WO2024011512A1 - Plaque d'électrode négative, procédé de préparation de plaque d'électrode négative, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique - Google Patents

Plaque d'électrode négative, procédé de préparation de plaque d'électrode négative, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique Download PDF

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WO2024011512A1
WO2024011512A1 PCT/CN2022/105761 CN2022105761W WO2024011512A1 WO 2024011512 A1 WO2024011512 A1 WO 2024011512A1 CN 2022105761 W CN2022105761 W CN 2022105761W WO 2024011512 A1 WO2024011512 A1 WO 2024011512A1
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negative electrode
ceramic material
carbon
lithium
optionally
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PCT/CN2022/105761
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English (en)
Chinese (zh)
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白文龙
吴益扬
游兴艳
武宝珍
王育文
郑蔚
叶永煌
吴凯
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宁德时代新能源科技股份有限公司
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Priority to PCT/CN2022/105761 priority Critical patent/WO2024011512A1/fr
Priority to CN202280005930.9A priority patent/CN116848658A/zh
Publication of WO2024011512A1 publication Critical patent/WO2024011512A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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 application relates to the technical field of secondary batteries, and in particular to a negative electrode plate, a method for preparing a negative electrode plate, a secondary battery, a battery module, a battery pack and an electrical device.
  • This application was made in view of the above problems, and its purpose is to provide a negative electrode sheet, a method for preparing a negative electrode sheet, a secondary battery, a battery module, a battery pack, and an electrical device.
  • the negative electrode sheet of this application can increase the desolvation rate of lithium ions, reduce the degree of lithium precipitation at the interface between the negative electrode sheet and the electrolyte, and reduce the consumption of active lithium ions, thereby improving the cycle life of the secondary battery.
  • the surface of the negative electrode sheet of this application can The formation of a SEI film with a smaller thickness shortens the migration path of lithium ions, increases the charging rate of secondary batteries, and reduces electrolyte consumption.
  • the first aspect of the present application provides a negative electrode sheet, which includes a ceramic material, a carbon-based negative active material and a binder; wherein, the relative dielectric constant ⁇ of the ceramic material and the unit cell parameters a and c are The value of the relational expression ⁇ /(c/a) is 78.8-197.9, and the weight ratio of ceramic materials to carbon-based negative active materials is 0.0052-0.115, optionally 0.0052-0.057.
  • this application improves the desolvation rate of lithium ions and the diffusion of lithium ions in the SEI film by combining ceramic materials with a specific relationship between relative dielectric constant and unit cell parameters and carbon-based negative active materials in a certain proportion. rate, reducing the risk of generating lithium dendrites, reducing the degree of lithium precipitation, forming a SEI film with a smaller thickness, reducing the consumption of active lithium ions and electrolyte, thereby improving the cycle performance and charging rate of secondary batteries. .
  • the ceramic material has a relative dielectric constant ⁇ of 80-200. Therefore, the relative dielectric constant of ceramic materials within the above range can further increase the lithium ion desolvation rate and the lithium ion diffusion rate in the SEI film to further reduce the risk of lithium precipitation and reduce the thickness of the SEI film, thereby further Improve the cycle performance and charging rate of secondary batteries.
  • the weight percentage of the ceramic material in the negative electrode sheet is 0.5%-10%, optionally 0.5%-5%.
  • the weight content of ceramic materials in the negative electrode sheet is within the above range, which can further increase the lithium ion desolvation rate and the lithium ion diffusion rate in the SEI film, further reduce the degree of lithium evolution, and further reduce the thickness of the SEI film. , thereby further improving the cycle performance and charging rate of secondary batteries.
  • the ceramic material is one or more selected from the group consisting of barium titanate, lead titanate, lithium niobate, lead zirconate titanate, lead metaniobate, and lead barium lithium niobate.
  • the relative dielectric constant of the above-mentioned types of ceramic materials is more consistent with that of the electrolyte, which can further increase the lithium ion desolvation rate and the lithium ion diffusion rate in the SEI film to reduce the risk of lithium dendrites.
  • the use of the above types of ceramic materials can further reduce the thickness of the SEI film, thereby further improving the cycle performance and charging rate of the secondary battery.
  • the particle size D v 50 of the ceramic material is 10-300 nm, optionally 50-200 nm.
  • ceramic materials in the above particle size range are more closely combined with carbon-based negative active materials to further improve the lithium ion desolvation effect and further reduce the thickness of the SEI film, thereby further improving the cycle performance and performance of secondary batteries. Charging rate.
  • the particle size D v 50 of the carbon-based negative active material is 1-15 ⁇ m, optionally 5-10 ⁇ m.
  • the bond between the carbon-based negative active material and the ceramic material in the above particle size range is closer, so as to further increase the desolvation rate of lithium ions and further reduce the thickness of the formed SEI film, thereby further improving the secondary battery cycle performance and charging rate.
  • the weight ratio of ceramic material to binder is 0.1-10, optionally 0.5-1.
  • the composite particles formed by the ceramic materials and binders in the above proportion range are more closely combined with the carbon-based negative active material to further increase the desolvation rate of lithium ions and further reduce the thickness of the SEI film formed, thereby further improving Cycling performance and charging rates of secondary batteries.
  • the binder is selected from the group consisting of polyacrylic acid, styrene-butadiene rubber, polyvinylidene fluoride, polyamideimide, polyvinyl alcohol, polyethyleneimine, polyimide, and poly(tert-butyl acrylate).
  • polyacrylic acid styrene-butadiene rubber
  • polyvinylidene fluoride polyamideimide
  • polyvinyl alcohol polyethyleneimine
  • polyimide poly(tert-butyl acrylate).
  • poly(tert-butyl acrylate) One or more of ester-triethoxyvinylsilane).
  • the weight average molecular weight of the binder is 500,000-4 million, optionally 1 million-2 million; optionally, the molecular weight distribution index of the binder is 2-10, more preferably 2-2 4.
  • the use of the above-mentioned binder can make the ceramic material and the carbon-based negative active material more tightly combined, further increase the desolvation rate of lithium ions, further reduce the thickness of the SEI film, further reduce the consumption of active lithium ions, thereby improving the secondary battery cycle performance and charging rate.
  • the ceramic material is barium titanate, and barium titanate includes two crystal forms: cubic crystal form and tetragonal crystal form; the tetragonal crystal form is preferred.
  • barium titanate has peaks at the following positions in an X-ray powder diffraction pattern expressed in 2 ⁇ angles using Cu-K ⁇ radiation: 22 ⁇ 1°, 31 ⁇ 1°, 38 ⁇ 1°, 45 ⁇ 1°, 56 ⁇ 1°.
  • barium titanate as a ceramic material can further increase the lithium ion desolvation rate and the lithium ion diffusion rate in the SEI film to further reduce the risk of lithium precipitation and reduce the thickness of the SEI film, thereby further improving the cycle of the secondary battery. performance and charging rates.
  • the carbon-based negative active material is selected from one or more of hard carbon, soft carbon, graphite, and Ketjen black.
  • the use of the above-mentioned carbon-based negative active materials can ensure that the battery core has a high energy density.
  • a second aspect of the application also provides a method for preparing a negative electrode sheet, including the following steps:
  • step (2) Use the negative electrode slurry including the ceramic material obtained in step (1), the carbon-based negative active material and the binder to prepare the negative electrode piece; wherein the weight ratio of the ceramic material to the carbon-based negative active material is 0.0052-0.115 , optional 0.0052-0.057.
  • this application improves the desolvation rate of lithium ions and the diffusion rate of lithium ions in the SEI film by combining ceramic materials with a specific relationship between dielectric constant and unit cell parameters and carbon-based negative active materials in a certain proportion. , reduces the risk of lithium dendrites, reduces the degree of lithium precipitation, forms a SEI film with a smaller thickness, reduces the consumption of active lithium ions and electrolyte, thereby reducing the interface film resistance of the negative electrode piece and improving Cycling performance and charging rates of secondary batteries.
  • step (1) the ceramic material is obtained by ball milling
  • the speed of the ball mill is 200-300r/min;
  • the ball milling time is 2-4h.
  • the above-mentioned ball milling process is used to obtain ceramic materials, whose relative dielectric constant has a specific relationship with the unit cell parameters.
  • Combining the ceramic materials with the carbon-based negative active material in a certain proportion can increase the lithium ion desolvation rate and the lithium ion in the SEI film.
  • the weight ratio of ceramic material to binder is 0.1-10, optionally 0.5-1.
  • a third aspect of the present application provides a secondary battery, including the negative electrode sheet of the first aspect of the present application or the negative electrode sheet prepared by the method of the second aspect of the present application, and an electrolyte.
  • the ratio of the relative dielectric constant of the electrolyte to the relative dielectric constant of the ceramic material in the negative electrode piece is 1:3-1:1, optionally 0.45:1-1:1.
  • the relative dielectric constants of the ceramic material and the electrolyte are matched to increase the lithium ion desolvation rate and the lithium ion diffusion rate in the SEI film, reduce the risk of lithium dendrites and the degree of lithium precipitation, and reduce the SEI film
  • the thickness reduces the consumption of active lithium ions and electrolyte, thereby reducing the interface resistance of the negative electrode piece and improving the cycle performance and charging rate of the secondary battery.
  • a fourth aspect of the present application provides a battery module including the secondary battery of the third aspect of the present application.
  • a fifth aspect of the present application provides a battery pack, including the battery module of the fourth aspect of the present application.
  • a sixth aspect of the present application provides an electrical device, including at least one selected from the group consisting of the secondary battery of the third aspect of the present application, the battery module of the fourth aspect of the present application, and the battery pack of the fifth aspect of the present application. kind.
  • FIG. 1 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 2 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 1 .
  • FIG. 3 is a schematic diagram of a battery module according to an embodiment of the present application.
  • Figure 4 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG. 4 .
  • FIG. 6 is a schematic diagram of a power consumption device using a secondary battery as a power source according to an embodiment of the present application.
  • Figure 7A is a photograph of the surface of the negative electrode piece in Example 1 of the present application.
  • Figure 7B is a photo of the surface of the negative electrode piece in Comparative Example 1 of the present application.
  • Figure 8 is an EDS energy spectrum diagram of the negative electrode plate in Example 1 of the present application.
  • Figure 9 is an XRD pattern of the ceramic material in Example 1 of the present application.
  • Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
  • a certain parameter is an integer ⁇ 2
  • a method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • step (c) means that step (c) can be added to the method in any order.
  • the method may include steps (a), (b) and (c), and may also include step (a). , (c) and (b), and may also include steps (c), (a) and (b), etc.
  • condition "A or B” is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; Or both A and B are true (or exist).
  • unit cell parameters means that the shape and size of the unit cell can be expressed by 6 parameters, namely lattice characteristic parameters, referred to as unit cell parameters. It is a set of parameters that determine the shape and size of the unit cell. It includes the three sets of edge lengths of the unit cell (i.e., the axial length of the crystal) a, b, and c and the angles between the three sets of edges (i.e., the axial angles of the crystal) ⁇ , ⁇ , and ⁇ .
  • Secondary batteries also known as rechargeable batteries or storage batteries, refer to batteries that can be recharged to activate active materials and continue to be used after the battery is discharged.
  • a secondary battery normally includes a positive electrode plate, a negative electrode plate, a separator and an electrolyte.
  • active ions such as lithium ions
  • the isolation film is placed between the positive electrode piece and the negative electrode piece. It mainly prevents the positive and negative electrodes from short-circuiting and allows active ions to pass through.
  • the electrolyte is between the positive electrode piece and the negative electrode piece and mainly plays the role of conducting active ions.
  • One embodiment of the present application provides a negative electrode sheet, including a ceramic material, a carbon-based negative active material, and a binder; wherein the relationship between the relative dielectric constant ⁇ of the ceramic material and the unit cell parameters a and c is ⁇ /( The value of c/a) is 78.8-197.9 (such as 89.1, 118.7), and the weight ratio of ceramic material to carbon-based negative active material is 0.0052-0.115, optionally 0.0052-0.057, more optionally 0.0104-0.054 or 0.01 -0.05, such as 0.0103, 0.0105, 0.0326.
  • the desolvation rate of lithium ions and the diffusion rate of lithium ions in the SEI film are the limiting steps, causing lithium ions to be easily enriched at the interface between the SEI film and the negative electrode sheet.
  • the lithium ions Lithium dendrites are generated when the enrichment amount breaks through the nucleation barrier; due to the excellent conductivity of lithium metal, lithium ions preferentially gather at the lithium dendrites and are reduced to metallic lithium, which intensifies the formation of lithium dendrites and intensifies the lithium precipitation.
  • the formation of lithium dendrites is accompanied by the rupture and continuous generation of the SEI film, further causing the consumption of active lithium ions and the consumption of electrolytes; the large consumption of active lithium and the problem of lithium precipitation cause secondary The cycle performance of the battery is reduced.
  • the SEI film formed on the surface of the current negative electrode piece is relatively thick, resulting in large electrolyte consumption, long migration path of lithium ions, large interface resistance of the negative electrode piece, and low charging rate of the secondary battery.
  • the carbon-based negative active material the desolvation barrier of lithium ions is reduced, the desolvation rate of lithium ions and the diffusion rate of lithium ions in the SEI film are increased, the risk of generating lithium dendrites is reduced, and the precipitation rate is also reduced.
  • the degree of lithium reduces the consumption of active lithium ions, thereby improving the cycle performance and charging rate of the secondary battery; moreover, the specific ceramic material of this application can generate a counter electric field during the charging process, and the electrolyte, ceramic material and carbon-based negative electrode The electron-poor state is formed at the three-phase interface of the active material, which can form a thinner SEI film, further reducing the consumption of active lithium ions and electrolyte, thereby further improving the cycle performance of the secondary battery.
  • the thickness of the SEI film is relatively Thinness shortens the migration path of lithium ions in the SEI film, also reduces the interface resistance of the negative electrode piece, and improves the charging rate of the secondary battery; at the same time, the ceramic material can generate a counter electric field to show negative charge, which helps to disperse and enrich it in the SEI
  • the lithium ions at the interface between the membrane and the negative electrode further reduce the risk of lithium dendrites.
  • the relative dielectric constant ⁇ of the ceramic material is 80-200, such as 90, 120. Therefore, the relative dielectric constant of ceramic materials within the above range can further increase the lithium ion desolvation rate and the lithium ion diffusion rate in the SEI film to further reduce the risk of lithium precipitation and reduce the thickness of the SEI film, thereby further Improve the cycle performance and charging rate of secondary batteries.
  • the weight percentage of the ceramic material in the negative electrode sheet is 0.5%-10%, optionally 0.5%-5%, such as 1% or 3%.
  • the weight content of ceramic materials in the negative electrode sheet is within the above range, which can further increase the lithium ion desolvation rate and the lithium ion diffusion rate in the SEI film, further reduce the degree of lithium evolution, and further reduce the thickness of the SEI film. , thereby further improving the cycle performance and charging rate of secondary batteries.
  • the ceramic material is one or more selected from the group consisting of barium titanate, lead titanate, lithium niobate, lead zirconate titanate, lead metaniobate, and lead barium lithium niobate, optionally Barium titanate and/or lead titanate.
  • the relative dielectric constant of the above-mentioned types of ceramic materials is more consistent with that of the electrolyte, which can further increase the lithium ion desolvation rate and the lithium ion diffusion rate in the SEI film to reduce the risk of lithium dendrites.
  • the use of the above types of ceramic materials can further reduce the thickness of the SEI film, thereby further improving the cycle performance and charging rate of the secondary battery.
  • the particle size D v 50 of the ceramic material is 10-300 nm, optionally 50-200 nm, such as 100 nm.
  • ceramic materials in the above particle size range are more closely combined with carbon-based negative active materials to further improve the lithium ion desolvation effect and further reduce the thickness of the SEI film, thereby further improving the cycle performance and performance of secondary batteries. Charging rate.
  • the particle size D v 50 of the carbon-based negative active material is 1-15 ⁇ m, optionally 5-10 ⁇ m.
  • the bond between the carbon-based negative active material and the ceramic material in the above particle size range is closer, so as to further increase the desolvation rate of lithium ions and further reduce the thickness of the formed SEI film, thereby further improving the secondary battery cycle performance and charging rate.
  • the weight ratio of ceramic material to binder is 0.1-10, optionally 0.5-1, such as 5.
  • the composite particles formed by the ceramic materials and binders in the above proportion range are more closely combined with the carbon-based negative active material to further increase the desolvation rate of lithium ions and further reduce the thickness of the SEI film formed, thereby further improving Cycling performance and charging rates of secondary batteries.
  • the binder is selected from the group consisting of polyacrylic acid, styrene-butadiene rubber, polyvinylidene fluoride, polyamideimide, polyvinyl alcohol, polyethyleneimine, polyimide, and poly(tert-butyl acrylate). ester-triethoxyvinylsilane), optionally styrene-butadiene rubber and/or polyvinylidene fluoride.
  • the weight average molecular weight of the binder is 500,000-4 million, optionally 1 million-2 million, such as 1.5 million; optionally, the molecular weight distribution index of the binder is 2-10, more preferably Choose 2-4.
  • the use of the above-mentioned binder can make the ceramic material and the carbon-based negative active material more tightly combined, further increase the desolvation rate of lithium ions, further reduce the thickness of the SEI film, further reduce the consumption of active lithium ions, thereby improving the secondary battery cycle performance and charging rate.
  • the ceramic material is barium titanate, and barium titanate includes two crystal forms: cubic crystal form and tetragonal crystal form; the tetragonal crystal form is preferred.
  • barium titanate has peaks at the following positions in an X-ray powder diffraction pattern expressed in 2 ⁇ angles using Cu-K ⁇ radiation: 22 ⁇ 1°, 31 ⁇ 1°, 38 ⁇ 1°, 45 ⁇ 1°, 56 ⁇ 1°.
  • barium titanate as a ceramic material can further increase the lithium ion desolvation rate and the lithium ion diffusion rate in the SEI film to further reduce the risk of lithium precipitation and reduce the thickness of the SEI film, thereby further improving the cycle of the secondary battery. performance and charging rate.
  • the carbon-based negative active material is one or more selected from the group consisting of hard carbon, soft carbon, graphite and Ketjen black, optionally hard carbon and/or graphite (such as artificial graphite).
  • hard carbon soft carbon
  • graphite such as artificial graphite
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector; ceramic material, carbon-based negative electrode active material and binder are included in the negative electrode film layer.
  • the negative electrode current collector has two opposite surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base material.
  • the composite current collector can be formed by forming metal materials (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode film layer optionally further includes a conductive agent.
  • the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode film layer optionally includes other auxiliaries, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
  • thickeners such as sodium carboxymethylcellulose (CMC-Na)
  • the relative dielectric constant of ceramic materials refers to the relative dielectric constant at room temperature (25 ⁇ 5°C), which has a well-known meaning in the art and can be tested using instruments and methods known in the art.
  • the particle size D v 50 is determined by a particle size tester.
  • the ratio c/a of the unit cell parameters c-axis and a-axis can be calculated based on the XRD pattern analysis of the material using the software that comes with the X-ray diffractometer.
  • the method of preparing the negative electrode sheet of the present application includes the following steps:
  • step (2) Use the negative electrode slurry including the ceramic material obtained in step (1), the carbon-based negative active material and the binder to prepare the negative electrode piece; wherein the weight ratio of the ceramic material to the carbon-based negative active material is 0.0052-0.115 , optionally 0.0052-0.057, more optionally 0.0104-0.054 or 0.01-0.05, such as 0.0103, 0.0105, 0.0326.
  • this application improves the desolvation rate of lithium ions and the diffusion rate of lithium ions in the SEI film by combining ceramic materials with a specific relationship between dielectric constant and unit cell parameters and carbon-based negative active materials in a certain proportion. , reduces the risk of lithium dendrites, reduces the degree of lithium precipitation, forms a SEI film with a smaller thickness, reduces the consumption of active lithium ions and electrolyte, thereby reducing the interface film resistance of the negative electrode piece and improving Cycling performance and charging rates of secondary batteries.
  • the ceramic material is obtained by ball milling
  • the speed of the ball mill is 200-300r/min;
  • the ball milling time is 2-4h, such as 3h.
  • the above-mentioned ball milling process is used to obtain ceramic materials, whose relative dielectric constant has a specific relationship with the unit cell parameters.
  • Combining the ceramic materials with the carbon-based negative active material in a certain proportion can increase the lithium ion desolvation rate and the lithium ion in the SEI film.
  • the weight ratio of ceramic material to binder is 0.1-10, optionally 0.5-1, such as 5.
  • the negative electrode slurry including the ceramic material obtained in step (1), the carbon-based negative active material and the binder is obtained by the following steps:
  • the ceramic material, carbon-based negative active material, binder and any other components obtained in step (1) are dispersed in a solvent (such as deionized water) to form a negative electrode slurry.
  • a solvent such as deionized water
  • using the negative electrode slurry to prepare the negative electrode sheet is achieved in the following manner:
  • the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode piece can be obtained.
  • the ceramic material is as described in "[Negative Electrode Plate]”.
  • the carbon-based negative active material is as described in "[Negative Electrode Sheet]”.
  • the binder is as described in "[Negative Electrode Plate]”.
  • the positive electrode sheet usually includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector.
  • the positive electrode film layer includes a positive electrode active material.
  • the positive electrode current collector has two surfaces facing each other in its own thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • the metal foil aluminum foil can be used.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer.
  • the composite current collector can be formed by forming metal materials (aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the cathode active material may be a cathode active material known in the art for batteries.
  • the cathode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
  • the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials of batteries can also be used. Only one type of these positive electrode active materials may be used alone, or two or more types may be used in combination.
  • lithium transition metal oxides may include, but are not limited to, lithium cobalt oxides (such as LiCoO 2 ), lithium nickel oxides (such as LiNiO 2 ), lithium manganese oxides (such as LiMnO 2 , LiMn 2 O 4 ), lithium Nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (can also be abbreviated to NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (can also be abbreviated to NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (can also be abbreviated to NCM 622 ), LiNi At least one of 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 ), lithium nickel cobalt aluminum oxide (such as Li Li
  • the olivine structure contains Examples of lithium phosphates may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), composites of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), lithium manganese phosphate and carbon. At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also referred to as LFP)
  • composites of lithium iron phosphate and carbon such as LiMnPO 4
  • LiMnPO 4 lithium manganese phosphate and carbon.
  • At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
  • the positive electrode film layer optionally further includes a binder.
  • the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene tripolymer. At least one of a meta-copolymer, a tetrafluoroethylene-hexafluoropropylene copolymer and a fluorine-containing acrylate resin.
  • the positive electrode film layer optionally further includes a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode sheet can be prepared by dispersing the above-mentioned components for preparing the positive electrode sheet, such as positive active material, conductive agent, binder and any other components in a solvent (such as N -methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode piece can be obtained.
  • a solvent such as N -methylpyrrolidone
  • the secondary battery further includes a separator film.
  • a separator film There is no particular restriction on the type of isolation membrane in this application. Any well-known porous structure isolation membrane with good chemical stability and mechanical stability can be used.
  • the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation film can be a single-layer film or a multi-layer composite film, with no special restrictions. When the isolation film is a multi-layer composite film, the materials of each layer can be the same or different, and there is no particular limitation.
  • the electrolyte plays a role in conducting ions between the positive and negative electrodes.
  • the type of electrolyte in this application can be selected according to needs.
  • the electrolyte can be liquid, gel, or completely solid.
  • the electrolyte is liquid and includes an electrolyte salt and a solvent.
  • the electrolyte salt may be selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluoroborate, lithium dioxaloborate, lithium difluorodioxalate phosphate and lithium tetrafluoroxalate phosphate.
  • the solvent may be selected from the group consisting of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, Butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate At least one of ester, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte optionally also includes additives.
  • additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain properties of the battery, such as additives that improve battery overcharge performance, additives that improve battery high-temperature or low-temperature performance, etc.
  • the dielectric constant of electrolytes is usually in the range of 30-80.
  • the ratio of the relative dielectric constant of the electrolyte to the relative dielectric constant of the ceramic material in the negative electrode piece is 1:3-1:1, optionally 0.45:1-1:1.
  • the relative dielectric constants of the ceramic material and the electrolyte are matched to increase the lithium ion desolvation rate and the lithium ion diffusion rate in the SEI film, reduce the risk of lithium dendrites and the degree of lithium precipitation, and reduce the SEI film
  • the thickness reduces the consumption of active lithium ions and electrolyte, thereby reducing the interface resistance of the negative electrode piece and improving the cycle performance and charging rate of the secondary battery.
  • the relative dielectric constant of the electrolyte can be measured by a relative dielectric constant tester.
  • a relative dielectric constant tester For details, refer to GB/T5594.4-1985.
  • the positive electrode piece, the negative electrode piece and the separator film can be made into an electrode assembly through a winding process or a lamination process.
  • the secondary battery may include an outer packaging.
  • the outer packaging can be used to package the above-mentioned electrode assembly and electrolyte.
  • the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the secondary battery may also be a soft bag, such as a bag-type soft bag.
  • the material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
  • FIG. 1 shows a square-structured secondary battery 5 as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose a receiving cavity.
  • the housing 51 has an opening communicating with the accommodation cavity, and the cover plate 53 can cover the opening to close the accommodation cavity.
  • the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the containing cavity.
  • the electrolyte soaks into the electrode assembly 52 .
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • secondary batteries can be assembled into battery modules, and the number of secondary batteries contained in the battery module can be one or more. The specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG. 3 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
  • the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having a receiving space in which a plurality of secondary batteries 5 are received.
  • the above-mentioned battery modules can also be assembled into a battery pack.
  • the number of battery modules contained in the battery pack can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box 2 and a lower box 3 .
  • the upper box 2 can be covered with the lower box 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application.
  • the secondary battery, battery module, or battery pack can be used as a power source for the power-consuming device, or as an energy storage unit of the power-consuming device.
  • Electric devices may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric Trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
  • secondary batteries, battery modules or battery packs can be selected according to its usage requirements.
  • FIG. 6 is an electrical device as an example.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, etc.
  • a battery pack or battery module can be used.
  • barium titanate particles (relative dielectric constant ⁇ is 30, particle size D v 50 is 100nm) and add it to the ball mill tank, and ball mill at 300r/min for 2 hours.
  • the relative dielectric constant ⁇ of the obtained barium titanate particles is 90
  • the value of unit cell parameter c/a is 1.010621
  • the value of the relationship between relative dielectric constant and unit cell parameter ⁇ /(c/a) is 89.05415581
  • the particle size D v 50 is 50 nm.
  • the negative active material artificial graphite (particle size D v 50 is 10 ⁇ m), conductive agent acetylene black, binder styrene-butadiene rubber (SBR) (weight average molecular weight is 1.5 million, molecular weight distribution index is 2), dispersant carboxymethyl Sodium cellulose (CMC-Na) and the barium titanate particles prepared in step (1) were dissolved in deionized water at a mass ratio of 96:1:1:1:1, stirred thoroughly and mixed evenly to prepare a negative electrode slurry; The negative electrode slurry was evenly coated on the negative electrode current collector copper foil with a thickness of 7 ⁇ m with an area density of 9.6 mg/cm 2 (after drying), and then dried, cold pressed, and cut to obtain negative electrode sheets.
  • SBR binder styrene-butadiene rubber
  • CMC-Na dispersant carboxymethyl Sodium cellulose
  • the positive active material lithium nickel cobalt manganate (LiNi 0.5 Co 0.2 Mn 0.3 O 2 ), the binder polyvinylidene fluoride (PVDF), and the conductive agent acetylene black in the solvent N-format in a mass ratio of 98:1:1.
  • pyrrolidone (NMP) stir and mix thoroughly under vacuum to prepare a positive electrode slurry; the positive electrode slurry is evenly coated on the positive electrode current collector with a thickness of 13 ⁇ m with an area density of 13.7 mg/cm 2 (after drying) on aluminum foil, and then dried, cold pressed, and cut to obtain the positive electrode piece.
  • a commercially available PP-PE copolymer microporous film with a thickness of 20 ⁇ m and an average pore diameter of 80 nm (purchased from Zhuogao Electronic Technology Co., Ltd., model 20) was used.
  • Examples 2-28 and Comparative Examples 1-9 are similar to the secondary battery preparation methods of Example 1, but the parameters are adjusted. The different parameters are detailed in Table 1. The rest are the same as Example 1. Among them, w1 represents the weight percentage of the ceramic material in the negative electrode sheet, w2 represents the weight percentage of the carbon-based negative active material in the negative electrode sheet, m1 represents the weight of the ceramic material in the negative electrode sheet, and m2 represents the weight percentage of the negative electrode active material in the negative electrode sheet.
  • the weight of the carbon-based negative active material, m3, represents the weight of the binder in the negative electrode piece; the weight percentages of the conductive agent and dispersant in the negative electrode slurry are the same.
  • the test conditions are 1KHz, 1.0V, 25 ⁇ 5°C.
  • the test standard can be based on GB/T 11297.11-2015.
  • Test method for the relative dielectric constant ⁇ of the electrolyte refer to GB/T5594.4-1985, and use the ZJD-C relative dielectric constant tester of Beijing AVIC Times Instrument Equipment Co., Ltd. to measure it.
  • Figure 9 is the XRD spectrum of the ceramic material in Example 1, including peaks at the following positions: 22 ⁇ 1°, 31 ⁇ 1°, 38 ⁇ 1°, 45 ⁇ 1°, 56 ⁇ 1°; the XRD comes with the software Analysis shows that barium titanate contains two crystal forms: cubic crystal form and tetragonal crystal form.
  • the dynamic performance of secondary batteries is evaluated by measuring the 4C charging resistance.
  • current A0 rate ⁇ A0 rated capacity
  • A0 rated capacity is the capacity obtained by assembling the pole pieces into a full battery
  • the capacity retention performance of secondary batteries was evaluated by measuring the fast charge cycle life at 25°C.
  • the secondary batteries prepared in the Examples and Comparative Examples were charged at a 2C rate, discharged at a 1C rate, and subjected to continuous cycle testing in the 3%-97% SOC range until the capacity of the secondary battery was less than 80% of the initial capacity. %, record the number of cycles.
  • the secondary batteries made of the negative electrode plates of the present application have longer fast-charging cycle life, better cycle performance, and faster charging rates.
  • Example 1 Comparing Example 1 with Examples 19-20, it can be seen that the fast charge cycle life of the secondary battery made by using the negative electrode sheet with a weight ratio of ceramic material and binder of 0.5-1 is further extended, and the cycle performance is further improved. Improved, the charging rate is further increased.
  • Example 1 Comparing Example 1 with Examples 7 and 21, it can be seen that the fast charge cycle life of the secondary battery made by the negative electrode plate of the ceramic material with a particle size D v 50 of 50-200 nm is further extended and the cycle performance is further improved. .
  • Example 1 Comparing Example 1 with Examples 11 and 22, it can be seen that the fast charging cycle life of the secondary battery made by using the negative electrode sheet with a particle size D v 50 of the carbon-based negative active material of 5-10 ⁇ m is further extended, and the cycle life is further extended. Performance is further improved and charging rates are further increased.
  • Example 1 Comparing Example 1 with Examples 23-24, it can be seen that the fast charging cycle life of the secondary battery made by the negative electrode sheet of the binder with a weight average molecular weight of 1 million to 2 million is further extended, and the cycle performance is further improved. improve.
  • Example 1 Comparing Example 1 with Example 25, it can be seen that the fast charging cycle life of the secondary battery produced by the negative electrode sheet of the binder with a molecular weight distribution index of 2-4 is further extended, the cycle performance is further improved, and the charging rate is Further improve.
  • Example 1 Comparing Example 1 with Example 27, it can be seen that the fast charge cycle life of the secondary battery made by using the negative electrode plate with a weight percentage of ceramic material of 0.5%-5% is further extended and the cycle performance is further improved. The charging rate is further improved.
  • Example 1 Comparing Example 1 with Example 28, it can be seen that the fast charge cycle life of the secondary battery produced by the present application using the ratio of the relative dielectric constant of the electrolyte to the relative dielectric constant of the ceramic material is 0.45:1-1:1. Extended, the cycle performance is further improved and the charging rate is further increased.

Abstract

La présente demande concerne une plaque d'électrode négative, un procédé de préparation de plaque d'électrode négative, une batterie secondaire, un module de batterie, un bloc-batterie et un dispositif électrique. La plaque d'électrode négative comprend un matériau céramique, un matériau actif d'électrode négative à base de carbone, et un liant, la valeur de la relation ε/(c/a) entre une constante diélectrique relative ε et des paramètres de réseau a et c du matériau céramique étant de 78,8 à 197,9, et le rapport pondéral du matériau céramique sur le matériau actif d'électrode négative à base de carbone étant de 0,0052 à 0,115. La plaque d'électrode négative de la présente demande peut augmenter le taux de désolvatation d'ions lithium, réduire le degré de placage de lithium sur une plaque d'électrode négative, réduire l'épaisseur d'un film SEI formé, et réduire la consommation d'ions lithium actifs, ce qui permet de réduire l'impédance d'interface de la plaque d'électrode négative, et d'améliorer la durée de vie et le taux de charge de batteries secondaires.
PCT/CN2022/105761 2022-07-14 2022-07-14 Plaque d'électrode négative, procédé de préparation de plaque d'électrode négative, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique WO2024011512A1 (fr)

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CN202280005930.9A CN116848658A (zh) 2022-07-14 2022-07-14 负极极片、制备负极极片的方法、二次电池、电池模块、电池包和用电装置

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CN117154001B (zh) * 2023-10-27 2024-02-20 中创新航科技集团股份有限公司 圆柱电池
CN117497767A (zh) * 2024-01-03 2024-02-02 宁德时代新能源科技股份有限公司 电极组件及其制备方法、电池单体、电池和用电装置
CN117497766A (zh) * 2024-01-03 2024-02-02 宁德时代新能源科技股份有限公司 负极极片及其制备方法、电池和用电装置

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JP2003055047A (ja) * 2001-08-22 2003-02-26 Sumitomo Metal Ind Ltd 誘電体セラミック材料
US20130260250A1 (en) * 2010-12-17 2013-10-03 Toyota Jidosha Kabushiki Kaisha Secondary battery
JP2016039114A (ja) * 2014-08-11 2016-03-22 トヨタ自動車株式会社 非水電解質二次電池
CN110299556A (zh) * 2018-03-22 2019-10-01 株式会社东芝 电极、二次电池、电池组和车辆
JP2020202124A (ja) * 2019-06-12 2020-12-17 トヨタ自動車株式会社 二次電池用電極材料
CN114551798A (zh) * 2020-11-26 2022-05-27 本田技研工业株式会社 锂离子二次电池用负极

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JP2003055047A (ja) * 2001-08-22 2003-02-26 Sumitomo Metal Ind Ltd 誘電体セラミック材料
US20130260250A1 (en) * 2010-12-17 2013-10-03 Toyota Jidosha Kabushiki Kaisha Secondary battery
JP2016039114A (ja) * 2014-08-11 2016-03-22 トヨタ自動車株式会社 非水電解質二次電池
CN110299556A (zh) * 2018-03-22 2019-10-01 株式会社东芝 电极、二次电池、电池组和车辆
JP2020202124A (ja) * 2019-06-12 2020-12-17 トヨタ自動車株式会社 二次電池用電極材料
CN114551798A (zh) * 2020-11-26 2022-05-27 本田技研工业株式会社 锂离子二次电池用负极

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