WO2025055463A1 - 负极活性浆料、电池负极片以及锂离子二次电池 - Google Patents

负极活性浆料、电池负极片以及锂离子二次电池 Download PDF

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WO2025055463A1
WO2025055463A1 PCT/CN2024/101606 CN2024101606W WO2025055463A1 WO 2025055463 A1 WO2025055463 A1 WO 2025055463A1 CN 2024101606 W CN2024101606 W CN 2024101606W WO 2025055463 A1 WO2025055463 A1 WO 2025055463A1
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negative electrode
lithium
silicon
electrode active
battery
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French (fr)
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张薇
皮智超
史建鹏
苟斌
李宇航
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Dongfeng Motor Group Co Ltd
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si 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
    • 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
    • H01M4/58—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 application relates to the technical field of lithium-ion secondary batteries, and in particular to a negative electrode active slurry, a battery negative electrode sheet and a lithium-ion secondary battery.
  • Silicon-based negative electrodes have a theoretical specific capacity of up to 4200mAh/g and are widely used in high-energy-density lithium-ion batteries.
  • silicon-based negative electrodes are prone to lithium deposition during the charging and discharging process, especially when lithium-ion batteries are overcharged. Due to insufficient negative electrode residue, a layer of lithium metal will be deposited on the negative electrode surface. On the one hand, lithium deposition will cause a large amount of lithium ion loss, resulting in increased internal resistance and capacity decay; on the other hand, if the deposited lithium continues to grow, lithium dendrites will be generated.
  • lithium dendrites will pierce the diaphragm, causing an internal short circuit and triggering thermal runaway, posing a great threat to the safety of the battery.
  • lithium deposition is divided into reversible lithium deposition and irreversible lithium deposition. As the battery ages, the amount of irreversible lithium deposition will accumulate, which will not only accelerate the capacity decay of the lithium-ion battery, but also cause internal short circuits due to the formation of lithium dendrites, causing safety problems.
  • the present application provides a negative electrode active slurry, a battery negative electrode sheet and a lithium ion secondary battery to solve the technical problem that lithium deposition is easily generated on the negative electrode surface of the existing silicon-based negative electrode lithium ion secondary battery during the charge and discharge process.
  • the present application provides a negative electrode active slurry, the raw material components of which include: a silicon-based negative electrode material and an inorganic lithium compound; wherein the inorganic lithium compound can react with active lithium to form a protective layer.
  • the inorganic lithium compound includes at least one of the following: lithium nitrate, lithium nitrite, lithium sulfide, lithium nitride, lithium oxide, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium carbonate, lithium hydroxide, lithium silicate, and lithium sulfate.
  • the silicon-based negative electrode material includes at least one of the following: silicon-carbon negative electrode, silicon negative electrode, and silicon-oxygen negative electrode.
  • the inorganic lithium compound is 0.05 weight% to 20 weight%.
  • the inorganic lithium compound is 2% to 10% by weight.
  • the raw material components of the negative electrode active slurry also include: a solvent, a conductive agent and a binder.
  • the solvent includes one of the following: water, N-methylpyrrolidone.
  • the present application provides a battery negative electrode sheet, comprising a negative electrode sheet substrate and the negative electrode active slurry described in any one of the embodiments of the first aspect attached to at least a portion of the surface of the negative electrode sheet substrate.
  • the present application provides a lithium-ion secondary battery, wherein the lithium-ion secondary battery comprises the battery negative electrode sheet described in any one of the embodiments of the second aspect.
  • the lithium-ion secondary battery includes the following: a lithium iron phosphate secondary battery, a lithium-nickel cobalt manganese ternary secondary battery.
  • the negative electrode active slurry provided by the present application has a silicon-based negative electrode material as an active material component in the battery, which can undergo electrochemical reactions during the charge and discharge process and is the source of energy in the battery; and a very small amount of inorganic lithium compound is added to the negative electrode slurry, which can react with the active lithium during the charge and discharge process to form a solid protective layer, reduce the growth of lithium dendrites, thereby inhibiting the occurrence of lithium precipitation on the negative electrode surface, and thereby extending the cycle life of the silicon-based negative electrode.
  • FIG. 1 is a scanning electron micrograph of the negative electrode active slurry provided in Example 1 of the present application.
  • A, B can be singular or plural.
  • at least one refers to one or more, and “plural” refers to two or more.
  • At least one refers to any combination of these items, including any combination of singular or plural items.
  • at least one of a, b, or c or “at least one of a, b and c” can both mean: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, c can be single or plural, respectively.
  • the present application provides a negative electrode active slurry, which is irregularly spherical, as shown in the scanning electron micrograph of the negative electrode active slurry shown in FIG1.
  • the raw material components of the negative electrode active slurry include: a silicon-based negative electrode material and an inorganic lithium compound; wherein the inorganic lithium compound can react with active lithium to form a protective layer.
  • the negative electrode active slurry provided in the embodiment of the present application has a silicon-based negative electrode material as an active material component in the battery, which can undergo electrochemical reactions during the charge and discharge process and is the source of energy in the battery; and a very small amount of inorganic lithium compound is added to the negative electrode slurry, which can react during the charge and discharge process to form a solid protective layer, reduce the growth of lithium dendrites, thereby inhibiting the occurrence of lithium precipitation on the negative electrode surface, and thereby extending the cycle life of the silicon-based negative electrode.
  • the inorganic lithium compound includes at least one of the following: lithium nitrate, lithium nitrite, lithium sulfide, lithium nitride, lithium oxide, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium carbonate, lithium hydroxide, lithium silicate, and lithium sulfate.
  • the role of the inorganic lithium compound is to generate a solid protective layer during the discharge process, reduce the growth of lithium dendrites, thereby inhibiting the occurrence of lithium precipitation on the surface of the negative electrode, and thus extending the cycle life of the silicon-based negative electrode.
  • the inorganic lithium compound can be one or more of lithium nitrate, lithium nitrite, lithium sulfide, lithium nitride, lithium oxide, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium carbonate, lithium hydroxide, lithium silicate, and lithium sulfate.
  • the inorganic lithium compound can be lithium nitrate.
  • the silicon-based negative electrode material includes at least one of the following: a silicon-carbon negative electrode, a silicon negative electrode, and a silicon-oxygen negative electrode.
  • the role of the silicon-based negative electrode material is: the active material component in the battery can undergo electrochemical reactions during the charging and discharging process and is the source of energy in the battery.
  • the silicon-based negative electrode material can be one or more of a silicon-carbon negative electrode, a silicon negative electrode, and a silicon-oxygen negative electrode.
  • the inorganic lithium compound is present in an amount of 0.05% to 20% by weight relative to 1 part by weight of the silicon-based negative electrode material.
  • the inorganic lithium compound is 2 to 10 weight percent relative to 1 weight percent of the silicon-based negative electrode material.
  • the negative electrode active slurry can adjust the thickness, composition and modulus of the protective layer by adjusting the amount of inorganic lithium compound. Controlling the amount of inorganic lithium compound can improve the performance of the battery while suppressing the growth of negative electrode lithium dendrites without reducing the reversible specific capacity of the negative electrode. If the amount of the inorganic lithium compound is too much, to a certain extent, an overly thick interface layer will be formed on the surface of the negative electrode during the charge and discharge process, resulting in uneven lithium deposition and dendrite growth; at the same time, it will also reduce the content of active substances in the pole piece, causing the energy density of silicon-based batteries to decrease.
  • the amount of the inorganic lithium compound can be 0.5% by weight, 1% by weight, 3% by weight, 5% by weight, 7% by weight, 9% by weight, 10% by weight, 15% by weight, 20% by weight, etc.
  • the inorganic lithium compound may be 2% to 10% by weight.
  • the raw material components of the negative electrode active slurry further include: a solvent, a conductive agent, and a binder.
  • the solvent includes one of the following: water, N-methylpyrrolidone.
  • the role of the above-mentioned conductive agent is to increase the electron transmission speed of the pole piece in the battery.
  • the conductive agent can be one or more of conductive graphite, Ketjen black, acetylene black and conductive carbon black (SuperP).
  • the role of the above-mentioned adhesive in the process of preparing the negative pole piece, it will show a strong bonding effect after being dissolved in the solvent, and finally the pole piece is prepared by coating.
  • the adhesive can be one or more of carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), polyacrylic acid (PAA), polyacrylonitrile (PAN), polytetrafluoroethylene (PTFE), and polyacrylate.
  • the role of the above-mentioned solvent in the process of preparing the negative pole piece, the adhesive can be dissolved, mixed evenly with the metal halide and the conductive agent adhesive to form a slurry, and finally coated to prepare the negative pole piece.
  • the solvent can be one or more of water and N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • the amount of the above-mentioned conductive agent, adhesive and solvent can be the amount commonly used in the art.
  • the cost of the negative active slurry is low, and large-scale industrial production can be achieved, which has a very high commercial value.
  • the present application provides a battery negative electrode sheet, comprising a negative electrode sheet substrate and the negative electrode active slurry described in any one of the embodiments of the first aspect attached to at least a portion of the surface of the negative electrode sheet substrate.
  • This negative electrode active slurry by adding a very small amount of inorganic lithium compound additives to the negative electrode slurry, is used in the preparation of battery negative electrode sheets and/or batteries, and can react during the charge and discharge process to form a solid protective layer, reduce the growth of lithium dendrites, thereby inhibiting the occurrence of lithium precipitation on the negative electrode surface, and thus extending the cycle life of the silicon-based negative electrode.
  • the negative electrode active slurry is applied to the negative electrode sheet of the battery, and can react to form a solid protective layer during the charge and discharge process, reduce the growth of lithium dendrites, thereby inhibiting the occurrence of lithium precipitation on the negative electrode surface, and further Prolong the cycle life of silicon-based negative electrodes.
  • the present application provides a lithium-ion secondary battery, wherein the lithium-ion secondary battery comprises the battery negative electrode sheet described in any one of the embodiments of the second aspect.
  • the negative electrode active slurry can adjust the thickness, composition and modulus of the protective layer by adjusting the amount of inorganic lithium compounds.
  • the protective layer formed by the negative electrode active slurry can provide a good ion channel and stably exist during the cycle process, avoiding direct contact between the electrolyte and lithium metal, preventing the occurrence of side reactions, and thus solving the continuous cracking and repair of the SEI film. Therefore, the negative electrode with composite layer protection can solve the safety problems caused by the growth of lithium dendrites at the negative electrode and the capacity reduction problem caused by the continuous reconstruction of the SEI film.
  • lithium ion battery negative electrode sheet When the above-mentioned lithium ion battery negative electrode sheet is used for the negative electrode of a lithium ion secondary battery, its cycle performance can be greatly improved, and the in-situ composite protective film preparation method is simple, the raw materials are easily available, and it is suitable for large-scale production.
  • the lithium-ion secondary battery includes one of the following: a lithium iron phosphate secondary battery, a lithium-nickel cobalt manganese ternary secondary battery.
  • lithium iron phosphate secondary batteries and lithium-nickel cobalt manganese ternary secondary batteries are preferred lithium ion secondary batteries.
  • the introduction of the negative electrode active slurry can reduce the volume strain of the negative electrode sheet and promote the rapid migration of lithium ions.
  • a silicon-carbon negative electrode containing (4% wt lithium nitrate), Ketjen black and a binder are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • lithium nitrate additive 0.5%wt, and the rest is the same as in Example 1.
  • the details are as follows:
  • a silicon-carbon negative electrode containing (0.5% lithium nitrate), Ketjen black and a binder (the weight ratio of sodium carboxymethyl cellulose and styrene-butadiene rubber is 1:1) are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • lithium nitrate additive 20%wt, and the rest is the same as in Example 1.
  • the details are as follows:
  • a silicon-carbon negative electrode containing (20% wt lithium nitrate), Ketjen black and a binder (the weight ratio of sodium carboxymethyl cellulose and styrene-butadiene rubber is 1:1) are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • the additive in the negative electrode slurry is 5%wt lithium nitrite, and the rest is the same as in Example 1.
  • the details are as follows:
  • a silicon-carbon negative electrode containing (5%wt lithium nitrite), Ketjen black and a binder are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • a silicon-carbon negative electrode containing (7%wt lithium sulfide), Ketjen black and a binder (the weight ratio of sodium carboxymethyl cellulose and styrene-butadiene rubber is 1:1) are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • the additive in the negative electrode slurry is 4%wt lithium nitride, and the rest is the same as in Example 1.
  • the details are as follows:
  • a silicon-carbon negative electrode containing (4% wt lithium nitride), Ketjen black and a binder are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • the additive in the negative electrode slurry is 10%wt lithium oxide, and the rest is the same as in Example 1.
  • the details are as follows:
  • the additive in the negative electrode slurry is 13%wt lithium fluoride, and the rest is the same as in Example 1.
  • the details are as follows:
  • a silicon-carbon negative electrode containing (13% wt lithium fluoride), Ketjen black and a binder are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • a silicon-carbon negative electrode containing (7% wt lithium chloride), Ketjen black and a binder (the weight ratio of sodium carboxymethyl cellulose and styrene-butadiene rubber is 1:1) are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • the additive in the negative electrode slurry is 5%wt lithium bromide, and the rest is the same as in Example 1.
  • the details are as follows:
  • the additive in the negative electrode slurry is 13%wt lithium iodide, and the rest is the same as in Example 1.
  • the details are as follows:
  • a silicon-carbon negative electrode containing (13%wt lithium iodide), Ketjen black and a binder are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • the additive in the negative electrode slurry is 15%wt lithium carbonate, and the rest is the same as in Example 1.
  • the details are as follows:
  • a silicon-carbon negative electrode containing (15% wt lithium carbonate), Ketjen black and a binder are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • the additive in the negative electrode slurry is 8%wt lithium hydroxide, and the rest is the same as in Example 1.
  • the details are as follows:
  • a silicon-carbon negative electrode containing (8% wt lithium hydroxide), Ketjen black and a binder are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • the additive in the negative electrode slurry is 13%wt lithium silicate, and the rest is the same as in Example 1.
  • the details are as follows:
  • a silicon-carbon negative electrode containing (13% wt lithium silicate), Ketjen black and a binder are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • the additive in the negative electrode slurry is 7%wt lithium sulfate, and the rest is the same as in Example 1.
  • the details are as follows:
  • a silicon-carbon negative electrode containing (7% wt lithium sulfate), Ketjen black and a binder are slurried at room temperature and pressure (weight ratio is 8:1:1, water is the solvent, and the solid content is 4wt%).
  • the negative electrode active slurries prepared in Examples 1-15 and Comparative Example 1 are applied to the preparation of negative electrode sheets for lithium ion batteries and lithium ion secondary batteries, the steps of which are as follows:
  • the negative electrode active slurry prepared in Examples 1-15 and Comparative Example 1 was uniformly coated on the corresponding carbon-coated copper foil substrate, and then After vacuum drying at 80°C for 12 h, the obtained thin film material was compressed under a pressure of 10 MPa and cut into electrode sheets with a diameter of 10 mm as the negative electrode of the simulated battery.
  • the negative electrode sheet, separator, electrolyte of 1M lithium hexafluorophosphate in ethylene carbonate and diethyl carbonate (volume ratio of 1:1) and LiNi0.8Co0.1Mn0.1O2 (NCM811) positive electrode sheet were assembled into button batteries in an argon-protected glove box.
  • the button cells assembled from the above-mentioned Examples 1-15 and Comparative Example 1 were subjected to a battery cycle test at a current density of 1 mA/cm2. The test results are shown in Table 1.
  • the battery containing lithium nitrate additive has higher The capacity retention rate reaches more than 97%. This is mainly because the battery containing lithium nitrate additive can generate a solid protective layer during the charge and discharge process, reduce the growth of lithium dendrites, thereby inhibiting the occurrence of lithium precipitation, and thus extending the cycle life of the silicon-carbon negative electrode.
  • the negative electrode active slurry provided in the embodiment of the present application has a silicon-based negative electrode material as an active material component in the battery, which can undergo electrochemical reactions during the charge and discharge process and is the source of energy in the battery; and a very small amount of inorganic lithium compound is added to the negative electrode slurry, which can react with the active lithium during the charge and discharge process to form a solid protective layer, reduce the growth of lithium dendrites, thereby inhibiting the occurrence of lithium precipitation on the negative electrode surface, and thereby extending the cycle life of the silicon-based negative electrode.

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Abstract

一种负极活性浆料、电池负极片以及锂离子二次电池，所述负极活性浆料的原料组分包括：硅基负极材料和无机锂化合物；其中，所述无机锂化合物能与活性锂发生反应，形成保护层。该原料组分中，硅基负极材料作为电池中的活性物质组分，可以在充放电过程中发生电化学反应，是电池中能量的源头；并在负极浆料中加入极少量的无机锂化合物添加剂，可以在充放电过程中发生反应生成坚固的保护层，减少锂枝晶的生长，从而抑制负极表面析锂现象的发生，进而延长硅基负极的循环寿命。

Description

负极活性浆料、电池负极片以及锂离子二次电池
相关申请的交叉引用
本申请要求于2023年09月13日提交的申请号为202311178296.1的中国专利申请的优先权，其全部内容通过引用并入本文。
技术领域
本申请涉及锂离子二次电池技术领域，尤其涉及一种负极活性浆料、电池负极片以及锂离子二次电池。
背景技术
硅基负极理论比容量高达4200mAh/g，被广泛应用于高能量密度锂离子电池。但硅基负极在充放电过程中易发生析锂，尤其锂离子电池在过充的情况下，由于负极余量不够会在负极表面析出一层锂金属，一方面，析锂会造成大量的锂离子损失，造成内阻增加和容量衰减；另一方面，如果析出的锂继续增长会生成锂枝晶，锂枝晶会刺穿隔膜造成内部短路触发热失控，对电池的安全性造成极大的威胁。也就是说，析锂分为可逆析锂和不可逆析锂，随着电池的老化，不可逆析锂量会累积，这不仅会使锂离子电池的容量加速衰减，还会由于形成锂枝晶而引发内短路造成安全问题。
因此，为了提高硅基负极的容量和循环性能，亟需开发一种抑制析锂发生的技术显得愈发重要。
发明内容
本申请提供了一种负极活性浆料、电池负极片以及锂离子二次电池，以解决现有硅基负极锂离子二次电池在充放电过程中负极表面易发生析锂现象的技术问题。
第一方面，本申请提供了一种负极活性浆料，所述负极活性浆料的原料组分包括：硅基负极材料和无机锂化合物；其中，所述无机锂化合物能与活性锂发生反应，形成保护层。
可选的优化技术方案：所述无机锂化合物包括如下至少一种：硝酸锂、亚硝酸锂、硫化锂、氮化锂、氧化锂、氟化锂、氯化锂、溴化锂、碘化锂、碳酸锂、氢氧化锂、硅酸锂、硫酸锂。
可选的优化技术方案：所述硅基负极材料包括如下至少一种：硅碳负极、硅负极、硅氧负极。
可选的优化技术方案：相对于1重量份的所述硅基负极材料，所述无机锂化合物为0.05％重量份～20％重量份。
可选的优化技术方案：相对于1重量份的所述硅基负极材料，所述无机锂化合物为2％重量份～10％重量份。
可选的优化技术方案：所述负极活性浆料的原料组分还包括：溶剂、导电剂以及粘合剂。
可选的优化技术方案：所述溶剂包括如下一种：水、N－甲基吡咯烷酮。
第二方面，本申请提供了一种电池负极片，所述电池负极片包括负极片基体以及附着于所述负极片基体至少部分表面的第一方面任意一项实施例所述的负极活性浆料。
第三方面，本申请提供了一种锂离子二次电池，所述锂离子二次电池包括第二方面任意一项实施例所述的电池负极片。
可选的优化技术方案：所述锂离子二次电池包括如下一种：锂磷酸铁锂二次电池、锂-镍钴锰三元二次电池。
本申请上述技术方案与现有技术相比具有如下优点：
本申请提供的该负极活性浆料，其原料组分中，硅基负极材料作为电池中的活性物质组分，可以在充放电过程中发生电化学反应，是电池中能量的源头；并在负极浆料中加入极少量的无机锂化合物，可以在充放电过程中，与活性锂发生反应，形成坚固的保护层，减少锂枝晶的生长，从而抑制负极表面易发生析锂现象的发生，进而延长硅基负极的循环寿命。
附图说明
此处的附图被并入说明书中并构成本说明书的一部分，示出了符合本申请的实施例，并与说明书一起用于解释本申请的原理。
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，对于本领域普通技术人员而言，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为本申请实施例1提供的负极活性浆料的扫描电子显微图片。
具体实施方式
为使本申请实施例的目的、技术方案和优点更加清楚，下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请的一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本申请保护的范围。
本申请的各种实施例可以以一个范围的形式存在；应当理解，以一范围形式的描述仅仅是因为方便及简洁，不应理解为对本申请范围的硬性限制；因此，应当认为所述的范围描述已经具体公开所有可能的子范围以及该范围内的单一数值。例如，应当认为从1到6的范围描述已经具体公开子范围，例如从1到3，从1到4，从1到5，从2到4，从2到6，从3 到6等，以及所述范围内的单一数字，例如1、2、3、4、5及6，此不管范围为何皆适用。另外，每当在本文中指出数值范围，是指包括所指范围内的任何引用的数字(分数或整数)。
在本申请中，在未作相反说明的情况下，使用的方位词如“上”和“下”具体为附图中的图面方向。另外，在本申请说明书的描述中，术语“包括”“包含”等是指“包括但不限于”。在本文中，诸如“第一”和“第二”等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。在本文中，“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。在本文中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“至少一种”、“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a,b,或c中的至少一项(个)”，或，“a,b,和c中的至少一项(个)”，均可以表示：a,b,c,a-b(即a和b),a-c,b-c,或a-b-c，其中a,b,c分别可以是单个，也可以是多个。
除非另有特别说明，本申请中用到的各种原材料、试剂、仪器和设备等，均可通过市场购买得到或者可通过现有方法制备得到。
第一方面，本申请提供了一种负极活性浆料，请参见图1所示的负极活性浆料的扫描电子显微图片，为不规则球状。所述负极活性浆料的原料组分包括：硅基负极材料和无机锂化合物；其中，所述无机锂化合物能与活性锂发生反应，形成保护层。
本申请实施例提供的该负极活性浆料，其原料组分中，硅基负极材料作为电池中的活性物质组分，可以在充放电过程中发生电化学反应，是电池中能量的源头；并在负极浆料中加入极少量的无机锂合物，可以在充放电过程中发生反应生成坚固的保护层，减少锂枝晶的生长，从而抑制负极表面易发生析锂现象的发生，进而延长硅基负极的循环寿命。
在一些实施方式中，所述无机锂化合物包括如下至少一种：硝酸锂、亚硝酸锂、硫化锂、氮化锂、氧化锂、氟化锂、氯化锂、溴化锂、碘化锂、碳酸锂、氢氧化锂、硅酸锂、硫酸锂。
在本申请实施例中，无机锂化合物的作用：在放电过程中生成坚固的保护层，减少锂枝晶的生长，从而抑制负极表面易发生析锂现象的发生，进而延长硅基负极的循环寿命，该无机锂化合物可以是硝酸锂、亚硝酸锂、硫化锂、氮化锂、氧化锂、氟化锂、氯化锂、溴化锂、碘化锂、碳酸锂、氢氧化锂、硅酸锂、硫酸锂中的一种或多种。优选地，该无机锂化合物可以是硝酸锂。
在一些实施方式中，所述硅基负极材料包括如下至少一种：硅碳负极、硅负极、硅氧负极。
在本申请实施例中，上述负极活性浆料的原料组分中，硅基负极材料的作用：电池中的活性物质组分，可以在充放电过程中发生电化学反应，是电池中能量的源头。该硅基负极材料可以为硅碳负极、硅负极、硅氧负极的一种或多种。
在一些实施方式中，相对于1重量份的所述硅基负极材料，所述无机锂化合物为0.05％重量份～20％重量份。
在一些实施方式中，相对于1重量份的所述硅基负极材料，所述无机锂化合物为2％重量份～10％重量份。
在本申请实施例中，该负极活性浆料可通过调控无机锂化合物的量来调控保护层厚度、组分和模量。控制无机锂化合物的用量，可以在抑制负极锂枝晶生长的同时，不降低负极可逆比容量，改善电池的性能。若该无机锂化合物的用量过多，在一定程度上会在充放电过程中负极表面形成过厚的界面层，导致不均匀的锂沉积和枝晶生长；同时也会降低极片中活性物质的含量，造成硅基电池能量密度下降.；若该无机锂化合物的用量过少，在一定程度上不能在负极表面形成均匀的界面层，导致不均匀的锂沉积和枝晶生长。具体地，该无机锂化合物的用量可以为0.5％重量份、1％重量份、3％重量份、5％重量份、7％重量份、9％重量份、10％重量份、15％重量份、20％重量份等。优选地，相对于1重量份所述的负极材料，所述无机锂化合物可以为2％重量份～10％重量份。
在一些实施方式中，所述负极活性浆料的原料组分还包括：溶剂、导电剂以及粘合剂。
在一些实施方式中，所述溶剂包括如下一种：水、N－甲基吡咯烷酮。
在本申请实施例中，上述导电剂的作用：提高电池中极片的电子传输速度，该导电剂可以为导电石墨、科琴黑、乙炔黑和导电碳黑(SuperP)中的一种或多种。上述粘合剂的作用：在负极极片制备过程中，其溶解于溶剂后会表现出强的粘结作用，最终通过涂敷，制备出极片，该粘合剂可以为羧甲基纤维素(CMC)、聚偏氟乙烯(PVDF)、聚丙烯酸(PAA)、聚丙烯腈(PAN)、聚四氟乙烯(PTFE)、聚丙烯酸酯中的一种或多种。上述溶剂的作用：在负极极片制备过程中，可以溶解粘合剂，与金属卤化物、导电剂粘合剂混合均匀后形成浆料，最后涂敷制备得到负极极片，该溶剂可以为水、N-甲基吡咯烷酮(NMP)中的一种或多种。此外，上述导电剂、粘合剂以及溶剂的用量均可以为本领域常用用量。该负极活性浆料的成本低廉，能够实现大规模工业化生成，具有极高的商业价值。
第二方面，本申请提供了一种电池负极片，所述电池负极片包括负极片基体以及附着于所述负极片基体至少部分表面的第一方面任意一项实施例所述的负极活性浆料。
常规硅基锂离子电池在循环过程中会存在不均匀锂沉积，导致锂枝晶生成，以及活性锂与电解质反应产生死锂，导致电池易发生短路，不可逆锂消耗，严重恶化电池性能。该负极活性浆料，在负极浆料中加入极少量的无机锂化合物添加剂，应用于制备电池负极片和/或制备电池中，可以在充放电过程中发生反应生成坚固的保护层，减少锂枝晶的生长，从而抑制负极表面易发生析锂现象的发生，进而延长硅基负极的循环寿命。
在本申请实施例中，该负极活性浆料应用于电池的负极片，可以在充放电过程中发生反应生成坚固的保护层，减少锂枝晶的生长，从而抑制负极表面易发生析锂现象的发生，进而 延长硅基负极的循环寿命。
第三方面，本申请提供了一种锂离子二次电池，所述锂离子二次电池包括第二方面任意一项实施例所述的电池负极片。
在本申请实施例中，该负极活性浆料可通过调控无机锂化合物的量来调控保护层厚度、组分和模量，该负极活性浆料所形成的保护层可以提供良好的离子通道，并且在循环过程中稳定存在，避免了电解质与锂金属的直接接触，阻止了副反应的发生，因此解决了SEI膜的不断破解与修复。因此，带有复合层保护的负极可以解决负极的锂枝晶生长带来的安全问题和SEI膜不断重构带来的容量下降问题，上述锂离子电池负极片用于锂离子二次电池的负极时，可以大幅度提高其循环性能，并且该原位复合保护膜制备方法简单，原料易得，适用于大规模生产。
在一些实施方式中，所述锂离子二次电池包括如下一种：锂磷酸铁锂二次电池、锂-镍钴锰三元二次电池。
在本申请实施例中，锂磷酸铁锂二次电池、锂-镍钴锰三元二次电池为优选的锂离子二次电池，在该锂离子二次电池工作时，该负极活性浆料的引入可以起到减少负极片体积应变的作用，并促进锂离子快速迁移。
下面结合具体的实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。下列实施例中未注明具体条件的实验方法，通常按照国家标准测定。若没有相应的国家标准，则按照通用的国际标准、常规条件、或按照制造厂商所建议的条件进行。
实施例1
负极活性浆料的制备：将含有(4％wt硝酸锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例2
硝酸锂添加剂的含量为0.5％wt，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(0.5％硝酸锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例3
硝酸锂添加剂的含量为20％wt，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(20％wt硝酸锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例4
负极浆料中的添加剂为5％wt亚硝酸锂，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(5％wt亚硝酸锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例5
负极浆料中的添加剂为7％wt硫化锂，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(7％wt硫化锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例6
负极浆料中的添加剂为4％wt氮化锂，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(4％wt氮化锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例7
负极浆料中的添加剂为10％wt氧化锂，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(10％wt氧化锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例8
负极浆料中的添加剂为13％wt氟化锂，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(13％wt氟化锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例9
负极浆料中的添加剂为7％wt氯化锂，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(7％wt氯化锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例10
负极浆料中的添加剂为5％wt溴化锂，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(5％wt溴化锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维 素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例11
负极浆料中的添加剂为13％wt碘化锂，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(13％wt碘化锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例12
负极浆料中的添加剂为15％wt碳酸锂，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(15％wt碳酸锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例13
负极浆料中的添加剂为8％wt氢氧化锂，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(8％wt氢氧化锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例14
负极浆料中的添加剂为13％wt硅酸锂，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(13％wt硅酸锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
实施例15
负极浆料中的添加剂为7％wt硫酸锂，其余均与实施例1相同。具体如下：
负极活性浆料的制备：将含有(7％wt硫酸锂)的硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
对比例1
负极活性浆料的制备：将硅碳负极、科琴黑和粘合剂(羧甲基纤维素钠和丁苯橡胶的重量比为1：1)在常温常压下制浆(重量比为8：1：1，水为溶剂，固含量4wt％)。
将实施例1-15制备和对比例1的负极活性浆料应用于锂离子电池负极片和锂离子二次电池的制备，其步骤：
将实施例1-15和对比例1制备的负极活性浆料均匀涂覆于对应的涂炭铜箔衬底上，然后 在80℃下真空干燥12h，将所得的薄膜材料在10MPa压力下压紧，将其裁减成直径为10mm的电极片，作为模拟电池的负极，将上述负极片、隔膜、电解液为1M六氟磷酸锂的碳酸乙烯酯和碳酸二乙酯(体积比为1:1)以及LiNi0.8Co0.1Mn0.1O2(NCM811)正极片在氩气保护的手套箱中组装成扣式电池。
将上述实施例1-15与对比例1所组装的扣式电池在1mA/cm2电流密度，进行电池的循环测试。其测试结果请参见表1。
表1锂离子二次电池的循环性能测试结果
从表1可以看出含硝酸锂添加剂的电池相比不含添加剂的电池循环300圈后具有更高的 容量保持率，达到97％以上。其主要是因为含硝酸锂添加剂的电池可以在充放电过程中生成坚固的保护层，减少锂枝晶的生长，从而抑制析锂现象的发生，进而延长硅碳负极的循环寿命。
本申请上述实施例的上述技术方案与现有技术相比具有如下优点：
本申请实施例提供的该负极活性浆料，其原料组分中，硅基负极材料作为电池中的活性物质组分，可以在充放电过程中发生电化学反应，是电池中能量的源头；并在负极浆料中加入极少量的无机锂化合物，可以在充放电过程中，与活性锂发生反应，形成坚固的保护层，减少锂枝晶的生长，从而抑制负极表面易发生析锂现象的发生，进而延长硅基负极的循环寿命。
以上所述仅是本申请的具体实施方式，使本领域技术人员能够理解或实现本申请。对这些实施例的多种修改对本领域的技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本申请的精神或范围的情况下，在其它实施例中实现。因此，本申请将不会被限制于本文所示的这些实施例，而是要符合与本文所申请的原理和新颖特点相一致的最宽的范围。

Claims (10)

  1. 一种负极活性浆料，所述负极活性浆料的原料组分包括：硅基负极材料和无机锂化合物；其中，所述无机锂化合物能与活性锂发生反应，形成保护层。
  2. 根据权利要求1所述的负极活性浆料，其中，所述无机锂化合物包括如下至少一种：硝酸锂、亚硝酸锂、硫化锂、氮化锂、氧化锂、氟化锂、氯化锂、溴化锂、碘化锂、碳酸锂、氢氧化锂、硅酸锂、硫酸锂。
  3. 根据权利要求1所述的负极活性浆料，其中，所述硅基负极材料包括如下至少一种：硅碳负极、硅负极、硅氧负极。
  4. 根据权利要求1～3任意一项所述的负极活性浆料，其中，相对于1重量份的所述硅基负极材料，所述无机锂化合物为0.05％重量份～20％重量份。
  5. 根据权利要求4所述的负极活性浆料，其中，相对于1重量份的所述硅基负极材料，所述无机锂化合物为2％重量份～10％重量份。
  6. 根据权利要求1所述的负极活性浆料，其中，所述负极活性浆料的原料组分还包括：溶剂、导电剂以及粘合剂。
  7. 根据权利要求6所述的负极活性浆料，其中，所述溶剂包括如下一种：水、N－甲基吡咯烷酮。
  8. 一种电池负极片，所述电池负极片包括负极片基体以及附着于所述负极片基体至少部分表面的权利要求1～7任意一项所述的负极活性浆料。
  9. 一种锂离子二次电池，所述锂离子二次电池包括权利要求8所述的电池负极片。
  10. 根据权利要求9所述的锂离子二次电池，其中，所述锂离子二次电池包括如下一种：锂磷酸铁锂二次电池、锂-镍钴锰三元二次电池。
PCT/CN2024/101606 2023-09-13 2024-06-26 负极活性浆料、电池负极片以及锂离子二次电池 Pending WO2025055463A1 (zh)

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