WO2024072059A1 - Anode et batterie secondaire - Google Patents

Anode et batterie secondaire Download PDF

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Publication number
WO2024072059A1
WO2024072059A1 PCT/KR2023/014944 KR2023014944W WO2024072059A1 WO 2024072059 A1 WO2024072059 A1 WO 2024072059A1 KR 2023014944 W KR2023014944 W KR 2023014944W WO 2024072059 A1 WO2024072059 A1 WO 2024072059A1
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Prior art keywords
active material
negative electrode
weight
material layer
electrode active
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PCT/KR2023/014944
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English (en)
Korean (ko)
Inventor
김슬기
이경섭
김민수
박규태
박려림
백소라
유광호
정원희
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주식회사 엘지에너지솔루션
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Priority claimed from KR1020230129257A external-priority patent/KR20240046065A/ko
Application filed by 주식회사 엘지에너지솔루션 filed Critical 주식회사 엘지에너지솔루션
Publication of WO2024072059A1 publication Critical patent/WO2024072059A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode for a secondary battery and a secondary battery containing the same.
  • Secondary batteries are universally applied not only to portable devices but also to electric vehicles (EVs) and hybrid vehicles (HEVs) that are driven by an electrical drive source.
  • EVs electric vehicles
  • HEVs hybrid vehicles
  • secondary batteries include a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte.
  • electrodes such as positive electrodes and negative electrodes may have an electrode active material layer provided on a current collector.
  • the present invention seeks to provide a negative electrode for a secondary battery that can provide a secondary battery with improved charging performance and lifespan, and a secondary battery containing the same.
  • a first negative electrode active material layer provided on the current collector
  • It includes a second negative electrode active material layer provided on the first negative electrode active material layer,
  • At least one of the first and second negative electrode active material layers includes lithium-substituted carboxymethyl cellulose,
  • the first negative electrode active material layer includes a carbon-based active material, and only the second negative electrode active material layer includes a silicon-based active material.
  • Another embodiment of the present invention provides a secondary battery including the negative electrode, positive electrode, and separator for the secondary battery.
  • silicon-based active materials may have lower electrical conductivity than carbon-based active materials, so if the silicon-based active material is evenly distributed in the thickness direction of the negative electrode active material layer (T in Figure 1), it may cause non-uniformity in the entire electrode in terms of electrical conductivity. This may be detrimental to charging performance (normal charging).
  • the silicon-based active material is included only in the second anode active material layer ( Figure 1, 202) in the two-layer structure, the electrical conductivity can be increased, thereby lowering the mutual contact resistance, and in addition, lithium substitution with high electrical/ion mobility of Li
  • carboxymethyl cellulose When lithium-substituted carboxymethyl cellulose is applied, the mobility of Li ions increases, so it is possible to secure life durability that is slightly inferior when the silicon-based active material is included only in the second negative electrode active material layer.
  • the flux of lithium ions is formed to be relatively larger than during normal charging (normal cycle).
  • the rapid charging performance of the cell can be improved if the negative electrode active material can quickly receive lithium ions.
  • silicon-based active materials accept lithium ions through alloying and start charging from a lower potential, they are more advantageous in improving fast charging performance than graphite-based anode active materials that accept lithium ions through intercalation. do.
  • the silicon-based active material reacts quickly with lithium ions, greatly improving fast charging performance. there is.
  • Figure 1 illustrates a cathode according to an exemplary embodiment of the present invention.
  • a negative electrode for a secondary battery includes a current collector; A first negative electrode active material layer provided on the current collector; and a second negative electrode active material layer provided on the first negative electrode active material layer, wherein at least one of the first and second negative electrode active material layers includes lithium-substituted carboxymethyl cellulose, and the first negative electrode active material layer includes It contains a carbon-based active material, and only the second negative electrode active material layer contains a silicon-based active material.
  • the negative electrode for a secondary battery is characterized by including lithium-substituted carboxymethyl cellulose along with two layers of negative electrode active material. The distribution of the silicon-based active material can be confirmed through SEM images of the electrode cross-section. Therefore, the area where the silicon-based active material exists can be defined as the second negative electrode active material layer.
  • Figure 1 illustrates a negative electrode including a first negative electrode active material layer 201, a second negative electrode active material layer 202, and a current collector 101.
  • the present inventors have found that the lithium-substituted carboxymethyl cellulose has an advantage over the sodium-substituted carboxymethyl cellulose in improving the charging performance and securing the lifespan of the battery, especially in combination with the multilayer structure of the negative electrode active material layer containing a silicon-based active material.
  • the present invention was developed by discovering that when used, the charging performance and lifespan of the battery can be further maximized through a synergistic effect.
  • the lithium-substituted carboxymethyl cellulose may be included in both the first and second negative electrode active material layers, and may be included in one layer of the first negative electrode active material layer or the second negative electrode active material layer.
  • the lithium-substituted carboxymethyl cellulose may be included in more amount in the second anode active material layer than in the first anode active material layer, or may be included only in the second anode active material layer.
  • one or both of the first and second negative electrode active material layers may include lithium-substituted carboxymethyl cellulose and may not contain sodium-substituted carboxymethyl cellulose at all, but in another embodiment, In addition, it may further include sodium-substituted carboxymethylcellulose.
  • one of the first and second negative electrode active material layers may include lithium-substituted carboxymethyl cellulose, and the other may include sodium-substituted carboxymethyl cellulose.
  • lithium-substituted carboxymethyl cellulose and sodium-substituted carboxymethyl cellulose are the only carboxymethyl cellulose salts included in the electrode.
  • the silicon-based active material includes at least one of SiOx (0 ⁇ x ⁇ 2), SiMy (M is a metal, 1 ⁇ y ⁇ 4), and Si/C.
  • the silicon-based active material may include only one type, or two or more types may be included together.
  • the second anode active material layer including the silicon-based active material may further include a carbon-based active material.
  • the silicon-based active material is used in an amount of 1 part by weight to 40 parts by weight, for example, 2 parts by weight to 35 parts by weight, and 3 parts by weight to 30 parts by weight. parts, 5 to 25 parts by weight, and 7 to 15 parts by weight.
  • the first negative electrode active material layer includes a carbon-based active material, and only the second negative electrode active material layer includes a silicon-based active material. In this case, the first negative electrode active material layer does not include a silicon-based active material.
  • the silicon-based active material containing SiOx (0 ⁇ x ⁇ 2) may be a silicon-based composite particle containing SiOx (0 ⁇ x ⁇ 2) and pores.
  • composite particles or composites mean that two or more materials or substances are physically aggregated without chemical bonding.
  • the SiO x (0 ⁇ x ⁇ 2) corresponds to a matrix within the silicon-based composite particles.
  • the SiO x (0 ⁇ x ⁇ 2) may be in a form containing Si and SiO 2 , and the Si may be in a phase. That is, x corresponds to the number ratio of O to Si included in the SiO x (0 ⁇ x ⁇ 2).
  • the silicon-based composite particles include the SiO x (0 ⁇ x ⁇ 2), the discharge capacity of the secondary battery can be improved.
  • the silicon-based composite particle may further include at least one of an Mg compound and a Li compound.
  • the Mg compound and Li compound may correspond to a matrix within the silicon-based composite particle.
  • the Mg compound and/or Li compound may be present inside and/or on the surface of the SiO x (0 ⁇ x ⁇ 2).
  • the initial efficiency of the battery may be improved by the Mg compound and/or Li compound.
  • the Mg compound may include at least one selected from the group consisting of Mg silicate, Mg silicide, and Mg oxide.
  • the Mg silicate may include at least one of Mg 2 SiO 4 and MgSiO 3 .
  • the Mg silicide may include Mg 2 Si.
  • the Mg oxide may include MgO.
  • the Mg element may be included in an amount of 0.1% by weight to 20% by weight, or may be included in an amount of 0.1% by weight to 10% by weight based on a total of 100% by weight of the silicon-based active material. Specifically, the Mg element may be included in an amount of 0.5% to 8% by weight or 0.8% to 4% by weight.
  • the Mg compound can be included in an appropriate amount in the silicon-based active material, so the volume change of the silicon-based active material can be easily suppressed during charging and discharging of the battery, and the discharge capacity and initial efficiency of the battery can be improved.
  • the Li compound may include at least one selected from the group consisting of Li silicate, Li silicide, and Li oxide.
  • the Li silicate may include at least one of Li 2 SiO 3 , Li 4 SiO 4 and Li 2 Si 2 O 5 .
  • the Li silicide may include Li 7 Si 2 .
  • the Li oxide may include Li 2 O.
  • the Li compound may include a lithium silicate form.
  • the lithium silicate is expressed as Li a Si b O c (2 ⁇ a ⁇ 4, 0 ⁇ b ⁇ 2, 2 ⁇ c ⁇ 5), and can be divided into crystalline lithium silicate and amorphous lithium silicate.
  • the crystalline lithium silicate may exist in the silicon-based composite particle in the form of at least one type of lithium silicate selected from the group consisting of Li 2 SiO 3 , Li 4 SiO 4 , and Li 2 Si 2 O 5
  • the amorphous lithium silicate may be Li It may be in the form of a Si b O c (2 ⁇ a ⁇ 4, 0 ⁇ b ⁇ 2, 2 ⁇ c ⁇ 5), but is not limited to the above form.
  • the Li element may be included in an amount of 0.1% by weight to 20% by weight, or may be included in an amount of 0.1% by weight to 10% by weight based on a total of 100% by weight of the silicon-based active material. Specifically, the Li element may be included in an amount of 0.5% by weight to 8% by weight, and more specifically, it may be included in an amount of 0.5% by weight to 4% by weight.
  • the Li compound can be included in an appropriate amount in the silicon-based active material, so the change in volume of the negative electrode active material during charging and discharging of the battery can be easily suppressed, and the discharge capacity and initial efficiency of the battery can be improved.
  • the content of the Mg element or Li element can be confirmed through ICP analysis.
  • ICP analysis a certain amount (about 0.01 g) of the negative electrode active material is accurately separated, transferred to a platinum crucible, and completely decomposed on a hot plate by adding nitric acid, hydrofluoric acid, and sulfuric acid. Then, using an induced plasma luminescence spectrometer (ICPAES, Perkin-Elmer 7300), the intensity of the standard solution (5 mg/kg) prepared using the standard solution (5 mg/kg) is measured at the unique wavelength of the Mg element or Li element, and a standard calibration curve is prepared. .
  • ICPAES induced plasma luminescence spectrometer
  • the pretreated sample solution and blank sample are introduced into the device, the intensity of each is measured to calculate the actual intensity, the concentration of each component is calculated compared to the calibration curve prepared above, and then converted so that the sum of all becomes the theoretical value.
  • the Mg element or Li element content of the manufactured silicon-based active material can be analyzed.
  • a carbon layer may be provided on the surface and/or inside the pores of the silicon-based composite particle.
  • the carbon layer conductivity is imparted to the silicon-based composite particles, and the initial efficiency, lifespan characteristics, and battery capacity characteristics of a secondary battery containing a negative electrode active material containing the silicon-based composite particles can be improved.
  • the total weight of the carbon layer may be 5% to 40% by weight based on a total of 100% by weight of the silicon-based composite particles.
  • the carbon layer may include at least one of amorphous carbon and crystalline carbon.
  • the average particle diameter (D 50 ) of the silicon-based composite particles may be 2 ⁇ m to 15 ⁇ m, specifically 3 ⁇ m to 12 ⁇ m, and more specifically 4 ⁇ m to 10 ⁇ m. When the above range is satisfied, side reactions between the silicon-based composite particles and the electrolyte solution are controlled, and the discharge capacity and initial efficiency of the battery can be effectively implemented.
  • the average particle size (D 50 ) can be defined as the particle size corresponding to 50% of the volume accumulation in the particle size distribution curve.
  • the average particle diameter (D 50 ) can be measured using, for example, a laser diffraction method.
  • the laser diffraction method is generally capable of measuring particle diameters ranging from the submicron region to several millimeters, and can obtain results with high reproducibility and high resolution.
  • the silicon-based active material containing Si/C is a composite of Si and C, and is distinguished from silicon carbide, denoted as SiC.
  • the silicon carbon composite may be a composite of silicon, graphite, etc., and may form a structure surrounded by graphene or amorphous carbon around a core composite of silicon, graphite, etc.
  • the silicon dispersed in the silicon carbon composite may be nano silicon.
  • the average particle diameter (D 50 ) of the active material containing Si/C may be 2 ⁇ m to 15 ⁇ m, specifically 3 ⁇ m to 12 ⁇ m, and more specifically 4 ⁇ m to 10 ⁇ m.
  • a carbon layer may be provided on the surface of the active material containing Si/C.
  • the carbon-based active material may be graphite, and the graphite may be natural graphite, graphite graphite, or a mixture thereof.
  • the first negative electrode active material layer contains 80 parts by weight to 99.8 parts by weight, for example, 90 parts by weight to 99 parts by weight, and 93 parts by weight of the carbon-based negative electrode active material. It may contain from 97 parts by weight.
  • the second negative electrode active material layer will contain 60 parts by weight or more and 99 parts by weight or less of the carbon-based negative electrode active material, for example, 75 to 98 parts by weight, 85 to 95 parts by weight. You can.
  • the amount of the negative electrode active material in 100 parts by weight of the negative electrode active material layer is 80 parts by weight or more and 99.8 parts by weight or less, preferably 90 parts by weight or more and 99.5 parts by weight or less, more preferably 95 parts by weight or more. It may be included in less than one part by weight.
  • one or both of the first and second negative electrode active material layers include lithium-substituted carboxymethyl cellulose.
  • the lithium-substituted carboxymethyl cellulose may have a degree of substitution of the hydroxy (-OH) group by the lithium carboxymethyl group (-CH COOLi) of 0.1 or more, for example, 0.5 or more, specifically 0.7 to 1.3, or 0.8 to 1.2. , more specifically, may be 0.8 to 1.0.
  • the lithium-substituted carboxymethyl cellulose may have a molecular weight (Mn) of 300,000 to 1,000,000, for example, 350,000 to 900,000, and specifically 500,000 to 900,000.
  • the lithium-substituted carboxymethyl cellulose may be included in a negative electrode active material layer containing a silicon-based active material, or may be included in a negative electrode active material layer containing only a carbon-based active material and not a silicon-based active material.
  • the lithium-substituted carboxymethyl cellulose may be included in a second negative electrode active material layer including a silicon-based active material and a carbon-based active material.
  • the lithium-substituted carboxymethyl cellulose may be included only in the first negative electrode active material layer, only in the second negative electrode active material layer, or in both the first and second negative electrode active material layers.
  • the lithium-substituted carboxymethyl cellulose is 0.1 to 5 parts by weight, for example, 0.1 to 3 parts by weight, 0.2 to 3 parts by weight, 0.3 to 2 parts by weight, 0.5 parts by weight, based on 100 parts by weight of the total weight of the first and second negative electrode active material layers. It may be included in an amount of from 1 part by weight.
  • the lithium-substituted carboxymethyl cellulose is used in an amount of 0.1 to 5 parts by weight, for example, 0.1 to 3 parts by weight, 0.2 to 3 parts by weight, 0.3 to 2 parts by weight, based on 100 parts by weight of the first negative electrode active material layer or the second negative electrode active material layer containing it. It may be included in 0.5 to 1 part by weight.
  • the negative electrode active material layer may further include a negative electrode binder in addition to the silicon-based active material and the carbon-based active material.
  • the negative electrode binder may serve to improve adhesion between negative electrode active material particles and adhesion between the negative electrode active material particles and the negative electrode current collector.
  • the cathode binder those known in the art can be used, and non-limiting examples include polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride, poly Acrylonitrile, polymethylmethacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, Polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluororubber, polyacrylic acid, and their hydrogen is replaced by Li, Na or Ca, etc. It may include at least one selected from the
  • the negative electrode binder may be included in an amount of 0.1 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the negative electrode active material layer, for example, preferably 0.3 parts by weight or more and 20 parts by weight or less, more preferably 0.5 parts by weight or more and 10 parts by weight or less. can be included.
  • the negative electrode active material layer may not contain a conductive material, but may further include a conductive material if necessary.
  • the conductive material included in the negative electrode active material layer is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • graphite such as natural graphite or artificial graphite
  • Carbon black such as acetylene black, Ketjen black, channel black, Paneth black, lamp black, and thermal black
  • Conductive fibers such as carbon fiber and metal fiber
  • Conductive tubes such as carbon nanotubes
  • Metal powders such as fluorocarbon, aluminum, and nickel powder
  • Conductive whiskers such as zinc oxide and potassium titanate
  • Conductive metal oxides such as titanium oxide
  • Conductive materials such as polyphenylene derivatives may be used.
  • the content of the conductive material in the negative electrode active material layer may be 0.01 to 20 parts by weight, preferably 0.03 to 18 parts by weight, based on 100 parts by weight of the negative electrode active material layer.
  • the carbon-based active material is graphite such as natural graphite or artificial graphite
  • the weight portion of the graphite used as the carbon-based active material is not considered when defining the total weight portion of the conductive material.
  • the conductive material selected according to the negative electrode is graphite
  • the weight portion of the conductive material described is not included when defining the total weight portion of the carbon-based negative electrode active material. Therefore, when graphite is selected as both the carbon-based negative electrode active material and the negative electrode conductive material, the total weight of graphite corresponds to the sum of the weight parts of graphite used as the carbon-based negative electrode active material and the weight of graphite used as the negative electrode conductive material.
  • the conductive material included in the negative electrode active material layer is carbon black such as acetylene black, Ketjen black, channel black, Paneth black, lamp black, and thermal black; Conductive fibers such as carbon fiber and metal fiber; Conductive tubes such as carbon nanotubes may be used.
  • the thickness of the first and second negative electrode active material layers may be respectively 30 ⁇ m or more and 100 ⁇ m or less, for example, 45 ⁇ m or more and 75 ⁇ m or less.
  • the sum of the thicknesses of the first and second negative electrode active material layers may be 90 ⁇ m or more and 150 ⁇ m or less.
  • the negative electrode current collector may be any conductive material without causing chemical changes in the battery, and is not particularly limited.
  • the current collector may be copper, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel surface treated with carbon, nickel, titanium, silver, etc.
  • a transition metal that easily adsorbs carbon such as copper or nickel, can be used as a current collector.
  • the thickness of the current collector may be 1 ⁇ m to 500 ⁇ m, but the thickness of the current collector is not limited thereto.
  • Additional embodiments of the present specification provide a secondary battery including a negative electrode, a positive electrode, and a separator according to the above-described embodiments.
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector and including the positive electrode active material.
  • the thickness of the positive electrode active material layer may be 20 ⁇ m or more and 500 ⁇ m or less.
  • the positive electrode current collector is not particularly limited as long as it is conductive without causing chemical changes in the battery, for example, stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon, nickel, titanium on the surface of aluminum or stainless steel. , surface treated with silver, etc. may be used.
  • the positive electrode current collector may typically have a thickness of 1 to 500 ⁇ m, and fine irregularities may be formed on the surface of the current collector to increase the adhesion of the positive electrode active material.
  • it can be used in various forms such as films, sheets, foils, nets, porous materials, foams, and non-woven materials.
  • the positive electrode may include a lithium complex transition metal compound containing nickel (Ni) and cobalt (Co) as an active material.
  • the lithium composite transition metal compound may further include at least one of manganese and aluminum.
  • the lithium complex transition metal compound may contain 80 mol% or more of nickel among metals other than lithium, for example, 80 mol% or more and less than 100 mol%.
  • the amount of the positive electrode active material in 100 parts by weight of the positive electrode active material layer is 80 parts by weight or more and 99.9 parts by weight or less, preferably 90 parts by weight or more and 99.9 parts by weight or less, more preferably 95 parts by weight or more and 99.8 parts by weight or less. can be included.
  • the positive electrode active material layer according to the above-described embodiment may further include a positive electrode binder and a conductive material.
  • the positive electrode binder may serve to improve adhesion between positive electrode active material particles and adhesion between the positive electrode active material particles and the positive electrode current collector.
  • the anode binder may be those known in the art, and non-limiting examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), and polyvinylidene fluoride (PVDF).
  • Alcohol polyacrylonitrile, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene.
  • EPDM -Propylene-diene polymer
  • SBR styrene butadiene rubber
  • fluororubber or various copolymers thereof, etc., of which one type alone or a mixture of two or more types may be used.
  • the positive electrode binder may be included in an amount of 0.1 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the positive electrode active material layer, for example, preferably 0.3 parts by weight or more and 18 parts by weight or less, more preferably 0.5 parts by weight or more and 15 parts by weight or less. can be included.
  • the conductive material included in the positive electrode active material layer is used to provide conductivity to the electrode, and can be used without particular restrictions as long as it does not cause chemical changes within the battery and has electronic conductivity.
  • Specific examples include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, summer black, carbon fiber, and carbon nanotube; Metal powders or metal fibers such as copper, nickel, aluminum, and silver; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Or conductive polymers such as polyphenylene derivatives, etc., of which one type alone or a mixture of two or more types may be used.
  • the conductive material is a single-walled carbon nanotube (SWCNT); and multi-walled carbon nanotubes (MWCNTs).
  • the conductive material may be included in an amount of 0.1 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the composition for the positive electrode active material layer, for example, preferably 0.2 parts by weight or more and 7 parts by weight or less, more preferably 0.3 parts by weight or more and 5 parts by weight or less. can be included.
  • the sum of the weight of the first and second negative electrode active material layers of the negative electrode may be 170 to 280 mg/25 cm 2 .
  • the weight is based on the weight (solid content) after drying, excluding solvent. This range is advantageous for high energy density and fast charging characteristics.
  • the positive electrode and the negative electrode can be manufactured according to a conventional positive electrode and negative electrode manufacturing method except for using the positive and negative electrode active materials described above. Specifically, it can be manufactured by applying a composition for forming an active material layer containing the above-described active material and, optionally, a binder and a conductive material onto a current collector, followed by drying and rolling. At this time, the types and contents of the positive and negative electrode active materials, binders, and conductive materials are as described above.
  • the solvent may be a solvent commonly used in the art, such as dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, or Water, etc.
  • the positive electrode and the negative electrode may be manufactured by casting the composition for forming the active material layer on a separate support and then peeling off the support and laminating the film obtained on the current collector.
  • the separator separates the cathode from the anode and provides a passage for lithium ions. It can be used without particular restrictions as long as it is normally used as a separator in secondary batteries. In particular, it has low resistance to ion movement in the electrolyte and has an electrolyte moisturizing ability. Excellent is desirable.
  • porous polymer films for example, porous polymer films made of polyolefin polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, or these. A laminated structure of two or more layers may be used.
  • porous non-woven fabrics for example, non-woven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers, etc.
  • a coated separator containing ceramic components or polymer materials may be used to ensure heat resistance or mechanical strength, and may optionally be used in a single-layer or multi-layer structure.
  • the electrolytes include, but are not limited to, organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel-type polymer electrolytes, solid inorganic electrolytes, and molten inorganic electrolytes that can be used in the manufacture of lithium secondary batteries.
  • the electrolyte may include a non-aqueous organic solvent and a metal salt.
  • non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butylo lactone, and 1,2-dimethyl.
  • Triesters trimethoxy methane, dioxoran derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl pyropionate, propionic acid.
  • Aprotic organic solvents such as ethyl may be used.
  • ethylene carbonate and propylene carbonate which are cyclic carbonates
  • cyclic carbonates are high-viscosity organic solvents and have a high dielectric constant, so they can be preferably used because they easily dissociate lithium salts.
  • These cyclic carbonates include dimethyl carbonate and diethyl carbonate. If linear carbonates of the same low viscosity and low dielectric constant are mixed and used in an appropriate ratio, an electrolyte with high electrical conductivity can be made and can be used more preferably.
  • the metal salt may be a lithium salt, and the lithium salt is a material that is easily soluble in the non-aqueous electrolyte solution.
  • anions of the lithium salt include F-, Cl-, I-, NO 3 -, N(CN) ) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3 ) 2 PF 4 -, (CF 3 ) 3 PF 3 -, (CF 3 ) 4 PF 2 -, (CF 3 ) 5 PF- , (CF 3 ) 6 P-, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2 ) 2 N-, (FSO 2 ) 2 N-, CF 3 CF 2 (CF 3 ) 2 CO-, (CF 3 SO 2 ) 2 CH-, (SF 5 ) 3 C-, (CF 3 SO 2 ) 3 C-, CF 3 (CF 2 ) 7 SO 3 -, CF 3 CO 2 -, CH 3
  • the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and trifluoroethylene for the purpose of improving battery life characteristics, suppressing battery capacity reduction, and improving battery discharge capacity.
  • One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol, or aluminum trichloride may be further included.
  • the secondary battery according to an exemplary embodiment of the present invention includes an assembly including a positive electrode, a negative electrode, a separator, and an electrolyte, and may be a lithium secondary battery.
  • a further embodiment of the present invention provides a battery module including the above-described secondary battery as a unit cell and a battery pack including the same. Since the battery module and battery pack include the secondary battery with high capacity, high rate characteristics, and cycle characteristics, they are medium-to-large devices selected from the group consisting of electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, and power storage systems. It can be used as a power source.
  • secondary batteries according to embodiments of the present invention stably exhibit excellent discharge capacity, output characteristics, and cycle performance, they are used not only in portable devices such as mobile phones, laptop computers, and digital cameras, but also in electric vehicles, hybrid electric vehicles, and plug-in devices. It can be used as a power source for medium-to-large devices selected from the group consisting of hybrid electric vehicles and power storage systems.
  • the battery module or battery pack may include a power tool; Electric vehicles, including electric vehicles (EV), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEV); Alternatively, it can be used as a power source for any one or more mid- to large-sized devices among power storage systems.
  • PVDF methylpyrrolidone
  • NMP methylpyrrolidone
  • the positive electrode slurry prepared above was applied on an Al current collector, dried, and rolled at room temperature to produce a positive electrode.
  • the first negative electrode active material layer consists of carbon-based active material (including artificial graphite and natural graphite in a weight ratio of 8:2), conductive material (carbon black), binder (SBR), and thickener (Li-CMC) at a ratio of 96:1:2:1.
  • a negative electrode slurry was prepared by adding it to a distilled water solvent at a weight ratio of (the solid content of the negative electrode slurry is included in 50 parts by weight of the total negative electrode slurry).
  • the second negative electrode active material layer includes a Mg-doped SiO active material and a carbon-based active material (including artificial graphite and natural graphite in a weight ratio of 8:2) (5 weight of the Mg-doped SiO active material based on 100 parts by weight of the total negative electrode active material). (10 parts by weight based on 100 parts by weight of the negative electrode active material in the second negative electrode active material layer), conductive material (carbon black), binder (SBR), and thickener (Li-CMC) in distilled water at a weight ratio of 96:1:2:1.
  • a negative electrode slurry was prepared by adding it to a solvent (the solid content of the negative electrode slurry is included in 50 parts by weight of the total negative electrode slurry).
  • the second negative electrode active material layer slurry was sequentially applied on the first negative electrode active material layer, and the first and second negative electrode active material layers were dried simultaneously and then rolled at room temperature. Thus, a cathode was produced.
  • a cell was manufactured by assembling a separator between the anode and cathode prepared above, injecting an electrolyte solution, and then activating it.
  • Electrolyte composition 1M LiPF 6 , ethylene carbonate (EC)/ethylmethyl carbonate (EMC) (volume ratio 3/7), vinylene carbonate (VC)/propane sultone (PS, propane sultone) (3 parts by weight each in electrolyte, (included in 1.5 parts by weight)
  • the electrode and cell were manufactured in the same manner as in Example 1, except that the slurry thickener of the first negative electrode active material layer was manufactured with Na-CMC instead of Li-CMC.
  • the electrode and cell were manufactured in the same manner as in Example 1, except that the slurry thickener of the second negative electrode active material layer was manufactured with Na-CMC instead of Li-CMC.
  • the electrode and cell were manufactured in the same manner as in Example 1, except that the slurry thickener for the first and second negative electrode active material layers was manufactured with Na-CMC instead of Li-CMC.
  • the electrode and cell were manufactured in the same manner as in Comparative Example 1, except that the anode was manufactured using only a carbon-based active material as the anode active material in both the first and second anode active material layer slurries.
  • the first negative electrode active material layer slurry of Example 5 was applied in a single layer to the Cu current collector (the thickness of the single layer was the same as the thickness of the first and second negative electrode active material layers of Example 5), and the second negative electrode active material layer was not formed. Electrodes and cells were manufactured in the same manner as in Example 5 except that they were not used.
  • the electrode was prepared in the same manner as in Example 5, except that the thickener of the first negative electrode active material layer slurry of Example 5 included Na-CMC instead of Li-CMC, was applied in a single layer on the Cu current collector, and the second negative electrode active material layer was not formed. and cells were produced.
  • the slurry of the second negative electrode active material layer of Example 1 was first applied to the Cu current collector using the slurry of the first negative electrode active material layer, and the slurry of the first negative electrode active material layer of Example 1 was used as the slurry of the second negative electrode active material layer.
  • An electrode and a cell were manufactured in the same manner as in Example 1, except that the electrode was sequentially applied on the first negative electrode active material layer.
  • a negative electrode active material containing Mg-doped SiO active material and a carbon-based active material (including artificial graphite and natural graphite in a weight ratio of 8:2) is used, and the first negative electrode active material layer and The electrode and cell were manufactured in the same manner as in Example 1, except that the Mg-doped SiO active material contained in both second negative electrode active material layers was included in an amount of 5 parts by weight based on 100 parts by weight of all negative electrode active materials.
  • the manufactured cell was subjected to constant current/constant voltage (CC/CV) charging (0.05C-cut) and 0.33C constant current (CC) discharging (2.5V-cut) three times up to 4.2V at 0.33C, and the third discharge capacity was measured. . Afterwards, after charging as above, the SOC was set to 50% with 0.33C discharge, and the resistance was measured (initial resistance) by pulse discharging at 2.5C for 10 seconds. The results are shown in Table 2 below.
  • the manufactured cells are charged by constant current/constant voltage (CC/CV) up to 4.2V (0.05C-cut) and discharged by 0.33C constant current (CC) (2.5V-cut) by C-rate (0.1C / 2.0C). Charging capacity was measured according to C-rate. Based on the measured charging capacity, the cell charging C-rate performance (2.0C charging capacity/0.1C charging capacity x 100) was calculated and shown in Table 2.
  • the cycle was performed with constant current/constant voltage (CC/CV) charging (0.05C-cut) and 0.33C constant current (CC) discharging (2.5V-cut) up to 4.2V at 0.33C at high temperature (45°C).
  • CC/CV constant current/constant voltage
  • CC constant current
  • CC constant current
  • First negative electrode active material layer Second negative electrode active material layer graphite content (compared to total weight of active material) Silicone-based active material content (compared to total weight of active material) C.M.C. graphite content (compared to total weight of active material) Silicone-based active material content (compared to total weight of active material) C.M.C.
  • Example 1 100% - Li-CMC 90% SiO 10% Li-CMC Example 2 100% - Na-CMC 90% SiO 10% Li-CMC Example 3 100% - Li-CMC 90% SiO 10% Na-CMC Comparative Example 1 100% - Na-CMC 90% SiO 10% Na-CMC Comparative Example 2 100% - Na-CMC 100% - Na-CMC Comparative Example 3 95% SiO 5% Li-CMC - - - Comparative Example 4 95% SiO 5% Na-CMC - - - Comparative Example 5 90% SiO 10% Li-CMC 100% - Li-CMC Comparative Example 6 95% SiO 5% Li-CMC 95% SiO 5% Li-CMC
  • Example 1 1.766 97.8
  • Example 2 1.783 97.4
  • Example 3 1.821 97.1 Comparative Example 1 1.898 95.9 Comparative Example 2 2.003 91.3
  • Comparative Example 3 1.838 96.7 Comparative Example 4 1.921 95.5
  • Comparative Example 5 1.845 96.1 Comparative Example 6 1.837 96.8
  • Example showed superior effects compared to the cell resistance performance and cell charging C-rate performance of the Comparative Example. Additionally, the cells manufactured in the examples also maintained excellent lifetime performance.

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Abstract

La présente invention concerne une anode pour une batterie secondaire, et une batterie secondaire la comprenant, l'anode comprenant : un collecteur de courant ; une première couche de matériau actif d'anode disposée sur le collecteur de courant ; et une seconde couche de matériau actif d'anode disposée sur la première couche de matériau actif d'anode, la première couche de matériau actif d'anode et/ou la seconde couche de matériau actif d'anode comprenant de la carboxyméthylcellulose lithiée, la première couche de matériau actif d'anode comprenant un matériau actif à base de carbone, et seule la seconde couche de matériau actif d'anode comprenant un matériau actif à base de silicium.
PCT/KR2023/014944 2022-09-30 2023-09-27 Anode et batterie secondaire WO2024072059A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009081067A (ja) * 2007-09-26 2009-04-16 Sanyo Electric Co Ltd 非水電解質二次電池
JP2014022039A (ja) * 2012-07-12 2014-02-03 Dai Ichi Kogyo Seiyaku Co Ltd リチウム二次電池用負極バインダー
JP2016066529A (ja) * 2014-09-25 2016-04-28 信越化学工業株式会社 非水電解質二次電池用負極及び非水電解質二次電池
JP2018067480A (ja) * 2016-10-20 2018-04-26 トヨタ自動車株式会社 リチウムイオン二次電池用負極の製造方法
KR20190065172A (ko) * 2017-12-01 2019-06-11 주식회사 엘지화학 음극 및 이를 포함하는 이차전지
CN111933892A (zh) * 2020-07-27 2020-11-13 珠海冠宇电池股份有限公司 一种负极片及其制备方法和包括该负极片的锂离子二次电池
JP2022074704A (ja) * 2020-11-05 2022-05-18 プライムプラネットエナジー＆ソリューションズ株式会社 非水電解質二次電池用負極板の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009081067A (ja) * 2007-09-26 2009-04-16 Sanyo Electric Co Ltd 非水電解質二次電池
JP2014022039A (ja) * 2012-07-12 2014-02-03 Dai Ichi Kogyo Seiyaku Co Ltd リチウム二次電池用負極バインダー
JP2016066529A (ja) * 2014-09-25 2016-04-28 信越化学工業株式会社 非水電解質二次電池用負極及び非水電解質二次電池
JP2018067480A (ja) * 2016-10-20 2018-04-26 トヨタ自動車株式会社 リチウムイオン二次電池用負極の製造方法
KR20190065172A (ko) * 2017-12-01 2019-06-11 주식회사 엘지화학 음극 및 이를 포함하는 이차전지
CN111933892A (zh) * 2020-07-27 2020-11-13 珠海冠宇电池股份有限公司 一种负极片及其制备方法和包括该负极片的锂离子二次电池
JP2022074704A (ja) * 2020-11-05 2022-05-18 プライムプラネットエナジー＆ソリューションズ株式会社 非水電解質二次電池用負極板の製造方法

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