WO2022012296A1 - 疏水电极及其制备方法和电池 - Google Patents

疏水电极及其制备方法和电池 Download PDF

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WO2022012296A1
WO2022012296A1 PCT/CN2021/102126 CN2021102126W WO2022012296A1 WO 2022012296 A1 WO2022012296 A1 WO 2022012296A1 CN 2021102126 W CN2021102126 W CN 2021102126W WO 2022012296 A1 WO2022012296 A1 WO 2022012296A1
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electrode
hydrophobic
material layer
present disclosure
hydrophobic material
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French (fr)
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刘昱
陈璞
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Rehab Energy Inc
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Rehab Energy Inc
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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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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 disclosure belongs to the field of batteries, and in particular relates to a hydrophobic electrode, a preparation method thereof, and a battery.
  • the current treatment method for the hydrophobic effect on the surface of the air electrode is mainly to form neat nano-raised lines on the surface of the carbon film to change the surface tension of the air electrode.
  • the formation of nano-raised lines usually requires the simultaneous use of laser etching and rolling methods, which is complicated in operation and difficult to control, and cannot be applied in large-scale industrial production.
  • an object of the present disclosure is to propose a hydrophobic electrode, a preparation method thereof, and a battery, the hydrophobic electrode has excellent cycle stability, so that the battery loaded with the hydrophobic electrode has excellent cycle performance, safety performance and capacity Retention.
  • the present disclosure proposes a hydrophobic electrode.
  • the hydrophobic electrode includes:
  • a hydrophobic material layer, the hydrophobic material layer is provided on at least a part of the surface of the electrode base.
  • the hydrophobic electrode of the embodiments of the present disclosure by forming a hydrophobic material layer on the surface of the electrode substrate, the direct contact between the active substance in the electrode substrate and the electrolyte is prevented, the dissolution of the active substance is alleviated, and the cycle stability of the electrode is improved, so that the The battery loaded with the hydrophobic electrode has excellent cycle performance and safety performance, and at the same time, by adopting a hydrophobic material layer, the hydrophobic material layer repels the combination of water molecules in the electrolyte and the metal ions eluted from the active material through the hydrophobic force, that is, the active material is obtained. The dissolved metal ions in the substance cannot migrate into the electrolyte, thereby improving the capacity retention rate of the battery loaded with the hydrophobic electrode.
  • hydrophobic electrodes according to the above embodiments of the present disclosure may also have the following additional technical features:
  • the thickness of the hydrophobic material layer is 0.05-995 ⁇ m.
  • the battery loaded with the hydrophobic electrode has excellent cycle performance and capacity retention rate.
  • the hydrophobic material layer includes at least one of paraffin, epoxy, polytetrafluoroethylene, fluorinated polyethylene, polyamide, polyacrylonitrile, polyolefin, and polycarbonate.
  • the battery loaded with the hydrophobic electrode has excellent cycle performance and safety performance.
  • the electrode base body includes: a conductive electrode sheet; and a slurry layer, the slurry layer is provided on at least a part of the surface of the conductive electrode sheet.
  • the conductive electrode sheet is a conductive polyethylene film, graphite foil, carbon cloth, carbon fiber, or a mesh or foil material containing stainless steel, titanium, aluminum, copper, nickel metal or alloy.
  • the slurry layer includes an active material, a binder, a conductive agent, and a solvent.
  • the active material includes at least one of MnO 2 , LiMn 2 O 4 , ZnMn 2 O 4 , LiFePO 4 and LiCoO 2 .
  • the present disclosure proposes a method for preparing the above-mentioned hydrophobic electrode. According to an embodiment of the present disclosure, the method includes:
  • a slurry containing a hydrophobic material is applied on at least a part of the electrode substrate, so as to form a hydrophobic material layer on at least a part of the surface of the electrode substrate, the hydrophobic material is The material layer can prevent the direct contact between the active material in the electrode matrix and the electrolyte, reduce the dissolution of the active material, and improve the cycle stability of the electrode, so that the battery loaded with the hydrophobic electrode has excellent cycle performance and safety performance, and at the same time
  • the hydrophobic material layer repels the water molecules in the electrolyte from combining with the metal ions dissolved from the active material through the hydrophobic force, so that the dissolved metal ions in the active material cannot migrate into the electrolyte, thereby improving the loading of the electrolyte. Capacity retention of batteries with hydrophobic electrodes.
  • the method for preparing a hydrophobic electrode according to the above embodiments of the present disclosure may also have the following additional technical features:
  • the mass concentration of the slurry containing the hydrophobic material is 0.1-10 wt %. Therefore, on the one hand, the bonding strength between the hydrophobic material layer and the electrode substrate can be improved, and on the other hand, the slurry containing the hydrophobic material can be uniformly spread on the surface of the electrode substrate, so as to avoid the formation of burrs on the electrode surface and pierce the battery separator, and improve the safety of the battery. .
  • the application method includes spin coating, brush coating, dipping or spraying. Therefore, the application method is simple to operate and easy to control, and can be applied to industrial production on a large scale.
  • the present disclosure proposes a battery.
  • the positive electrode of the battery is the above-mentioned hydrophobic electrode or a hydrophobic electrode obtained by the above-mentioned method.
  • the battery has excellent cycle performance and safety performance as well as capacity retention.
  • FIG. 1 is a schematic diagram of a longitudinal cross-sectional structure of a hydrophobic electrode according to an embodiment of the present disclosure
  • FIG. 2 is a schematic longitudinal cross-sectional structural diagram of an electrode substrate in a hydrophobic electrode according to an embodiment of the present disclosure
  • FIG. 3 is a schematic flowchart of a method for preparing a hydrophobic electrode according to an embodiment of the present disclosure
  • a is the SEM image on the surface of the positive pole piece of Comparative Example 1;
  • a is the contact angle test chart of the positive pole piece of Comparative Example 1;
  • b is the contact angle test diagram of forming the hydrophobic material layer on the positive pole piece of Example 1;
  • FIG. 6 is a comparison diagram of the capacity decay of the batteries of Example 1 and Comparative Example 1.
  • FIG. 6 is a comparison diagram of the capacity decay of the batteries of Example 1 and Comparative Example 1.
  • the present disclosure proposes a hydrophobic electrode.
  • the hydrophobic electrode includes: an electrode base 100 and a hydrophobic material layer 200 .
  • the electrode base 100 includes a conductive electrode sheet 11 and a slurry layer 12 , wherein the slurry layer 12 is provided on at least a part of the surface of the conductive electrode sheet 11 , and preferably the slurry layer 12 covers on the entire surface of the conductive electrode sheet 11 .
  • the conductive electrode sheet used in this application is a conductive polyethylene film, graphite foil, carbon cloth, carbon fiber, or contains stainless steel, titanium, aluminum, copper, nickel, etc.
  • At least one of metal or alloy mesh materials or foil materials, and the slurry layer 12 used in this application includes active substances, binders, conductive agents and solvents, and those skilled in the art can choose according to actual needs.
  • Specific active materials, binders, conductive agents and solvents for example, the active materials include at least one of MnO 2 , LiMn 2 O 4 , ZnMn 2 O 4 , LiFePO 4 and LiCoO 2 ;
  • the conductive agents are acetylene black, graphite , at least one of carbon nanotubes and graphene
  • the binder is at least one of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and styrene butadiene rubber (SBR)
  • the solvent is N-methyl At least one of pyrrolidone, sodium carboxymethyl cellulose aqueous solution and hydroxypropyl methyl cellulose aqueous solution. It should be noted that those skilled in the art can
  • the hydrophobic material layer 200 is provided on at least a part of the surface of the electrode base 100 , preferably, the hydrophobic material layer 200 covers the entire surface of the electrode base 100 .
  • the inventors found that by forming a hydrophobic material layer on the surface of the electrode substrate, the direct contact between the active substance in the electrode substrate and the electrolyte is prevented, the dissolution of the active substance is reduced, and the cycle stability of the electrode is improved, so that the hydrophobic electrode is loaded with the hydrophobic electrode.
  • the battery has excellent cycle performance and safety performance.
  • the hydrophobic material layer repels the water molecules in the electrolyte and the metal ions dissolved from the active material through the hydrophobic force.
  • the ions cannot migrate into the electrolyte, thereby improving the capacity retention rate of the battery loaded with this hydrophobic electrode.
  • the thickness of the hydrophobic material layer 100 is 0.05-995 ⁇ m, for example, the thickness is 1-20 ⁇ m.
  • the hydrophobic material layer 100 includes at least one of paraffin, epoxy, polytetrafluoroethylene, fluorinated polyethylene, polyamide, polyacrylonitrile, polyolefin, and polycarbonate.
  • the present disclosure proposes a method for preparing the above-mentioned hydrophobic electrode. According to an embodiment of the present disclosure, referring to FIG. 3 , the method includes:
  • the electrode substrate is the electrode substrate 100 described above, which will not be repeated here.
  • a slurry containing a hydrophobic material is applied on at least a portion of the electrode substrate to form a hydrophobic material layer on at least a portion of the surface of the electrode substrate.
  • the inventors have found that by applying a slurry containing a hydrophobic material on at least a portion of the electrode substrate to form a layer of hydrophobic material on at least a portion of the surface of the electrode substrate, the layer of hydrophobic material can prevent activity in the electrode substrate
  • the direct contact between the substance and the electrolyte reduces the dissolution of the active substance and improves the cycle stability of the electrode, so that the battery loaded with the hydrophobic electrode has excellent cycle performance and safety performance.
  • the layer repels the combination of water molecules in the electrolyte and the metal ions dissolved from the active material through the hydrophobic force, so that the dissolved metal ions in the active material cannot migrate into the electrolyte, thereby improving the capacity retention rate of the battery loaded with the hydrophobic electrode. It should be noted that the thickness and type of the hydrophobic material layer are the same as those described above, and are not repeated here.
  • the mass concentration of the slurry containing the hydrophobic material is 0.1-10 wt %, for example, 0.1 wt %, 0.2 wt %... 9.9 wt %, 10 wt %.
  • the inventors found that if the mass concentration of the slurry is too low, the resulting hydrophobic material layer has a low bonding strength with the electrode substrate, and if the mass concentration of the slurry is too high, the slurry containing the hydrophobic material cannot be used in the electrode.
  • the surface of the substrate spreads evenly, resulting in the formation of burrs on the electrode surface and piercing the battery separator.
  • the use of the hydrophobic slurry in this concentration range can improve the bonding strength between the hydrophobic material layer and the electrode substrate, and at the same time improve the safety of the battery.
  • those skilled in the art can choose the application mode of the above slurry according to actual needs, for example, including but not limited to spin coating, brush coating, dipping or spraying. Therefore, the application method is simple to operate and easy to control, and can be applied to industrial production on a large scale. It should be noted that the features and advantages described above for the hydrophobic electrode are also applicable to the method for preparing the hydrophobic electrode, which will not be repeated here.
  • the present disclosure proposes a battery.
  • the positive electrode of the battery is the above-mentioned hydrophobic electrode or a hydrophobic electrode obtained by the above-mentioned method.
  • the battery has excellent cycle performance and safety performance as well as capacity retention. It should be noted that the features and advantages described above with respect to the hydrophobic electrode and the preparation method thereof are also applicable to the battery, and will not be repeated here.
  • the active material of the positive electrode is MnO 2 (70wt%), acetylene black as the conductive agent (20wt%), polyvinylidene fluoride as the binder (10wt%), N-methyl-pyrrolidone as the solvent ( The mass ratio of solvent to binder is 46:1) and stir to form a uniform slurry, then coat the slurry on the conductive polyethylene film, and form a slurry layer on the polyethylene film, that is, the positive pole piece is made , after vacuum drying the positive pole piece at 60°C, spin-coating the paraffin solution with a concentration of 1 wt% on the surface of the dried positive pole piece (as shown in b in Figure 4), the spin coating speed is 1200r /min, after drying again, a hydrophobic material layer (the thickness of the hydrophobic material layer is 5 ⁇ m) is formed on the surface of the positive electrode, and the contact angle test result of the hydrophobic material layer is shown in b in Figure 5.
  • a charge-discharge battery with metallic zinc as the negative electrode and paraffin-coated MnO 2 as the positive electrode was obtained.
  • the test is conducted with a current of 0.5A/g, firstly, the constant current discharge is carried out at 100mA/g to 1V, and then the constant current charge is carried out at 100mA/g. shown in Figure 6).
  • the hydrophobic material is changed to epoxy resin, the concentration of the slurry containing epoxy resin is 1wt%, the thickness of the hydrophobic material layer is 3.5 ⁇ m, and the conductive electrode sheet is graphite foil, other preparation conditions and test conditions are the same as those in Example 1. same. After being activated for 4 times by constant current charging and discharging at 100 mA/g current density, and then 1000 times by charging and discharging at 500 mA/g constant current, the capacity decay was 24%.
  • Example 1 Except that the positive electrode active material was changed to ZnMn 2 O 4 , other preparation conditions were the same as those in Example 1, and a secondary battery with zinc as the negative electrode and paraffin-coated ZnMn 2 O 4 as the positive electrode was obtained.
  • the test conditions were also the same as in Example 1. According to the test results, the capacity decay ratios after 1000 cycles after activation were also obtained to be 22% respectively.
  • the concentration of the slurry containing polytetrafluoroethylene is 0.1 wt%
  • the conductive electrode sheet is a mesh material containing copper and nickel
  • other preparation conditions and test conditions are the same as those in Example 1. . After 4 times of activation by constant current charge and discharge at 100mA/g current density, and after 1000 times of charge and discharge at 500mA/g constant current, the capacity decay is 35%.
  • Example 1 Except that the hydrophobic material is changed to fluorinated polyethylene, the concentration of the slurry containing fluorinated polyethylene is 5wt%, and the conductive electrode sheet is a foil-like material containing aluminum and copper, other preparation conditions and test conditions are the same as those in Example 1. After being activated for 4 times by constant current charging and discharging at 100 mA/g current density, and then 1000 times by charging and discharging at 500 mA/g constant current, the capacity decay was 16%. However, due to the high concentration of the hydrophobic slurry, the initial capacity was lower, and the initial capacity was 93% of that of Example 1.
  • Example 1 Except that the hydrophobic material is changed to polycarbonate, the concentration of the slurry containing polycarbonate is 10 wt %, and the conductive electrode sheet is graphite foil, other preparation conditions and test conditions are the same as those in Example 1. After being activated for 4 times by constant current charging and discharging at 100 mA/g current density, and then 1000 times by charging and discharging at 500 mA/g constant current, the capacity decay was 15%. However, due to the high concentration of the hydrophobic material slurry, the initial capacity was low, and the initial capacity was 90% of that of Example 1.
  • the active material of the positive electrode is MnO 2 (70wt%), acetylene black as a conductive agent (20wt%), polyvinylidene fluoride as a binder (10wt%), N-methyl-pyrrolidone as a solvent (the combination of solvent and binder).
  • the mass ratio is 46:1) and stir to form a uniform slurry, which is coated on a conductive polyethylene film, and a slurry layer is formed on the polyethylene film, that is, a positive pole piece is made (as shown in a in Figure 4).
  • the contact angle test results of the positive pole piece are shown in a in Figure 5.
  • the positive pole piece was vacuum dried at 60 °C, it was immersed in a pH 4 adjusted with zinc oxide including 2 mol/L ZnSO 4 and 0.2mol / L of MnSO 4 in a mixed electrolyte, and assembled into metal zinc negative electrode of the secondary battery.
  • a pH 4 adjusted with zinc oxide including 2 mol/L ZnSO 4 and 0.2mol / L of MnSO 4 in a mixed electrolyte was immersed in a pH 4 adjusted with zinc oxide including 2 mol/L ZnSO 4 and 0.2mol / L of MnSO 4 in a mixed electrolyte, and assembled into metal zinc negative electrode of the secondary battery.
  • 100mA/g of current density was used for 4 times of charge-discharge activation, and then 1000 times of constant current charge and discharge with 0.5A/g current density, the cycle capacity decreased by 86%.

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Abstract

公开了一种疏水电极及其制备方法和电池，其中，所述疏水电极包括：电极基体和疏水材料层，所述疏水材料层设在所述电极基体的至少一部分表面上。

Description

疏水电极及其制备方法和电池
优先权信息
本公开请求于2020年07月16日向中国国家知识产权局提交的、专利申请号为202010684380.0、申请名称为“疏水电极及其制备方法和电池”的中国专利申请的优先权，并且其全部内容通过引用结合在本公开中。
技术领域
本公开属于电池领域，具体涉及一种疏水电极及其制备方法和电池。
背景技术
在电化学储能领域，目前空气电极表面疏水效应的处理方法主要是让碳膜表面形成整齐的纳米凸起纹路，改变空气电极的表面张力。而形成纳米凸起纹路通常需要同时采用激光刻蚀的方法和辊压机滚压的方法，操作复杂，不易控制，无法大规模应用于工业生产。
因此，现有电极的疏水方法有待改进。
公开内容
本公开旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本公开的一个目的在于提出一种疏水电极及其制备方法和电池，该疏水电极具有优异的循环稳定性，从而使得装载有该疏水电极的电池具有优异的循环性能、安全性能和容量保留率。
在本公开的第一个方面，本公开提出了一种疏水电极。根据本公开的实施例，所述疏水电极包括：
电极基体；
疏水材料层，所述疏水材料层设在所述电极基体的至少一部分表面上。
根据本公开实施例的疏水电极，通过在电极基体表面形成疏水材料层，从而阻止电极基体中的活性物质与电解液的直接接触，减轻活性物质的溶解，提高该电极的循环稳定性，从而使得装载有该疏水电极的电池具有优异的循环性能和安全性能，同时通过采用疏水材料层，该疏水材料层通过疏水作用力来排斥电解液中水分子与活性物质溶出的金属离子结合，即使得活性物质中溶出的金属离子无法迁移到电解液中，进而提升装载该疏水电极的电池的容量保留率。
另外，根据本公开上述实施例的疏水电极还可以具有如下附加的技术特征：
在本公开的一些实施例中，所述疏水材料层的厚度为0.05～995μm。由此，使得装载有 该疏水电极的电池具有优异的循环性能和容量保留率。
在本公开的一些实施例中，所述疏水材料层包括石蜡、环氧树脂、聚四氟乙烯、氟化聚乙烯、聚酰胺、聚丙烯腈、聚烯烃和聚碳酸酯中的至少之一。由此，使得装载有该疏水电极的电池具有优异的循环性能和安全性能。
在本公开的一些实施例中，所述电极基体包括：导电极片；浆料层，所述浆料层设在所述导电极片的至少一部分表面上。
在本公开的一些实施例中，所述导电极片为导电聚乙烯膜、石墨箔、碳布、碳纤维或含有不锈钢、钛、铝、铜、镍金属或合金的网状材料或箔状材料。
在本公开的一些实施例中，所述浆料层包括活性物质、粘结剂、导电剂和溶剂。
在本公开的一些实施例中，所述活性物质包括MnO 2、LiMn 2O 4、ZnMn 2O 4、LiFePO 4和LiCoO 2中的至少之一。
在本公开的第二个方面，本公开提出了一种制备上述疏水电极的方法。根据本公开的实施例，所述方法包括：
(1)提供电极基体；
(2)将含有疏水材料的浆料施加在所述电极基体的至少一部分上，以便在所述电极基体表面的至少一部分上形成疏水材料层。
根据本公开实施例的制备上述疏水电极的方法，通过将含有疏水材料的浆料施加在所述电极基体的至少一部分上，以便在所述电极基体表面的至少一部分上形成疏水材料层，该疏水材料层可以阻止电极基体中的活性物质与电解液的直接接触，减轻活性物质的溶解，提高该电极的循环稳定性，从而使得装载有该疏水电极的电池具有优异的循环性能和安全性能，同时通过采用疏水材料层，该疏水材料层通过疏水作用力来排斥电解液中水分子与活性物质溶出的金属离子结合，即使得活性物质中溶出的金属离子无法迁移到电解液中，进而提升装载该疏水电极的电池的容量保留率。
另外，根据本公开上述实施例的制备疏水电极的方法还可以具有如下附加的技术特征：
在本公开的一些实施例中，在步骤(2)中，所述含有疏水材料的浆料的质量浓度为0.1～10wt％。由此，一方面可以提高疏水材料层与电极基体的结合强度，再一方面保证含有疏水材料的浆料在电极基体表面均匀铺展，避免电极表面形成毛刺而刺穿电池隔膜，提高电池的安全性。
在本公开的一些实施例中，在步骤(2)中，所述施加方式包括旋涂覆、毛刷涂覆、浸渍或喷涂。由此，该施加方式操作简单且过程容易控制，可以大规模应用于工业生产。
在本公开的第三个方面，本公开提出了一种电池。根据本公开的实施例，所述电池的正极为上述的疏水电极或采用上述的方法得到的疏水电极。由此，该电池具有优异的循环性 能和安全性能以及容量保留率。
本公开的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本公开的实践了解到。
附图说明
本公开的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1是根据本公开一个实施例的疏水电极的纵截面结构示意图；
图2是根据本公开一个实施例的疏水电极中电极基体的纵截面结构示意图；
图3是根据本公开一个实施例的制备疏水电极的方法流程示意图；
图4中a是对比例1的正极极片的表面上的SEM图；
图4中b实施例1的石蜡溶液旋涂敷在干燥后的正极极片的表面上的SEM图；
图5中a是对比例1的正极极片的接触角测试图；
图5中b是实施例1的在正极极片形成疏水材料层的接触角测试图；
图6是实施例1和对比例1的电池的容量衰减对比图。
具体实施方式
下面详细描述本公开的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本公开，而不能理解为对本公开的限制。
在本公开的一个方面，本公开提出了一种疏水电极。根据本公开的实施例，参考图1，该疏水电极包括：电极基体100和疏水材料层200。
根据本公开的实施例，参考图2，电极基体100包括导电极片11和浆料层12，其中浆料层12设在导电极片11的至少一部分表面上，优选地浆料层12包覆在整个导电极片11的表面上。本领域技术人员可以根据实际需要选择具体的导电极片11类型，例如，本申请采用的导电极片为导电聚乙烯膜、石墨箔、碳布、碳纤维或含有不锈钢、钛、铝、铜、镍金属或合金的网状材料或箔状材料中的至少之一，同时本申请采用的浆料层12包括活性物质、粘结剂、导电剂和溶剂，其中，本领域技术人员可以根据实际需要选择具体的活性物质、粘结剂、导电剂和溶剂，例如，活性物质包括MnO 2、LiMn 2O 4、ZnMn 2O 4、LiFePO 4和LiCoO 2中的至少之一；导电剂为乙炔黑、石墨、碳纳米管和石墨烯中的至少之一，粘结剂为聚四氟乙烯(PTFE)、聚偏氟乙烯(PVDF)和丁苯橡胶(SBR)中的至少之一，溶剂为N-甲基-吡咯烷酮、羧甲基纤维素钠水溶液和羟丙基甲基纤维素水溶液中的至少之一。需要说明 的是，本领域技术人员可以根据实际需要选择组成浆料层中活性物质、导电剂、粘结剂和溶剂的混合比例。
根据本公开的实施例，参考图1，疏水材料层200设在电极基体100的至少一部分表面上，优选，疏水材料层200包覆在电极基体100的整个表面上。发明人发现，通过在电极基体表面形成疏水材料层，从而阻止电极基体中的活性物质与电解液的直接接触，减轻活性物质的溶解，提高该电极的循环稳定性，从而使得装载有该疏水电极的电池具有优异的循环性能和安全性能，同时通过采用疏水材料层，该疏水材料层通过疏水作用力来排斥电解液中水分子与活性物质溶出的金属离子结合，即使得活性物质中溶出的金属离子无法迁移到电解液中，进而提升装载该疏水电极的电池的容量保留率。
进一步地，上述疏水材料层100的厚度为0.05～995μm，例如厚度为1～20μm。发明人发现，若疏水材料层过薄，疏水效果不明显，正极材料可能存在溶出现象；而若疏水材料层过厚，导致离子扩散路径变长，内阻增大，容量发挥不佳。同时疏水材料层100包括石蜡、环氧树脂、聚四氟乙烯、氟化聚乙烯、聚酰胺、聚丙烯腈、聚烯烃和聚碳酸酯中的至少之一。
在本公开的第二个方面，本公开提出了一种制备上述疏水电极的方法。根据本公开的实施例，参考图3，该方法包括：
S100：提供电极基体
该步骤中，该电极基体为上文描述的电极基体100，此处不再赘述。
S200：将含有疏水材料的浆料施加在所述电极基体的至少一部分上
该步骤中，将含有疏水材料的浆料施加在电极基体的至少一部分上，以便在电极基体表面的至少一部分上形成疏水材料层。发明人发现，通过将含有疏水材料的浆料施加在所述电极基体的至少一部分上，以便在所述电极基体表面的至少一部分上形成疏水材料层，该疏水材料层可以阻止电极基体中的活性物质与电解液的直接接触，减轻活性物质的溶解，提高该电极的循环稳定性，从而使得装载有该疏水电极的电池具有优异的循环性能和安全性能，同时通过采用疏水材料层，该疏水材料层通过疏水作用力来排斥电解液中水分子与活性物质溶出的金属离子结合，即使得活性物质中溶出的金属离子无法迁移到电解液中，进而提升装载该疏水电极的电池的容量保留率。需要说明的是，疏水材料层的厚度和类型同于上文描述，此处不再赘述。
进一步地，所述含有疏水材料的浆料的质量浓度为0.1～10wt％，例如0.1wt％、0.2wt％……9.9wt％、10wt％。发明人发现，若该浆料质量浓度过低，则导致形成的疏水材料层与电极基体的结合强度较低，而若该浆料质量浓度过高，使得该含有疏水材料的浆料无法在电极基体表面均匀铺展而导致电极表面形成毛刺而刺穿电池隔膜。由此，采用该浓 度范围的疏水的浆料，可以在提高疏水材料层与电极基体的结合强度同时提高电池的安全性。同时，本领域技术人员可以根据实际需要选择上述浆料的施加方式，例如包括但不限于旋涂覆、毛刷涂覆、浸渍或喷涂。由此，该施加方式操作简单且过程容易控制，可以大规模应用于工业生产。需要说明的是，上述针对疏水电极所描述的特征和优点同样适用于该制备疏水电极的方法，此处不再赘述。
在本公开的第三个方面，本公开提出了一种电池。根据本公开的实施例，所述电池的正极为上述的疏水电极或采用上述的方法得到的疏水电极。由此，该电池具有优异的循环性能和安全性能以及容量保留率。需要说明的是，上述针对疏水电极及其制备方法所描述的特征和优点同样适用于该电池，此处不再赘述。
下面详细描述本公开的实施例，需要说明的是下面描述的实施例是示例性的，仅用于解释本公开，而不能理解为对本公开的限制。另外，如果没有明确说明，在下面的实施例中所采用的所有试剂均为市场上可以购得的，或者可以按照本文或已知的方法合成的，对于没有列出的反应条件，也均为本领域技术人员容易获得的。
实施例1
以金属锌为负极，正极的活性物质为MnO 2(70wt％)、乙炔黑作为导电剂(20wt％)、聚偏氟乙烯为粘结剂(10wt％)、N-甲基-吡咯烷酮为溶剂(溶剂与粘结剂的质量比为46:1)搅拌为均匀的浆料，然后将浆料涂布在导电的聚乙烯膜上，在聚乙烯膜上形成浆料层，即制成正极极片，将该正极极片于60℃真空干燥后，将浓度为1wt％的石蜡溶液旋涂覆在干燥后的正极极片的表面上(如图4中b所示)，旋涂覆转速为1200r/min，再次干燥后，在正极极片表面形成疏水材料层(疏水材料层的厚度为5μm)，该疏水材料层的接触角测试结果如图5中b所示，然后将其浸没在用氧化锌调节的pH为4的包括2mol/L的ZnSO 4和0.2mol/L的MnSO 4的混合电解液中，从而得到以金属锌为负极，石蜡包覆的MnO 2为正极的充放电电池。以0.5A/g的电流进行测试，先以100mA/g进行恒流放电到1V，然后以100mA/g进行恒流充电，经过4次活化后的1000次循环后电池的容量衰减18％(如图6所示)。
实施例2
除了疏水材料改为环氧树脂以及含有环氧树脂的浆料的浓度为1wt％、疏水材料层的厚度为3.5μm以及导电极片为石墨箔外，其它制备条件和测试条件均与实施例1相同。以100mA/g电流密度恒流充放电活化4次后，再用500mA/g恒流充放电1000次后，容量衰减为24％。
实施例3
除了正极活性物质改为ZnMn 2O 4，其它制备条件均与实施例1相同，得到以锌为负极， 石蜡包覆的ZnMn 2O 4为正极的二次电池。测试条件也与实施例1相同。根据测试结果，同样获得活化后循环1000次后容量衰减比例分别为22％。
实施例4
除了疏水材料改为聚四氟乙烯、含有聚四氟乙烯的浆料的浓度为0.1wt％以及导电极片为含有铜镍的网状材料外，其它制备条件和测试条件均与实施例1相同。以100mA/g电流密度恒流充放电活化4次后，再用500mA/g恒流充放电1000次后，容量衰减为35％。
实施例5
除了疏水材料改为氟化聚乙烯、含有氟化聚乙烯的浆料的浓度为5wt％以及导电极片为含有铝铜的箔状材料外，其它制备条件和测试条件均与实施例1相同。以100mA/g电流密度恒流充放电活化4次后，再用500mA/g恒流充放电1000次后，容量衰减为16％。但因为疏水浆料浓度高，初始容量较低，初始容量为实施例1的93％。
实施例6
除了疏水材料改为聚碳酸酯、含有聚碳酸酯的浆料的浓度为10wt％以及导电极片为石墨箔外，其它制备条件和测试条件均与实施例1相同。以100mA/g电流密度恒流充放电活化4次后，再用500mA/g恒流充放电1000次后，容量衰减为15％。但因为疏水材料浆料浓度高，初始容量较低，初始容量为实施例1的90％。
对比例1
正极的活性物质为MnO 2(70wt％)、乙炔黑作为导电剂(20wt％)、聚偏氟乙烯为粘结剂(10wt％)、N-甲基-吡咯烷酮为溶剂(溶剂与粘结剂的质量比为46:1)搅拌为均匀的浆料，涂在导电的聚乙烯膜上，在聚乙烯膜上形成浆料层，即制成正极极片(如图4中a所示)，该正极极片的接触角测试结果如图5中a所示，将该正极极片于60℃真空干燥后，然后将其浸没在用氧化锌调节的pH为4的包括2mol/L的ZnSO 4和0.2mol/L的MnSO 4的混合电解液中，与金属锌负极组装成二次电池。首先用100mA/g的电流密度进行充放电活化4次，再用0.5A/g电流密度恒流充放电1000次后，循环容量衰减86％。
对比例2
除了正极活性物质改为ZnMn 2O 4外，其它制备条件均与对比例1相同。另外，测试条件也与实施例1相同。根据测试结果，同样获得了活化后循环1000次后的容量衰减比率为67％。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本公开的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针 对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本公开的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本公开的限制，本领域的普通技术人员在本公开的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (11)

  1. 一种疏水电极，其中，包括：
    电极基体；
    疏水材料层，所述疏水材料层设在所述电极基体的至少一部分表面上。
  2. 根据权利要求1所述的疏水电极，其中，所述疏水材料层的厚度为0.05～995μm。
  3. 根据权利要求1或2所述的疏水电极，其中，所述疏水材料层包括石蜡、环氧树脂、聚四氟乙烯、氟化聚乙烯、聚酰胺、聚丙烯腈、聚烯烃和聚碳酸酯中的至少之一。
  4. 根据权利要求1-3中任一项所述的疏水电极，其中，所述电极基体包括：
    导电极片；
    浆料层，所述浆料层设在所述导电极片的至少一部分表面上。
  5. 根据权利要求1-4中任一项所述的疏水电极，其中，所述导电极片为导电聚乙烯膜、石墨箔、碳布、碳纤维或含有不锈钢、钛、铝、铜、镍金属或合金的网状材料或箔状材料。
  6. 根据权利要求1-5中任一项所述的疏水电极，其中，所述浆料层包括活性物质、粘结剂、导电剂和溶剂。
  7. 根据权利要求1-6中任一项所述的疏水电极，其中，所述活性物质包括MnO 2、LiMn 2O 4、ZnMn 2O 4、LiFePO 4和LiCoO 2中的至少之一。
  8. 一种制备权利要求1-7中任一项所述的疏水电极的方法，其中，包括：
    (1)提供电极基体；
    (2)将含有疏水材料的浆料施加在所述电极基体的至少一部分上，以便在所述电极基体表面的至少一部分上形成疏水材料层。
  9. 根据权利要求8所述的方法，其中，在步骤(2)中，所述含有疏水材料的浆料的质量浓度为0.1～10wt％。
  10. 根据权利要求8或9所述的方法，其中，在步骤(2)中，所述施加方式包括旋涂覆、毛刷涂覆、浸渍或喷涂。
  11. 一种电池，其中，所述电池的正极为权利要求1-7中任一项所述的疏水电极或采用权利要求8-10中任一项所述的方法得到的疏水电极。
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CN112002906A (zh) * 2020-07-16 2020-11-27 瑞海泊有限公司 疏水电极及其制备方法和电池

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