying, and pressurizing the solid electrolyte layer (30).
  • the lithium ion secondary battery (100) of the present invention does not require application of high external pressure using an end plate or the like, and can provide improved discharge capacity even when the external pressure applied to the positive electrode (10), negative electrode (20), and solid electrolyte layer (30) during use is 1 MPa or less.
  • a charging method of a lithium ion secondary battery (100) may be to charge (i.e., overcharge) the lithium ion secondary battery (100) beyond the charging capacity of the negative electrode active material layer (24).
  • lithium may be absorbed into the negative electrode active material layer (24). If charging exceeds the charge capacity of the negative electrode active material layer (24), as shown in FIG. 9, lithium may be precipitated on the back of the negative electrode active material layer (24), that is, between the negative electrode current collector (22) and the negative electrode active material layer (24), and a metal layer (26) that did not exist during manufacturing may be formed by this lithium.
  • lithium in the negative electrode active material layer (24) and the metal layer (26) may be ionized and move toward the positive electrode (10). Therefore, lithium may be used as the negative electrode active material in the lithium ion secondary battery (100) of the present invention.
  • the negative electrode active material layer (24) coats the metal layer (26), it functions as a protective layer for the metal layer (26) and can suppress the precipitation and growth of dendritic metallic lithium. In this way, short circuit and capacity reduction of the lithium ion secondary battery (100) can be suppressed, and further, the characteristics of the lithium ion secondary battery (100) can be improved.
  • the metal layer (26) is not formed in advance, the manufacturing cost of the lithium ion secondary battery (100) can be reduced.
  • the metal layer (26) is not limited to being formed between the negative electrode current collector (22) and the negative electrode active material layer (24) as shown in Fig. 9, but may also be formed inside the negative electrode active material layer (24). In addition, the metal layer (26) may be formed both between the negative electrode current collector (22) and the negative electrode active material layer (24) and inside the negative electrode active material layer (24).
  • the lithium ion secondary battery (100) of the present invention may be manufactured as a unit cell having a structure of positive electrode/separator/negative electrode, a bi-cell having a structure of positive electrode/separator/negative electrode/separator/positive electrode, or a laminated battery having a structure of repeating unit cells.
  • the shape of the lithium ion secondary battery (100) of the present invention is not particularly limited, and examples thereof include coin-shaped, button-shaped, sheet-shaped, stacked, cylindrical, flat, and cone-shaped batteries. Furthermore, the lithium ion secondary battery (100) can be applied to large-scale batteries used in electric vehicles, etc. For example, the lithium ion secondary battery (100) can be used in hybrid vehicles such as plug-in hybrid electric vehicles (PHEVs). Furthermore, the lithium ion secondary battery can be used in fields requiring a large amount of power storage. For example, it can be used in electric bicycles or power tools.
  • PHEVs plug-in hybrid electric vehicles
  • Example 1 Manufacturing of a lithium-ion secondary battery
  • magnesium nitrate hexahydrate (Mg( NO3 ) 2 ⁇ 6H2O ) and 0.337 g of 2,5-dihydroxyterephthalic acid were dissolved in 153 ml of a solution of dimethylformamide, ethanol, and water in a volume ratio of 15:1:1. Then, 10% NaOH aqueous solution was slowly added to adjust the pH to 9.5, mixed for 1 hour, sealed, and then heat-treated in a kiln at 125°C for 26 hours. Afterwards, the reactants were added to methanol, and the precipitate was vacuum-dried to prepare Mg-MOF-74.
  • Mg-MOF-74 obtained in was heat-treated at 600°C for 6 hours under an argon gas atmosphere to prepare a Mg(O)/C composite.
  • the particle size of the prepared Mg(O)/C composite was 50 nm.
  • the weight ratio of Mg:C in the Mg(O)/C composite was 1:1.5.
  • the above mixture was stirred with a thinky mixer to adjust the viscosity. After adjusting the viscosity, 2 mm zirconia balls were added and stirred again with the mixer to prepare a slurry.
  • NBD n-Butylyl butylate
  • the positive electrode manufactured above was cut into a square size of 4 cm 2 , the solid electrolyte manufactured above was cut into a square size of 5.76 cm 2 , and the negative electrode manufactured above was cut into a square size of 4.84 cm 2 , and then these were laminated to manufacture a lithium ion secondary battery.
  • a lithium ion secondary battery was manufactured in the same manner as in Example 1, except that the pH was adjusted to 10 in “(1) Manufacturing of Mg-MOF-74” of Example 1.
  • the particle size of the manufactured Mg(O)/C complex was 50 nm, and this Mg(O)/C complex was used to manufacture the negative electrode.
  • a lithium ion secondary battery was manufactured in the same manner as in Example 1, except that the pH was adjusted to 8.5 in “(1) Manufacturing of Mg-MOF-74” of Example 1.
  • the particle size of the manufactured Mg(O)/C complex was 5 ⁇ m, and this Mg(O)/C complex was used to manufacture the cathode.
  • a lithium ion secondary battery was manufactured in the same manner as in Comparative Example 1, except that in “(1) Manufacturing of Mg-MOF-74” of Example 1, dimethylformamide, ethanol, and water were mixed in a volume ratio of 38:1:1 instead of 15:1:1.
  • the particle size of the manufactured Mg(O)/C complex was 15 ⁇ m, and this Mg(O)/C complex was used to manufacture the cathode.
  • a lithium ion secondary battery was manufactured in the same manner as in Comparative Example 1, except that 0.674 g of 2,5-dihydroxyterephthalic acid was used instead of 0.337 g in “(1) Manufacturing of Mg-MOF-74” of Example 1.
  • the particle size of the manufactured Mg(O)/C composite was 20 ⁇ m, and this Mg(O)/C composite was used to manufacture the cathode.
  • a lithium ion secondary battery was manufactured in the same manner as in Comparative Example 1, except that the heat treatment was performed for 16 hours instead of 26 hours in the kiln in “(1) Manufacturing of Mg-MOF-74” of Example 1.
  • the particle size of the manufactured Mg(O)/C complex was 10 ⁇ m, and this Mg(O)/C complex was used to manufacture the cathode.
  • a lithium ion secondary battery was manufactured in the same manner as in Comparative Example 1, except that 460 ml of a solution containing dimethylformamide, ethanol, and water mixed in a volume ratio of 15:1:1 was used instead of 153 ml in “(1) Manufacturing of Mg-MOF-74” of Example 1.
  • the particle size of the manufactured Mg(O)/C complex was 2 ⁇ m, and this Mg(O)/C complex was used to manufacture the cathode.
  • a lithium ion secondary battery was manufactured in the same manner as in Comparative Example 1, except that instead of using a mixture of Mg(O)/C complex and carbon black at a weight ratio of 1:1 in “(3) Manufacturing of negative electrode” of Example 1, the Mg(O)/C complex was not used and twice as much carbon black was used.
  • the lithium ion secondary batteries manufactured in Examples 1 to 2 and Comparative Examples 1 to 6 were operated at an operating voltage range of 2.5 V to 4.3 V and an operating temperature of 60°C to evaluate the discharge amount.
  • the discharge capacity retention rate and charge/discharge efficiency of the secondary battery manufactured in Example 1 were measured by CC charging and CC discharging at 0.2C at an operating voltage range of 2.5 V to 4.3 V and an operating temperature of 60°C, and the results are shown in Fig. 5.
  • the Mg(O)/C composite manufactured in Example 1 was used to form a negative electrode, and lithium metal was used as a counter electrode to pelletize and manufacture a half-cell.
  • the activity of the Mg(O)/C composite was measured while the half-cell was CC-charged and CC-discharged at a current of 0.1 C in the operating voltage range of 0 V to 1.5 V.
  • the activity confirmation results are shown in Fig. 6.
  • the Mg(O)/C composite of the present invention exhibited activity distinct from that of non-graphite active materials.
  • Solid electrolyte layer 4 Positive electrode active material layer

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Abstract

La présente invention concerne : un matériau d'électrode négative comprenant un composite Mg(O)/C, qui est un carbure de structure organométallique de magnésium 74 (Mg-MOF-74), O étant présent ou absent dans le composite Mg(O)/C ; une électrode négative comprenant le matériau d'électrode négative ; une batterie secondaire au lithium-ion comprenant l'électrode négative ; et un procédé de fabrication du composite Mg(O)/C.
PCT/KR2025/099657 2024-03-12 2025-03-11 Matériau d'électrode négative comprenant un composite mg(o)/c, électrode négative, batterie secondaire au lithium-ion et procédé de fabrication de composite mg(o)/c Pending WO2025193043A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2024-0034255 2024-03-12
KR20240034255 2024-03-12
KR10-2025-0031510 2025-03-11
KR1020250031510A KR20250138670A (ko) 2024-03-12 2025-03-11 Mg(O)/C 복합체를 포함하는 음극재, 음극, 리튬이온 이차전지, 및 상기 Mg(O)/C 복합체의 제조방법

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WO2025193043A1 true WO2025193043A1 (fr) 2025-09-18

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PCT/KR2025/099657 Pending WO2025193043A1 (fr) 2024-03-12 2025-03-11 Matériau d'électrode négative comprenant un composite mg(o)/c, électrode négative, batterie secondaire au lithium-ion et procédé de fabrication de composite mg(o)/c

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WO (1) WO2025193043A1 (fr)

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