WO2021017598A1 - 一种制造具有保护层的电极的方法 - Google Patents

一种制造具有保护层的电极的方法 Download PDF

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WO2021017598A1
WO2021017598A1 PCT/CN2020/092478 CN2020092478W WO2021017598A1 WO 2021017598 A1 WO2021017598 A1 WO 2021017598A1 CN 2020092478 W CN2020092478 W CN 2020092478W WO 2021017598 A1 WO2021017598 A1 WO 2021017598A1
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electrode
protective layer
manufacturing
cathode
graphene
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French (fr)
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潘中来
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瑞新材料科技(香港)有限公司
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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
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    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a method for manufacturing an electrode with a protective layer, and belongs to the technical field of secondary batteries.
  • Rechargeable batteries are usually used as power sources and can be adjusted to meet the needs of low-cost and large-scale grid-scale energy storage systems.
  • lithium-ion batteries have great advantages due to high electron density and low self-discharge rate.
  • traditional lithium-ion batteries are non-aqueous batteries, which require the use of flammable organic electrolytes, which are costly and have poor safety.
  • Alternative solutions need to be considered.
  • water-based electrolyte-based rechargeable batteries with safety, high power, and large capacity have been widely studied.
  • aqueous electrolyte battery (zinc ion battery) with zinc metal anode has a wide application prospect due to its high stability, low cost and non-toxic characteristics.
  • Manganese-based cathode materials are widely used as cathode materials for rechargeable batteries (including water-based rechargeable zinc batteries) due to their numerous oxidation states (+2, +3, +4). Manganese-based cathode materials can utilize a large number of redox couples to provide batteries with high thermal stability, low cost, environmental protection, high capacity and long life. However, there are some problems in applying manganese-based cathode materials to water-based rechargeable zinc batteries.
  • the prior art generally adopts doping or applying protective coating additives in the cathode to increase the structural stability of the electrode during electrochemical cycling.
  • Patent CN201710011769.7 discloses that adding another layer of graphene protective layer on the cathode material layer can improve battery performance.
  • the method for preparing the protective layer is: 1) Disperse graphene or graphene derivative in an organic solvent to form a graphene or graphene derivative dispersion; 2) Then, combine the graphene obtained above Or the graphene derivative dispersion is added dropwise to the subphase surface in the LB film tank of the LB film forming equipment, so that the graphene or graphene derivative dispersion is spread on the subphase surface, when the graphene or graphene derivative is dispersed After the droplets are added to the surface of the subphase, the organic solvent will carry the graphene or graphene derivative particles to spread out on the surface of the subphase.
  • the organic solvent evaporates, leaving the graphene or graphene derivative particles dispersed and spread on the surface of the subphase; 3) Then, the graphene or graphene derivative particles spread on the surface of the subphase are spread on the surface of the subphase with a sliding barrier Compress to a preset film-forming molding pressure to form dense nano-films of graphene or graphene derivatives on the subphase surface; 4) Finally, transfer the graphene or graphene derivative thin films to the cathode active material layer.
  • the methods include vertical lifting method, horizontal attachment method or subphase reduction method. It can be seen that this method is complicated, requires special equipment, and has a high cost.
  • the technical problem solved by the present invention is to provide a low-cost method for manufacturing an electrode with a protective layer.
  • the method for manufacturing an electrode with a protective layer of the present invention includes the following steps:
  • the electrode pad is taken out vertically from the coating liquid at a speed of 1-9 mm/s, and dried to obtain an electrode with a protective layer, wherein the coating liquid is a dispersion liquid or the upper layer is a dispersion liquid and the lower layer is a liquid with water;
  • the dispersion liquid contains graphene or a graphene derivative.
  • the following method is used to prepare a dispersion of graphene or graphene derivatives: adding graphene or graphene derivatives to solvent 1, stirring, and then ultrasonic treatment, then adding solvent 2 and stirring to obtain Dispersions.
  • the solvent 1 may include water, alcohol, ester or ketone, and the solvent 2 may include water, alcohol, alkyl halide, ether or ketone.
  • solvent 1 includes methanol, ethanol, isopropanol or acetone;
  • solvent 2 includes ethanol, 1,2-dichloroethane, chloroform or acetone.
  • the volume ratio of solvent 1 and solvent 2 is 1:1 to 1:20. In a specific embodiment, the volume ratio of solvent 1 to solvent 2 is 1:5 to 1:15.
  • the concentration of graphene or graphene derivative in the dispersion is 0.025 to 1 mg/mL. In a specific embodiment, the concentration of graphene or graphene derivative in the dispersion is 0.075 to 1 mg/mL.
  • the electrode plates are taken out of the coating solution at a uniform speed.
  • the coating liquid is a dispersion liquid.
  • the electrode plates are vertically immersed in the coating liquid at a constant speed of 1-9 mm/s, and after staying, they are taken out vertically from the coating liquid at a constant speed of 1-9 mm/s.
  • the residence time is 5-60 seconds.
  • the following steps are repeated at least once: after the removed electrode plates are dried, they are again vertically immersed in the coating liquid, and then taken out vertically from the coating liquid at a speed of 1-9 mm/s.
  • the graphene derivative of the present invention is graphene oxide or reduced graphene oxide.
  • the electrode is a cathode.
  • the cathode is prepared by the following method: mixing and stirring the cathode active material, conductive agent, binder and solvent uniformly to obtain cathode slurry, and then coating on the current collector and drying, Obtain the cathode.
  • the cathode active material includes at least one or more materials having the formula Li 1+x Mn y M z O k , wherein -1 ⁇ x ⁇ 0.5, 1 ⁇ y ⁇ 2.5, 0 ⁇ z ⁇ 1, 3 ⁇ k ⁇ 6.
  • the cathode active material is selected from at least one of LiMn 2 O 4 and MnO 2 .
  • the present invention has the following beneficial effects:
  • the method of the invention can successfully prepare an electrode with a protective layer and improve the cycle performance of the battery. Moreover, the method is simple, has strong operability, does not require special equipment, is low in cost, and does not require toxic reagents such as hydrazine hydrate, is safe and environmentally friendly, and can be applied to industrialized mass production.
  • Figure 1 is a schematic diagram of flat float coating and suspension coating.
  • Figure 2 shows the cycle performance of a battery composed of cathodes obtained after flat floating coating and suspension coating.
  • Figure 3 shows the cycle performance of the battery composed of cathodes obtained in Examples 1 to 3.
  • Figure 4 shows the cycle performance of a battery with a cathode composition obtained in Comparative Example 1.
  • Figure 5 shows the cycle performance of the battery composed of cathodes obtained in Examples 4 to 5 and Comparative Example 2.
  • an electrode refers to a cathode or an anode, which is composed of a current collector and an active material layer on the surface of the current collector.
  • the electrode with a protective layer of the present invention has a protective layer on the outer surface of the electrode, that is, the The protective layer is located on the surface of the active material layer away from the current collector.
  • the protective layer is composed of graphene or graphene derivatives.
  • the graphene derivative of the present invention is graphene oxide or reduced graphene oxide.
  • a method of manufacturing an electrode with a protective layer of the present invention includes the following steps:
  • the electrode pad is taken out vertically from the coating liquid at a speed of 1-9 mm/s, and dried to obtain an electrode with a protective layer, wherein the coating liquid is a dispersion liquid or the upper layer is a dispersion liquid and the lower layer is a liquid with water;
  • the dispersion liquid contains graphene or a graphene derivative.
  • Dispersion is the uniform dispersion of solid particles in the liquid.
  • graphene is dispersed in a liquid, and the resulting dispersion is a graphene dispersion.
  • the graphene derivative is dispersed in a liquid, and the resulting dispersion is a graphene derivative dispersion.
  • the electrode plates are pulled out of the dispersion liquid surface at a certain speed, so that graphene or graphene derivatives are distributed and adsorbed on the surface of the plates, and after drying, an electrode with a protective layer is obtained.
  • the method is simple and does not require special equipment or special adhesives to prepare electrode plates with graphene protective layers and good performance.
  • the dispersion of graphene or graphene derivatives can be prepared by conventional methods, and only the graphene or graphene derivatives needs to be uniformly dispersed.
  • the following method is used to prepare the dispersion: adding graphene to solvent 1, stirring, and then ultrasonic treatment, then adding to solvent 2 and stirring to obtain a dispersion.
  • graphene is added to the solvent 1, stirred at room temperature for 30 minutes, and then subjected to ultrasonic treatment for 30 minutes.
  • Solvent 2 was added, and the solution was continuously stirred magnetically at room temperature for 30 minutes to obtain a uniform and well-balanced solution, that is, a dispersion.
  • the solvent 1 can be selected from water, alcohol, ester or ketone, and the solvent 2 can be selected from water, alcohol, alkyl halide, ether or ketone.
  • solvent 1 can be selected from methanol, ethanol, isopropanol or acetone;
  • solvent 2 can be selected from ethanol, 1,2-dichloroethane, chloroform or acetone.
  • Solvent 1 and solvent 2 can be combined arbitrarily without affecting the dispersion effect and the performance of the electrode obtained.
  • solvent 1 and solvent 2 can be both water, ethanol, acetone, or a combination of different solvents.
  • solvent 1 and solvent 2 are a combination of methanol and ethanol, or a combination of methanol and 1,2-dichloroethane.
  • the volume ratio of solvent 1 and solvent 2 is 1:1 to 1:20.
  • the volume ratio of solvent 1 to solvent 2 is 1:5 to 1:15.
  • the volume ratio of solvent 1 and solvent 2 may be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8 , 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, etc.
  • the concentration of graphene in the dispersion is 0.025 to 1 mg/mL.
  • the concentration of graphene in the dispersion is 0.075 to 1 mg/mL.
  • the concentration of graphene may be 0.075 mg/mL, 0.08 mg/mL, 0.1 mg/mL, 0.12 mg/mL, 0.15 mg/mL, 0.18 mg/mL, 0.2 mg/mL, 0.21mg/mL, 0.23mg/mL, 0.25mg/mL, 0.4mg/mL, 1mg/mL, etc.
  • the electrode plate is taken out from the coating solution at a specific angle and speed, so that graphene or graphene derivatives can be distributed and adsorbed on the surface of the electrode plate, and an electrode with a protective layer can be obtained.
  • the extraction rate is the key to the present invention. If the rate is too fast, it will affect the uniformity of the graphene or graphene derivative layer, and even fail to coat the protective layer, thereby affecting the electrode performance. If the rate is too slow, it will increase the operation. Cost, secondly, will result in a large difference between the immersed end and the non-immersed end of the electrode during the removal process, resulting in uneven thickness of the protective layer and affecting the cycle performance of the battery. The study found that the electrode plate was pulled out of the coating liquid surface at a speed of 1-9 mm/s, and the electrode with a protective layer obtained at this time had better performance.
  • the angle of pulling out will also affect the quality of the protective layer.
  • pulling out is vertical.
  • the vertical direction means that the axis of the electrode plate is perpendicular to the surface of the dispersion liquid.
  • the purpose of controlling the vertical pull-out is to accelerate the downflow of the dispersion liquid on the electrode surface, and prevent the excess dispersion liquid from stagnating on the electrode plate, causing defects similar to tumors and causing uneven surface of the protective layer.
  • the electrode plates are taken out at a uniform speed, and the take-out speed of the electrode plates can be variable, and the speed needs to be controlled at 0.1-10 mm/s, preferably, the control speed is 1-9 mm/s.
  • the extraction speed of the electrode plate can be 1mm/s, 1.5mm/s, 1.7mm/s, 2mm/s, 2.4mm/s, 2.8mm/s, 3mm/s, 3.5 mm/s, 4mm/s, 4.4mm/s, 5mm/s, 5.5mm/s, 6mm/s, 6.5mm/s, 7mm/s, 7.5mm/s, 8mm/s, 8.4mm/s, etc.
  • the extraction speed of the electrode plates is too slow, and the preparation process takes too long, which is not conducive to industrial mass production.
  • the coating of the present invention can be flat floating coating or suspension coating.
  • flat floating coating is the case where the upper layer of the coating liquid is the dispersion liquid and the lower layer is water. That is, the electrode is placed in water at a certain speed, and then a layer of dispersion liquid is spread on the water surface, and then the electrode is Pull out of the water at a certain speed to complete the coating.
  • the suspension coating that is, the coating liquid is directly a dispersion liquid, is to directly place the electrode in the dispersion liquid at a certain speed, and then pull the electrode out at a certain speed to complete the coating.
  • the electrode plates are vertically immersed in the coating liquid at a speed of 1-9 mm/s, and after staying, they are taken out vertically from the coating liquid at a speed of 1-9 mm/s. .
  • the immersion speed and the withdrawal speed of the electrode plates can be variable or uniform, and the immersion speed and the withdrawal speed can be the same or different.
  • the electrode plates are vertically immersed in the coating solution at a speed of 1mm/s, and after staying there, they are taken out vertically from the coating solution at a speed of 1mm/s; in another embodiment, the electrode plates Dip vertically into the coating solution at a speed of 8mm/s. After staying there, take it out of the coating solution vertically at a speed of 1mm/s; in another embodiment, the electrode plates are immersed vertically into the coating solution at a speed of 5mm/s.
  • the electrode plates are immersed vertically in the coating solution at a speed of 5mm/s, and after staying, The speed of 3mm/s is taken out vertically from the coating liquid; in another embodiment, the electrode plate is vertically immersed in the coating liquid at a speed of 3mm/s, and after staying, it is removed from the coating liquid at a speed of 3mm/s.
  • the electrode plate is vertically immersed in the coating solution at a speed of 3mm/s, and after staying there, it is removed vertically from the coating solution at a speed of 6mm/s; in another embodiment In the process, the electrode plates are vertically immersed in the coating liquid at a speed of 6 mm/s, and after staying there, they are taken out vertically from the coating liquid at a speed of 6 mm/s.
  • the residence time has a certain influence on the preparation of the protective layer.
  • the residence time is 5-60 seconds.
  • the residence time can be 5 seconds, 7 seconds, 10 seconds, 12 seconds, 15 seconds, 18 seconds, 20 seconds, 22 seconds, 24 seconds, 25 seconds, 27 seconds, 29 seconds, 30 seconds, 32 seconds, 35 seconds, 37 seconds, 40 seconds, 42 seconds, 45 seconds, 48 seconds, 50 seconds, 52 seconds, 55 seconds, 58 seconds, 60 seconds, etc.
  • the coating of the present invention may be performed only once, or may be repeated multiple times. That is, the following steps are repeated at least once: After the removed electrode plates are dried, they are vertically immersed in the coating solution, and then removed from the coating solution at a speed of 1-9 mm/s. Preferably, this step is repeated four times, that is, a total of five coatings.
  • Figure 2 shows the battery performance of a cathode with a graphene protective layer coated 5 times at a charge/discharge rate of 0.5C, where the concentration of the graphene dispersion used is 0.075mg/mL, the specific experimental conditions and the battery
  • the cycle performance data is shown in Table 1.
  • 188 laps@80% means that the cycle life of the battery at 80% capacity is 188 laps;
  • 278 laps@80% means that the cycle life of the battery at 80% capacity is 278 cycles;
  • 279 laps@80% means the battery is maintained The cycle life of 80% capacity is 279 cycles.
  • Fig. 2 It can be clearly seen from Fig. 2 that the method of the present invention can successfully form a graphene protective layer on the surface of the cathode, thereby improving the cycle performance of the battery.
  • the electrode is a cathode.
  • the cathode includes a current collector and a cathode material layer (a layer containing cathode active material) on the surface of the current collector.
  • the protective layer of the present invention is located on the surface of the cathode material layer away from the current collector.
  • the present invention has no special restrictions on the cathode current collector, and those skilled in the art can make selections according to needs.
  • the cathode current collector is usually used as a carrier for electron conduction and collection, and does not participate in the electrochemical reaction. That is, within the working voltage range of the battery, the cathode current collector can stably exist in the electrolyte without side reactions, so as to ensure that the battery has a stable Cycle performance.
  • the size of the cathode current collector can be determined according to the use of the battery. For example, if it is used in a large battery that requires high energy density, a cathode current collector with a large area can be used.
  • the thickness of the cathode current collector there is no particular limitation on the thickness of the cathode current collector, and it is usually about 1-100 ⁇ m.
  • the shape of the cathode current collector is also not particularly limited, and may be rectangular or circular, for example.
  • the material constituting the cathode current collector can be selected from aluminum, iron, copper, lead, titanium, silver, cobalt, aluminum alloy, stainless steel, copper alloy, and titanium alloy.
  • the cathode current collector can be selected From aluminum, titanium, aluminum alloy, stainless steel.
  • the cathode is prepared by the following method: the cathode active material, the conductive agent, the binder, and the solvent are mixed and evenly stirred to obtain the cathode slurry, which is then coated on the current collector and dried to obtain the cathode.
  • the cathode is prepared by the following method: the cathode mixture is formed by mixing the cathode active material, the conductive agent, the binder, and the solvent and mechanically stirring and mixing for 2 hours. The resulting mixture was then filtered with a mesh wire to obtain cathode slurry. The cathode is prepared by casting or coating the slurry on the cathode current collector and drying.
  • the cathode active material may be formed on one side of the current collector, or may be formed on both sides of the cathode current collector.
  • the cathode active material may include at least one or more materials having the formula Li 1+x Mn y M z O k , where -1 ⁇ x ⁇ 0.5, 1 ⁇ y ⁇ 2.5, 0 ⁇ z ⁇ 1, 3 ⁇ k ⁇ 6.
  • the cathode active material may include at least one or more materials selected from LiMn 2 O 4 and MnO 2 .
  • the battery performance of these manganese-based cathode water-based rechargeable zinc batteries is generally limited, and exhibits poor cycle performance during constant charge and discharge, which can be attributed to the formation of manganese ions at the cathode due to the dissolution of manganese ions into the electrolyte Inert by-products and Jahn-Teller distortion effect form lithium ion accumulation on the cathode surface, thereby limiting battery life.
  • H 2 O Decomposition (2H 2 O ⁇ O 2 + 4H + + 4e -) are common side effects in these cells, which will shorten the battery life.
  • the conductive network failure can be attributed to the oxidation of the conductive agent (C) (C+2H 2 O ⁇ CO 2 +4H + +4e - at low potential; C+xO 2 ⁇ COx at high potential). Therefore, a protective layer can be added to the cathode to improve cycle performance.
  • the conductive agent may include at least one or more materials selected from activated carbon, carbon black, graphene, graphite, carbon nanotubes, carbon fibers, and conductive polymers.
  • the conductive agent may include selected from activated carbon, carbon black, graphite At least one or more materials of alkene and carbon nanotubes.
  • the binder may include selected from polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimide, polyester, polyether, fluorinated polymer, polydivinyl polyethylene glycol, polyethylene oxide At least one or more materials of alcohol diacrylate, polyethylene glycol dimethacrylate and derivatives thereof, preferably, the adhesive may include at least one or more selected from polyvinylidene fluoride, Teflon and styrene butadiene rubber materials.
  • the solvent may include at least one or more materials selected from water, alcohols, esters, carbonates, ethers and ketones.
  • the solvent may include those selected from water, ethanol, acetone and N-methyl-2-pyrrolidone. At least one or more materials.
  • cathode slurry 150 g of LiMn 2 O 4 , 3.2 g of carbon black and 22.2 g of carbon nanotubes, 6.3 g of styrene-butadiene rubber and water were mechanically stirred and mixed at 1500 rpm for 2 hours. The resulting mixture was then filtered with a mesh wire to obtain cathode slurry. The cathode was prepared by casting the slurry on a titanium foil. After drying, cut the cathode plate into 44.5mm ⁇ 73.5mm for use.
  • the above-mentioned dipping process was repeated 4 more times to treat the cathode, and then the resulting cathode was dried at 50°C overnight. Then, the cathode, the zinc plate, and the separator were assembled to manufacture a battery cell, and immersed in an electrolyte solution under reduced pressure to perform charge and discharge tests.
  • the electrolyte is an aqueous solution of zinc sulfate and lithium sulfate.
  • the charging procedure is 0.5C constant current charging to 2.05V, constant voltage charging to 0.05C, and standing for 3 minutes.
  • the discharging procedure is constant current discharging to 1.4V and standing for 3 minutes.
  • the finished battery cell showed a specific discharge capacity of 87.9 mAh/g. At a charge/discharge rate of 0.5 C, the cycle life for the battery to maintain 80% capacity was 237 cycles.
  • cathode slurry 150 g of LiMn 2 O 4 , 3.2 g of carbon black and 31.9 g of carbon nanotubes, 6.7 g of styrene-butadiene rubber and water were mechanically stirred and mixed at 1500 rpm for 2 hours. The resulting mixture was then filtered with a mesh wire to obtain cathode slurry. The cathode was prepared by casting the slurry on a titanium foil. After drying, cut the cathode plate into 44.5mm ⁇ 73.5mm for use.
  • the above-mentioned dipping process was repeated 4 more times to treat the cathode, and dried at 50°C overnight. Then, the cathode, the zinc plate, and the separator were assembled to manufacture a battery cell, and immersed in an electrolyte solution under reduced pressure to perform charge and discharge tests.
  • the electrolyte is an aqueous solution of zinc sulfate and lithium sulfate.
  • the charging procedure is 0.5C constant current charging to 2.05V, constant voltage charging to 0.05C, and standing for 3 minutes.
  • the discharging procedure is constant current discharging to 1.4V and standing for 3 minutes.
  • the manufactured battery cell showed a specific discharge capacity of 94.9 mAh/g, and at a charge/discharge rate of 0.5C, the cycle life for the battery to maintain 80% capacity was 278 cycles.
  • cathode slurry 150 g of LiMn 2 O 4 , 3.2 g of carbon black and 31.9 g of carbon nanotubes, 6.7 g of styrene-butadiene rubber and water were mechanically stirred and mixed at 1500 rpm for 2 hours. The resulting mixture was then filtered with a mesh wire to obtain cathode slurry. The cathode was prepared by casting the slurry on a titanium foil. After drying, cut the cathode plate into 44.5mm ⁇ 73.5mm for use.
  • the electrolyte is an aqueous solution of zinc sulfate and lithium sulfate.
  • the charging procedure is 0.5C constant current charging to 2.05V, constant voltage charging to 0.05C, and standing for 3 minutes.
  • the discharging procedure is constant current discharging to 1.4V and standing for 3 minutes.
  • the manufactured battery cell showed a specific discharge capacity of 84.8 mAh/g, and at a charge/discharge rate of 0.5 C, the cycle life for the battery to maintain 80% capacity was 279 cycles.
  • cathode slurry 150 g of LiMn 2 O 4 , 3.2 g of carbon black and 22.3 g of carbon nanotubes, 6.6 g of styrene-butadiene rubber and water were mechanically stirred and mixed at 1500 rpm for 2 hours. The resulting mixture was then filtered with a mesh wire to obtain cathode slurry. The cathode was prepared by casting the slurry on a titanium foil. After drying, cut the cathode plate into 44.5mm ⁇ 73.5mm for use.
  • the above-mentioned dipping process was repeated 4 more times to treat the cathode, and dried at 50°C overnight, and then the battery was assembled. Then, the cathode, the zinc plate, and the separator were assembled to manufacture a battery cell, and immersed in an electrolyte solution under reduced pressure to perform charge and discharge tests.
  • the electrolyte is an aqueous solution of zinc sulfate and lithium sulfate.
  • the charging procedure is 1C constant current charging to 2.05V, constant voltage charging to 0.05C, and standing for 3 minutes, and the discharging procedure is 0.5C constant current discharge to 1.4V and standing for 3 minutes .
  • the manufactured battery cell showed a specific discharge capacity of 104.6 mAh/g, and the cycle life for the battery to maintain 80% capacity was 284 cycles at a charge/discharge rate of 1C/0.5C.
  • cathode slurry 150 g of LiMn 2 O 4 , 3.2 g of carbon black and 22.3 g of carbon nanotubes, 6.6 g of styrene-butadiene rubber and water were mechanically stirred and mixed at 1500 rpm for 2 hours. The resulting mixture was then filtered with a mesh wire to obtain cathode slurry. The cathode was prepared by casting the slurry on a titanium foil. After drying, cut the cathode plate into 44.5mm ⁇ 73.5mm for use.
  • the above-mentioned dipping process was repeated 4 more times to treat the cathode, and dried at 50°C overnight, and then the battery was assembled. Then, the cathode, the zinc plate, and the separator were assembled to manufacture a battery cell, and immersed in an electrolyte solution under reduced pressure to perform charge and discharge tests.
  • the electrolyte is an aqueous solution of zinc sulfate and lithium sulfate.
  • the charging procedure is 1C constant current charging to 2.05V, constant voltage charging to 0.05C, and standing for 3 minutes, and the discharging procedure is 0.5C constant current discharge to 1.4V and standing for 3 minutes .
  • the fabricated battery cell shows a specific discharge capacity of 100mAh/g. At a charge/discharge rate of 1C/0.5C, the battery retains 80% capacity and has a cycle life of 173 cycles. The uncoated graphene cathode at this rate, the battery The cycle life for maintaining 80% capacity is 147 cycles.
  • cathode slurry 150 g of LiMn 2 O 4 , 3.2 g of carbon black and 31.9 g of carbon nanotubes, 6.7 g of styrene-butadiene rubber and water were mechanically stirred and mixed at 1500 rpm for 2 hours. The resulting mixture was then filtered with a mesh wire to obtain cathode slurry. The cathode was prepared by casting the slurry on a titanium foil. After drying, cut the cathode plate into 44.5mm ⁇ 73.5mm for use.
  • the electrolyte is an aqueous solution of zinc sulfate and lithium sulfate.
  • the charging procedure is 0.5C constant current charging to 2.05V, constant voltage charging to 0.05C, and standing for 3 minutes.
  • the discharging procedure is constant current discharging to 1.4V and standing for 3 minutes.
  • the cycle performance of this battery is not improved at 0.5C charge/discharge rate.
  • the cycle life of maintaining 80% capacity is 188 cycles, and The battery after this process has a cycle life of 183 cycles while maintaining 80% capacity.
  • cathode slurry 150 g of LiMn 2 O 4 , 3.2 g of carbon black and 22.3 g of carbon nanotubes, 6.6 g of styrene-butadiene rubber and water were mechanically stirred and mixed at 1500 rpm for 2 hours. The resulting mixture was then filtered with a mesh wire to obtain cathode slurry. The cathode was prepared by casting the slurry on a titanium foil. After drying, cut the cathode plate into 44.5mm ⁇ 73.5mm for use.
  • the above-mentioned dipping process was repeated 4 more times to treat the cathode, and dried at 50°C overnight, and then the battery was assembled. Then, the cathode, the zinc plate, and the separator were assembled to manufacture a battery cell, and immersed in an electrolyte solution under reduced pressure to perform charge and discharge tests.
  • the electrolyte is an aqueous solution of zinc sulfate and lithium sulfate.
  • the charging procedure is 1C constant current charging to 2.05V, constant voltage charging to 0.05C, and standing for 3 minutes, and the discharging procedure is 0.5C constant current discharge to 1.4V and standing for 3 minutes .
  • the manufactured battery cell shows a specific discharge capacity of 96.7mAh/g. At a charge/discharge rate of 1C/0.5C, the cycle life of the battery to maintain 80% capacity is 40 cycles. When the battery pack is controlled without graphene coating, it maintains The cycle life of 80% capacity is 147 cycles.

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Abstract

本发明涉及一种制造具有保护层的电极的方法，属于二次电池技术领域。本发明解决的技术问题是提供一种低成本的制造具有保护层的电极的方法。该方法包括如下步骤：将电极板以1～9mm/s的速度从涂覆液中垂直取出，干燥，得到具有保护层的电极，其中，所述涂覆液为分散液或者上层为分散液下层为水的液体；所述分散液中包括石墨烯或石墨烯衍生物。本发明方法可以成功制备得到具有保护层的电极，提高电池的循环性能。且该方法简单，可操作性强，无需特殊的设备，成本较低，且无需水合肼等有毒试剂，安全环保，可适用于工业化大生产。

Description

一种制造具有保护层的电极的方法
相关申请的交叉引用
本申请要求在2019年7月26日提交的美国专利申请No.62879172的权益和优先权，该申请No.62879172的全部内容通过引用并入本文。
技术领域
本发明涉及一种制造具有保护层的电极的方法，属于二次电池技术领域。
背景技术
随着对小型便携式设备的要求不断提高，对电源的要求也越来越高，需要在寻求合适的，高效，紧凑，轻便和安全的可持续电源。
充电电池通常用作电源，可以进行调整以满足低成本和大型电网规模的储能系统的需求。虽然，锂离子电池由于高电子密度和低自放电率而具有很大的优势。但传统的锂离子电池为非水电池，需要使用易燃有机电解液，成本高且安全性差，需要考虑替代的方案。近来，具有安全、高功率、大容量的基于水性电解质的可充电电池被广泛研究。尤其是具有锌金属阳极的水性电解质电池(锌离子电池)，由于其具有高稳定性、低成本和无毒的特性，应用前景广泛。
锰基阴极材料由于其众多的氧化态(+2，+3，+4)而被广泛用作可充电电池(包括水性可充电锌电池)的阴极材料。锰基阴极材料能够利用大量的氧化还原电对，提供较高的热稳定性、廉价、环保、高容量和长寿命的电池。但是将锰基阴极材料在应用于水性可再充电锌电池时存在一些问题。
锰基阴极材料应用于水性可再充电锌电池时，在重复的充电和放电过程中，电池的容量衰减，循环寿命缩短。这主要是由于在使用中导电剂会氧化，而锰离子会溶解从而在阴极表面形成无活性的副产物。另外，Jahn-Teller畸变效应会导致阴极表面锂离子积聚，从而加剧锰离子的溶解，导致电池容量下降。此外，由于水分解产生的氧气环境，碳氧化问题也可能会影响导电性能，从而进一步降低电池循环寿命。所有这些上述副反应都可能极大地影响可充电电池的循环寿命。
目前，为了防止阴极退化，延长电池的寿命。现有技术中一般采取在阴极中掺杂或施加保护性涂层添加剂以增加电极在电化学循环过程中的结构稳定性。
专利CN201710011769.7公开了在阴极材料层上再增加一层石墨烯保护层，可以 改善电池性能。然而，该专利中，保护层的制备方法为：1)将石墨烯或石墨烯衍生物分散于有机溶剂中，形成石墨烯或石墨烯衍生物分散液；2)然后，将上述获得的石墨烯或石墨烯衍生物分散液滴加到LB成膜设备的LB膜槽中的亚相表面，使石墨烯或石墨烯衍生物分散液铺展于该亚相表面，当石墨烯或石墨烯衍生物分散液滴加到亚相表面后，有机溶剂会带着石墨烯或石墨烯衍生物粒子在亚相表面分散铺展开。经过一定时间之后，有机溶剂挥发，留下石墨烯或石墨烯衍生物粒子分散铺展于亚相的表面上；3)然后，用滑障将铺展于亚相表面的石墨烯或石墨烯衍生物粒子压缩至预设的成膜模压，从而在亚相表面形成石墨烯或石墨烯衍生物致密的纳米薄膜；4)最后，将石墨烯或石墨烯衍生物薄膜转移到阴极活性材料层上，所使用的方法包括垂直提拉法，水平附着法或亚相降低法等。可见，该方法复杂，需要依赖特殊的设备，成本较高。
发明内容
针对以上缺陷，本发明解决的技术问题是提供一种低成本的制造具有保护层的电极的方法。
本发明制造具有保护层的电极的方法，包括如下步骤：
将电极极板以1～9mm/s的速度从涂覆液中垂直取出，干燥，得到具有保护层的电极，其中，所述涂覆液为分散液或者上层为分散液下层为水的液体；所述分散液中含有石墨烯或石墨烯衍生物。
作为一种实施方式，采用如下方法制备得到石墨烯或石墨烯衍生物的分散液：将石墨烯或石墨烯衍生物加入溶剂1中，搅拌，然后超声处理后，再加入溶剂2，搅拌，得到分散液。
其中，所述溶剂1可以包括水、醇、酯或酮，溶剂2可以包括水，醇、卤代烷、醚或酮。在一个实施方式中，溶剂1包括甲醇，乙醇，异丙醇或丙酮；溶剂2包括乙醇、1,2-二氯乙烷、氯仿或丙酮。
在一个实施方式中，溶剂1和溶剂2的体积比为1:1～1:20。在一个具体的实施方式中，溶剂1和溶剂2的体积比为1:5～1:15。
作为一种实施方式，分散液中，石墨烯或石墨烯衍生物的浓度为0.025～1mg/mL。在一个具体的实施例中，分散液中，石墨烯或石墨烯衍生物的浓度为0.075～1mg/mL。
作为一种实施方式，电极极板从涂覆液中匀速取出。
作为一种实施方式，所述涂覆液为分散液。
在一个具体的实施方式中，将电极极板以1～9mm/s的速度匀速垂直浸入涂覆液中，停留后，再以1～9mm/s的速度匀速从涂覆液中垂直取出。
在一个实施方式中，停留的时间为5～60秒。
在一个具体的实施方式中，至少重复一次以下步骤：将取出后的电极极板干燥后，再次垂直浸入涂覆液中，再以1～9mm/s的速度从涂覆液中垂直取出。
作为一种实施方式，本发明的石墨烯衍生物，为氧化石墨烯或还原的氧化石墨烯。
作为一种实施方式，所述电极为阴极。
作为一种具体的实施方式，所述阴极采用如下方法制备得到：将阴极活性材料、导电剂、粘合剂和溶剂混合并搅拌均匀，得到阴极浆料，再涂布在集电器上，干燥，得到阴极。
在一个具体的实施方式中，阴极活性材料为包括至少一种或多种具有式Li 1+xMn yM zO k的材料，其中，-1≤x≤0.5，1≤y≤2.5，0≤z≤1，3≤k≤6。在一个实施例中，阴极活性材料选自LiMn 2O 4、MnO 2中的至少一种。
与现有技术相比，本发明具有如下有益效果：
本发明方法，可以成功制备得到具有保护层的电极，提高电池的循环性能。且该方法简单，可操作性强，无需特殊的设备，成本较低，且无需水合肼等有毒试剂，安全环保，可适用于工业化大生产。
附图说明
图1为平浮涂覆和悬浮涂覆的示意图。
图2为平浮涂覆和悬浮涂覆后所得阴极组成的电池的循环性能。
图3为实施例1～3所得阴极组成的电池的循环性能。
图4为对比例1所得阴极组成的电池的循环性能。
图5为实施例4～5,对比例2所得阴极组成的电池的循环性能。
具体实施方式
一般的，电极是指阴极或阳极，均由集流体和位于集流体表面的活性材料层组成，本发明具有保护层的电极，为在电极的外表面上具有一层保护层，即本发明的保护层位于活性材料层远离集流体的表面上。该保护层是由石墨烯或者石墨烯衍生物组成。
本发明的石墨烯衍生物，为氧化石墨烯或还原的氧化石墨烯。
本发明一种制造具有保护层的电极的方法，包括如下步骤：
将电极极板以1～9mm/s的速度从涂覆液中垂直取出，干燥，得到具有保护层的电极，其中，所述涂覆液为分散液或者上层为分散液下层为水的液体；所述分散液中含有石墨烯或石墨烯衍生物。
分散液是固体颗粒均匀分散于液体中。在本发明一个实施方式中，石墨烯分散于液体中，所得分散液为石墨烯分散液，在另一个实施方式中，石墨烯衍生物分散于液体中，所得分散液为石墨烯衍生物分散液。
本发明方法，将电极极板以一定速度提拉出分散液液面，让石墨烯或石墨烯衍生物分布吸附在极板表面，干燥后，即得具有保护层的电极。该方法简单，无需采用特殊的设备，也无需特殊的粘结剂即可制备得到具有石墨烯保护层的性能较好的电极板。
石墨烯或石墨烯衍生物的分散液可以采用常规方法制备，仅需将石墨烯或者石墨烯衍生物均匀分散即可。优选的，采用如下方法制备分散液：将石墨烯加入溶剂1中，搅拌，然后超声处理后，再加入溶剂2中，搅拌，得到分散液。
作为其中一个实施方式，将石墨烯加入溶剂1中，在室温下搅拌30分钟，随后进行超声波处理30分钟。加入溶剂2，并将溶液在室温下继续磁力搅拌30分钟，以获得均匀且匀称的溶液，即分散液。
优选的，溶剂1可以选自水、醇、酯或酮，溶剂2可以选自水，醇、卤代烷、醚或酮。作为优选的实施方式，溶剂1可以选自甲醇，乙醇，异丙醇或丙酮；溶剂2可以选自乙醇、1,2-二氯乙烷、氯仿或丙酮。溶剂1和溶剂2可以任意组合，均不影响分散效果以及所得电极的性能。比如，溶剂1和溶剂2可以都为水，乙醇，都为丙酮，也可以为不同溶剂的组合，比如溶剂1和溶剂2为甲醇和乙醇的组合、甲醇和1,2-二氯乙烷的组合、甲醇和氯仿的组合、甲醇和丙酮的组合、乙醇和1,2-二氯乙烷的组合、乙醇和氯仿的组合、乙醇和丙酮的组合、异丙醇和乙醇的组合、异丙醇和1,2-二氯乙烷的组合、异丙醇和氯仿的组合、异丙醇和丙酮的组合、丙酮和乙醇的组合、丙酮和1,2-二氯乙烷的组合、丙酮和氯仿的组合等等。
作为其中一种实施方式，溶剂1和溶剂2的体积比为1:1～1:20。优选的，溶剂1和溶剂2的体积比为1:5～1:15。在本发明的一些实施方式中，溶剂1和溶剂2的体积比可以为1:1、1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9、1:10、1:11、1:12、1:13、1:14、1:15、1:16、1:17、1:18、1:19、1:20等。
作为一种的实施方式，分散液中，石墨烯的浓度为0.025～1mg/mL。作为具体方 案，分散液中，石墨烯的浓度为0.075～1mg/mL。在本发明的一些实施方式中，石墨烯的浓度可以为0.075mg/mL、0.08mg/mL、0.1mg/mL、0.12mg/mL、0.15mg/mL、0.18mg/mL、0.2mg/mL、0.21mg/mL、0.23mg/mL、0.25mg/mL,0.4mg/mL,1mg/mL等。
采用特定的角度以及速度将电极板从涂覆液中取出，可以使得石墨烯或石墨烯衍生物分布吸附在极板表面，得到具有保护层的电极。
其中，取出速率是本发明的关键，速率过快，将会影响石墨烯或石墨烯衍生物层的均匀性，甚至无法涂上保护层，从而影响电极性能，而速率过慢，一来增加操作成本，二来会导致电极在取出过程中，浸没端与未浸没端的差异较大，从而造成保护层厚度不均一而影响电池的循环性能。研究发现，电极极板以1～9mm/s的速度拉出涂覆液液面，此时得到的具有保护层的电极性能较好。
拉出的角度也会影响保护层的质量，本发明为垂直拉出，所述的垂直是指电极板的轴线与分散液表面垂直。控制垂直拉出，主要是为了让滞留在电极表面的分散液加速下流，防止多余的分散液滞留在电极板上，产生类似于瘤的缺陷而造成保护层表面不平整。
电极极板为匀速取出，电极极板的取出速度可以为变速，需控制速度在0.1～10mm/s，优选的,控制速度在1～9mm/s。在本发明的一些实施方式中，电极极板的取出速度可以为1mm/s、1.5mm/s、1.7mm/s、2mm/s、2.4mm/s、2.8mm/s、3mm/s、3.5mm/s、4mm/s、4.4mm/s、5mm/s、5.5mm/s、6mm/s、6.5mm/s、7mm/s、7.5mm/s、8mm/s、8.4mm/s等。
电极极板取出速度过慢，制备工艺耗时过长，不利于工业上放量生产。
本发明的涂覆可以为平浮涂覆，也可以为悬浮涂覆。如图1所示，平浮涂覆为涂覆液上层为分散液下层为水的情况，即先将电极以一定速度置于水中，然后在水面上平铺一层分散液，再将电极以一定速度拉出水面，完成涂覆。而悬浮涂覆，即涂覆液直接为分散液，为直接将电极以一定速度置于分散液中，再将电极以一定速度拉出，完成涂覆。
优选的，当涂覆液为分散液时，将电极极板以1～9mm/s的速度垂直浸入涂覆液中，停留后，再以1～9mm/s的速度从涂覆液中垂直取出。
本发明中，电极极板的浸入速度和取出速度可以为变速，也可以为匀速，浸入速度和取出速度可以相同，也可以不同。在一个实施方式中，电极极板以1mm/s的速度 垂直浸入涂覆液中，停留后，再以1mm/s的速度从涂覆液中垂直取出；在另一个实施方式中，电极极板以8mm/s的速度垂直浸入涂覆液中，停留后，再以1mm/s的速度从涂覆液中垂直取出；在另一个实施方式中，电极极板以5mm/s的速度垂直浸入涂覆液中，停留后，再以5mm/s的速度从涂覆液中垂直取出；在另一个实施方式中，电极极板以5mm/s的速度垂直浸入涂覆液中，停留后，再以3mm/s的速度从涂覆液中垂直取出；在另一个实施方式中，电极极板以3mm/s的速度垂直浸入涂覆液中，停留后，再以3mm/s的速度从涂覆液中垂直取出；在另一个实施方式中，电极极板以3mm/s的速度垂直浸入涂覆液中，停留后，再以6mm/s的速度从涂覆液中垂直取出；在另一个实施方式中，电极极板以6mm/s的速度垂直浸入涂覆液中，停留后，再以6mm/s的速度从涂覆液中垂直取出。
停留时间对保护层的制备有一定的影响，优选的，b步骤中，停留的时间为5～60秒。在该停留时间内，得到的具有保护层的电极的性能较好。在本发明的一些实施方式中，停留的时间可以为5秒、7秒、10秒、12秒、15秒、18秒、20秒、22秒、24秒、25秒、27秒、29秒、30秒、32秒、35秒、37秒、40秒、42秒、45秒、48秒、50秒、52秒、55秒、58秒、60秒等。
为了提高涂覆效果，本发明的涂覆可以仅进行一次，也可以重复进行多次。即至少重复一次以下步骤：将取出后的电极极板干燥后，垂直浸入涂覆液中，再以1～9mm/s的速度从涂覆液中垂直取出。优选的，重复四次该步骤，即一共涂覆五次。
图2显示了在0.5C充电/放电速率下，涂覆5次的具有石墨烯保护层的阴极的电池性能，其中，所用石墨烯分散液的浓度为0.075mg/mL，具体的实验条件及电池的循环性能数据见表1。
表1
Figure PCTCN2020092478-appb-000001
“188圈@80％”表示电池保持80％容量的循环寿命为188圈；“278圈@80％”表示电池保持80％容量的循环寿命为278圈；“279圈@80％”表示电池保持80％容量 的循环寿命为279圈。
从图2可以明显看出，通过本发明方法，可以成功地在阴极表面形成石墨烯保护层，从而提高电池的循环性能。
作为其中一种实施方式，所述电极为阴极。
阴极包括集流体和位于集流体表面的阴极材料层(含阴极活性材料的层)，本发明的保护层位于阴极材料层远离集流体的表面上。
本发明对于阴极集流体没有特殊限制，本领域技术人员可以根据需要进行选择。阴极集流体通常作为电子传导和收集的载体，不参与电化学反应，即在电池工作电压范围内，阴极集流体能够稳定的存在于电解液中而基本不发生副反应，从而保证电池具有稳定的循环性能。阴极集流体的大小可根据电池的使用用途来确定。例如，如果在要求高能量密度的大型电池中使用，则可以使用面积大的阴极集流体。对阴极集流体的厚度没有特殊限制，通常为1～100μm左右。对于阴极集流体的形状也没有特别地限定，例如可以为长方形或圆形。对构成阴极集流体的材料没有特殊限制，阴极集流体可以选自铝，铁，铜，铅，钛，银，钴，铝合金，不锈钢，铜合金，钛合金，优选地，阴极集流体可以选自铝，钛，铝合金，不锈钢。
在一种实施方式中，采用如下方法制备得到阴极：将阴极活性材料、导电剂、粘合剂和溶剂混合并搅拌均匀，得到阴极浆料，再涂布在集电器上，干燥，得到阴极。
在一个典型的实施方式中，采用如下方法制备得到阴极：通过将阴极活性材料，导电剂，粘合剂和溶剂混合并机械搅拌并混合2小时来形成阴极混合物。然后将所得混合物用网线过滤以获得阴极浆料。通过将浆料浇铸或涂覆在阴极集流体上并干燥来制备阴极。
阴极活性物质可以形成于集流体的一面，也可以形成于阴极集流体的两面。阴极活性材料可以包括至少一种或多种具有式Li 1+xMn yM zO k的材料，其中，-1≤x≤0.5，1≤y≤2.5，0≤z≤1，3≤k≤6。优选地，阴极活性材料可包括选自LiMn 2O 4，MnO 2中的至少一种或多种材料。
这些锰基阴极水性可充电锌电池的电池性能通常受到限制，并且在恒定的充电和放电过程中表现出较差的循环性能，这可以归因于由于锰离子溶解到电解质中而在阴极形成的惰性副产物以及Jahn-Teller畸变效应在阴极表面形成锂离子积累，从而限制电池寿命。此外，H 2O分解(2H 2O→O 2+4H ++4e -)是在这些电池中常见的副反应， 这亦会缩短电池的使用寿命。导电网络故障可归因于导电剂(C)的氧化(在低电势下为C+2H 2O→CO 2+4H ++4e -；在高电势下为C+xO 2→COx)。因此，可以在阴极添加保护层来提高循环性能。
导电剂可以包括选自活性炭，炭黑，石墨烯，石墨，碳纳米管，碳纤维和导电聚合物中的至少一种或多种材料，优选地，导电剂可以包括选自活性炭，碳黑，石墨烯和碳纳米管中的至少一种或多种材料。
粘合剂可以包括选自聚环氧乙烷，聚环氧丙烷，聚丙烯腈，聚酰亚胺，聚酯，聚醚，氟化聚合物，聚二乙烯基聚乙二醇，聚乙二醇二丙烯酸酯，聚乙二醇二甲基丙烯酸酯及其衍生物中的至少一种或多种材料，优选地，粘合剂可以包括至少一种或多种选自聚偏二氟乙烯，聚四氟乙烯和丁苯橡胶的材料。
溶剂可以包括选自水，醇，酯，碳酸盐，醚和酮的至少一种或多种材料，优选地，溶剂可以包括选自水，乙醇，丙酮和N-甲基-2-吡咯烷酮的至少一种或多种材料。
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的实施例范围之中。
实施例1
将150g的LiMn 2O 4，3.2g的炭黑和22.2g的碳纳米管，6.3g的苯乙烯-丁二烯橡胶和水机械搅拌并在1500rpm下混合2小时。然后将所得混合物用网线过滤以获得阴极浆料。通过将浆料浇铸在钛箔上来制备阴极。干燥后，将阴极板切成44.5mm×73.5mm，备用。
称量10mg还原的氧化石墨烯并添加50mL乙醇，将所得溶液在室温搅拌30分钟，随后进行超声处理30分钟。之后，加入另外的350mL乙醇，并将溶液在室温下继续磁力搅拌30分钟，以获得均匀且匀称的溶液。然后将阴极以8.4mm/s的恒定速度垂直朝着还原的氧化石墨烯溶液向下移动，在阴极所有部分浸入溶液中后，将阴极保持静止10秒钟，然后再将阴极垂直移出，恒定速度为1.7mm/s。在50℃下干燥5分钟后，将上述浸渍过程再重复4次以处理阴极，然后将所得的阴极在50℃下干燥过夜。然后，将阴极，锌板和隔板组装以制造电池单元，并在减压下浸入电解质溶液中以进行充电和放电测试。
电解液为硫酸锌，硫酸锂的水溶液，充电程序为0.5C恒流充电至2.05V，恒压充电至0.05C，静置3分钟，放电程序为恒流放电至1.4V，静置3分钟。
制成的电池单元显示出87.9mAh/g的比放电容量，在0.5C的充电/放电速率下，电池保持80％容量的循环寿命为237圈。
实施例2
将150g的LiMn 2O 4，3.2g的炭黑和31.9g的碳纳米管，6.7g的苯乙烯-丁二烯橡胶和水机械搅拌并在1500rpm下混合2小时。然后将所得混合物用网线过滤以获得阴极浆料。通过将浆料浇铸在钛箔上来制备阴极。干燥后，将阴极板切成44.5mm×73.5mm，备用。
称量30mg还原的氧化石墨烯并添加50mL乙醇，将所得溶液在室温下搅拌30分钟，随后超声处理30分钟。之后，再添加350mL的1，2-二氯乙烷，并将该溶液在室温下继续磁力搅拌30分钟，以获得均匀且匀称的溶液。然后以1.7mm/s的恒定速度将阴极垂直向下移向500mL水中，在将阴极的所有部分浸入水中之后，然后向水面滴加0.04mL还原的氧化石墨烯溶液，保持静止60秒，然后再将阴极垂直移出。恒定速度为1.7mm/s。在50℃下干燥5分钟后，将上述浸渍过程再重复4次以处理阴极，并在50℃下干燥过夜。然后，将阴极，锌板和隔板组装以制造电池单元，并在减压下浸入电解质溶液中以进行充电和放电测试。电解液为硫酸锌，硫酸锂的水溶液，充电程序为0.5C恒流充电至2.05V，恒压充电至0.05C，静置3分钟，放电程序为恒流放电至1.4V，静置3分钟。
所制造的电池单元显示出94.9mAh/g的比放电容量，在0.5C充电/放电速率下，电池保持80％容量的循环寿命为278圈。
实施例3
将150g的LiMn 2O 4，3.2g的炭黑和31.9g的碳纳米管，6.7g的苯乙烯-丁二烯橡胶和水机械搅拌并在1500rpm下混合2小时。然后将所得混合物用网线过滤以获得阴极浆料。通过将浆料浇铸在钛箔上来制备阴极。干燥后，将阴极板切成44.5mm×73.5mm，备用。
称量30mg还原的氧化石墨烯并添加50mL乙醇，将所得溶液在室温下搅拌30分钟，随后超声处理30分钟。之后，再添加350mL的1，2-二氯乙烷，并将该溶液在室温下继续磁力搅拌30分钟，以获得均匀且匀称的溶液。然后以8.4mm/s的恒定速度将阴极垂直向下移向还原的氧化石墨烯溶液，在将阴极的所有部分浸入溶液中之后，将阴极保持静止60秒，然后再将阴极垂直移出，恒定速度为1.7mm/s。在50℃下干燥5 分钟后，将上述浸渍过程再重复4次以处理阴极，并在50℃下干燥过夜，然后组装电池。然后，将阴极，锌板和隔板组装以制造电池单元，并在减压下浸入电解质溶液中以进行充电和放电测试。电解液为硫酸锌，硫酸锂的水溶液，充电程序为0.5C恒流充电至2.05V，恒压充电至0.05C，静置3分钟，放电程序为恒流放电至1.4V，静置3分钟。
所制造的电池单元显示出84.8mAh/g的比放电容量，在0.5C充电/放电速率下，电池保持80％容量的循环寿命为279圈。
实施例4
将150g的LiMn 2O 4，3.2g的炭黑和22.3g的碳纳米管，6.6g的苯乙烯-丁二烯橡胶和水机械搅拌并在1500rpm下混合2小时。然后将所得混合物用网线过滤以获得阴极浆料。通过将浆料浇铸在钛箔上来制备阴极。干燥后，将阴极板切成44.5mm×73.5mm，备用。
称量250mg石墨烯并添加250mL乙醇，将所得溶液在室温下搅拌30分钟，随后超声处理30分钟。之后，再将该溶液在室温下继续磁力搅拌30分钟，以获得均匀且匀称的溶液。然后以8.4mm/s的恒定速度将阴极垂直向下移向石墨烯溶液，在将阴极的所有部分浸入溶液中之后，将阴极保持静止10秒，然后再将阴极垂直移出，恒定速度为8.4mm/s。在50℃下干燥5分钟后，将上述浸渍过程再重复4次以处理阴极，并在50℃下干燥过夜，然后组装电池。然后，将阴极，锌板和隔板组装以制造电池单元，并在减压下浸入电解质溶液中以进行充电和放电测试。电解液为硫酸锌，硫酸锂的水溶液，充电程序为1C恒流充电至2.05V，恒压充电至0.05C，静置3分钟，放电程序为0.5C恒流放电至1.4V，静置3分钟。
所制造的电池单元显示出104.6mAh/g的比放电容量，在1C/0.5C充电/放电速率下，电池保持80％容量的循环寿命为284圈。
实施例5
将150g的LiMn 2O 4，3.2g的炭黑和22.3g的碳纳米管，6.6g的苯乙烯-丁二烯橡胶和水机械搅拌并在1500rpm下混合2小时。然后将所得混合物用网线过滤以获得阴极浆料。通过将浆料浇铸在钛箔上来制备阴极。干燥后，将阴极板切成44.5mm×73.5mm，备用。
称量250mg氧化石墨烯并添加250mL乙醇，将所得溶液在室温下搅拌30分钟，随后超声处理30分钟。之后，再将该溶液在室温下继续磁力搅拌30分钟，以获得均匀且匀称的溶液。然后以8.4mm/s的恒定速度将阴极垂直向下移向氧化石墨烯溶液，在将阴极的所有部分浸入溶液中之后，将阴极保持静止10秒，然后再将阴极垂直移出，恒定速度为1.7mm/s。在50℃下干燥5分钟后，将上述浸渍过程再重复4次以处理阴极，并在50℃下干燥过夜，然后组装电池。然后，将阴极，锌板和隔板组装以制造电池单元，并在减压下浸入电解质溶液中以进行充电和放电测试。电解液为硫酸锌，硫酸锂的水溶液，充电程序为1C恒流充电至2.05V，恒压充电至0.05C，静置3分钟，放电程序为0.5C恒流放电至1.4V，静置3分钟。
所制造的电池单元显示出100mAh/g的比放电容量，在1C/0.5C充电/放电速率下，电池保持80％容量的循环寿命为173圈，无涂覆石墨烯阴极在该倍率下，电池保持80％容量的循环寿命为147圈。
对比例1
将150g的LiMn 2O 4，3.2g的炭黑和31.9g的碳纳米管，6.7g的苯乙烯-丁二烯橡胶和水机械搅拌并在1500rpm下混合2小时。然后将所得混合物用网线过滤以获得阴极浆料。通过将浆料浇铸在钛箔上来制备阴极。干燥后，将阴极板切成44.5mm×73.5mm，备用。
称量30mg还原的氧化石墨烯，并添加400mL乙醇，将所得溶液在室温下搅拌30分钟，随后超声处理30分钟。之后，再将该溶液在室温下继续磁力搅拌30分钟，以获得均匀且匀称的溶液。然后以10mm/s的恒定速度将带有活性物质的阴极极板垂直向下移向还原的氧化石墨烯溶液，在将极板的所有部分浸入溶液中之后，保持静止10秒，然后再以10mm/s速度将极板垂直拉出石墨烯分散液，50度干燥3min，重复上述涂覆过程4次，之后50℃烘干极片，然后，将阴极，锌板和隔板组装以制造电池单元，并在减压下浸入电解质溶液中以进行充电和放电测试。电解液为硫酸锌，硫酸锂的水溶液，充电程序为0.5C恒流充电至2.05V，恒压充电至0.05C，静置3分钟，放电程序为恒流放电至1.4V，静置3分钟。
该电池与无石墨烯涂覆的控制组电池对比，在0.5C充电/放电速率下，循环性能无提升，控制组电池无石墨烯涂覆时，保持80％容量的循环寿命为188圈，而经过该工艺处理后的电池，保持80％容量的循环寿命为183圈。
对比例2
将150g的LiMn 2O 4，3.2g的炭黑和22.3g的碳纳米管，6.6g的苯乙烯-丁二烯橡胶和水机械搅拌并在1500rpm下混合2小时。然后将所得混合物用网线过滤以获得阴极浆料。通过将浆料浇铸在钛箔上来制备阴极。干燥后，将阴极板切成44.5mm×73.5mm，备用。
称量250mg石墨烯并添加250mL乙醇，将所得溶液在室温下搅拌30分钟，随后超声处理30分钟。之后，再将该溶液在室温下继续磁力搅拌30分钟，以获得均匀且匀称的溶液。然后以0.5mm/s的恒定速度将阴极垂直向下移向石墨烯溶液，在将阴极的所有部分浸入溶液中之后，将阴极保持静止10秒，然后再将阴极垂直移出，恒定速度为0.5mm/s。在50℃下干燥5分钟后，将上述浸渍过程再重复4次以处理阴极，并在50℃下干燥过夜，然后组装电池。然后，将阴极，锌板和隔板组装以制造电池单元，并在减压下浸入电解质溶液中以进行充电和放电测试。电解液为硫酸锌，硫酸锂的水溶液，充电程序为1C恒流充电至2.05V，恒压充电至0.05C，静置3分钟，放电程序为0.5C恒流放电至1.4V，静置3分钟。
所制造的电池单元显示出96.7mAh/g的比放电容量，在1C/0.5C充电/放电速率下，电池保持80％容量的循环寿命为40圈，控制组电池无石墨烯涂覆时，保持80％容量的循环寿命为147圈。

Claims (18)

  1. 一种制造具有保护层的电极的方法，其特征在于，包括如下步骤：
    将电极极板以1～9mm/s的速度从涂覆液中垂直取出，干燥，得到具有保护层的电极，其中，所述涂覆液为分散液或者上层为分散液下层为水的液体；所述分散液中含有石墨烯或石墨烯衍生物。
  2. 根据权利要求1所述的制造具有保护层的电极的方法，其特征在于：采用如下方法制备得到分散液：将石墨烯或石墨烯衍生物加入溶剂1中，搅拌，然后超声处理后，再加入溶剂2，搅拌，得到分散液。
  3. 根据权利要求2所述的制造具有保护层的电极的方法，其特征在于：所述溶剂1包括水、醇、酯或酮，溶剂2包括水，醇、卤代烷、醚或酮。
  4. 根据权利要求3所述的制造具有保护层的电极的方法，其特征在于：溶剂1包括甲醇，乙醇，异丙醇或丙酮；溶剂2包括乙醇、1,2-二氯乙烷、氯仿或丙酮。
  5. 根据权利要求2所述的制造具有保护层的电极的方法，其特征在于：溶剂1和溶剂2的体积比为1:1～1:20。
  6. 根据权利要求5所述的制造具有保护层的电极的方法，其特征在于：溶剂1和溶剂2的体积比为1:5～1:15。
  7. 根据权利要求1所述的制造具有保护层的电极的方法，其特征在于：分散液中，石墨烯或石墨烯衍生物的浓度为0.025～1mg/mL。
  8. 根据权利要求7所述的制造具有保护层的电极的方法，其特征在于：分散液中，石墨烯或石墨烯衍生物的浓度为0.075～1mg/mL。
  9. 根据权利要求1所述的制造具有保护层的电极的方法，其特征在于：电极极板从涂覆液中匀速取出。
  10. 根据权利要求1所述的制造具有保护层的电极的方法，其特征在于：所述涂覆液为分散液。
  11. 根据权利要求10所述的制造具有保护层的电极的方法，其特征在于：将电极极板以1～9mm/s的速度匀速垂直浸入涂覆液中，停留后，再以1～9mm/s的速度匀速从涂覆液中垂直取出。
  12. 根据权利要求11所述的制造具有保护层的电极的方法，其特征在于：停留的时间为5～60秒。
  13. 根据权利要求1所述的制造具有保护层的电极的方法，其特征在于：至少重复一次以下步骤：将取出后的电极极板干燥后，再次垂直浸入涂覆液中，再以1～9mm/s的速度从涂覆液中垂直取出。
  14. 根据权利要求1所述的制造具有保护层的电极的方法，其特征在于：所述石墨烯衍生物为氧化石墨烯或还原的氧化石墨烯。
  15. 根据权利要求1所述的制造具有保护层的电极的方法，其特征在于：所述电极为阴极。
  16. 根据权利要求15所述的制造具有保护层的电极的方法，其特征在于：所述阴极采用如下方法制备得到：将阴极活性材料、导电剂、粘合剂和溶剂混合并搅拌均匀，得到阴极浆料，再涂布在集电器上，干燥，得到阴极。
  17. 根据权利要求16所述的制造具有保护层的电极的方法，其特征在于：阴极活性材料为包括至少一种或多种具有式Li 1+xMn yM zO k的材料，其中，-1≤x≤0.5，1≤y≤2.5，0≤z≤1，3≤k≤6。
  18. 根据权利要求17所述的制造具有保护层的电极的方法，其特征在于：阴极活性材料选自LiMn 2O 4、MnO 2中的至少一种。
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