WO2020155565A1 - 用于氯化铝—-碳电池的正极材料的制备方法及使用方法 - Google Patents

用于氯化铝—-碳电池的正极材料的制备方法及使用方法 Download PDF

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WO2020155565A1
WO2020155565A1 PCT/CN2019/095554 CN2019095554W WO2020155565A1 WO 2020155565 A1 WO2020155565 A1 WO 2020155565A1 CN 2019095554 W CN2019095554 W CN 2019095554W WO 2020155565 A1 WO2020155565 A1 WO 2020155565A1
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carbon
aluminum chloride
carbon fiber
positive electrode
fiber cloth
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English (en)
French (fr)
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高炳亮
刘成员
李启明
刘智伟
牛宏坤
王兆文
胡宪伟
石忠宁
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东北大学
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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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/58—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention belongs to the technical field of aluminum batteries, and particularly relates to a method for preparing and using a cathode material for aluminum chloride-carbon batteries.
  • Lithium-ion batteries have been practically used due to their advantages of low self-discharge and high mass specific capacity, and have achieved industrial production; however, the natural abundance of lithium is low, and defects such as flammability in the air and easy formation of dendrites limit the It is further commercialized.
  • the anode material of aluminum ion battery is metal aluminum or alloy. Aluminum is abundant in nature and stably exists in the air. Its mass specific capacity density can reach 2980mAh/g, and its volume specific capacity density can reach 8040mAh. /cm 3 .
  • CN2015109 02386.X discloses the use of an improved hummers method to prepare graphene oxide, and then a hydrazine hydrate reducing agent to prepare graphene cathode materials
  • CN201610390212.4 discloses the use of chemical vapor deposition to deposit multiple layers of graphene on foam metal to prepare porous three-dimensional graphene cathode materials
  • CN201610845761.6 discloses electrospinning equipment for graphene oxide or graphene oxide inorganic salt mixture Preparation of graphene oxide cloth and reduced graphene cloth cathode material
  • CN201610281036.0 discloses adding organic carbon source and graphite material to a solvent to perform high-pressure solvothermal reaction and high-temperature carbonization to prepare a cathode active material, and then adopt a coating method to prepare the cathode material
  • CN201711173282.5 discloses that graphite foam powder prepared by
  • the graphite foam slurry is coated on a substrate. After drying, A graphite foam layer is formed on the upper surface, and the substrate coated with the graphite foam layer is immersed in the first setting solution, and after the substrate is dissolved, the graphite foam layer is post-processed to obtain the graphite foam sheet cathode material;
  • a graphene oxide foam is prepared by a freeze-drying method, and then the graphene foam is obtained by chemical reduction, and a high-temperature heat treatment is performed for thermal reduction to obtain a super high-conductivity graphene foam cathode material;
  • CN201710685318.1 discloses that expanded graphite is subjected to a high temperature of 2000-3000 °C After treatment, it is pressed into a film under a pressure of 1.5-35 MPa as the anode of the aluminum ion battery.
  • the preparation methods of high-performance cathode materials mainly focus on the hummers method and chemical vapor deposition.
  • Graphene oxide cloth or reduced graphene cloth is prepared by multi-product method and electrospinning technology; these preparation methods have complex processes, high costs, and high equipment requirements, which hinder their commercial development.
  • the object of the present invention is to provide a method for preparing a positive electrode material for aluminum chloride-carbon batteries and a method of using it.
  • the pulverized carbon material with a graphite structure is adsorbed on a carbon fiber cloth and used as aluminum.
  • the cathode material of the ion battery simplifies the process and reduces the cost while improving the performance of the aluminum battery.
  • the method for preparing a cathode material for aluminum chloride-carbon batteries of the present invention is carried out in the following steps:
  • the carbon fiber is placed in ethanol for ultrasonic cleaning for 30-60 minutes, and then placed in deionized water for ultrasonic cleaning for 30-60 minutes. After being taken out, it is placed under vacuum and dried at 80-150°C for 12-24 hours , Obtain pretreated carbon fiber cloth;
  • the carbon raw material is dispersed in an organic solvent, and the carbon raw material in the organic solvent is crushed by ultrasonic treatment or high-shear stirring and made into a suspension;
  • the carbon raw material is natural graphite, porous activated carbon, Highly oriented graphite or graphitized expanded graphite with a purity of 99.5-99.9% ;
  • the organic solvent is absolute ethanol, N-methylpyrrolidone, dimethylformamide, dimethylacetamide or dimethylsulfoxide; carbon
  • the mass ratio of raw material to organic solvent is (1 ⁇ 10): 100;
  • the ultrasonic treatment time is 0.5-12 h.
  • the stirring rate of the high-shear stirring is 1000 ⁇ 2000rpm, and the time is 0.5 ⁇ 6h.
  • the density of the carbon material on the surface of the carbon fiber cloth is 0.5-10 mg/cm 2 .
  • the method of using the cathode material for aluminum chloride-carbon batteries of the present invention is:
  • the positive electrode material used for aluminum chloride-carbon batteries is used as the positive electrode, aluminum foil is used as the negative electrode, and glass
  • the fiber filter paper is used as the separator, and the positive electrode, the negative electrode, the separator and the electrolyte are assembled into an aluminum chloride-carbon battery.
  • the above-mentioned aluminum chloride-carbon battery also includes a current collector and a soft case; the current collector is carbon fiber cloth, metallic molybdenum, metallic tungsten, or metal foil attached with a titanium nitride coating, wherein the metallic foil is The material is nickel metal, stainless steel, copper metal, metal alloy, or metal alloy.
  • the above-mentioned electrolyte is aluminum chloride-1-ethyl-3-methylimidazole chloride, aluminum chloride-1-butyl-3-methylimidazole chloride, aluminum chloride-triethylamine hydrochloride, aluminum chloride - urea, aluminum chloride - acetamide, aluminum chloride - propionamide or aluminum chloride - butyramide; A1C1 3 mole percent of the electrolyte is 52 to 67%.
  • LiCl, LiBr, NaCl, NaBr, EC ethylene carbonate
  • THF tetrahydrofuran
  • DCE tetrahydrofuran
  • the preparation process is simple and controllable. Active material suspensions of different concentrations can be obtained by controlling the mass ratio of the carbon material raw material to the organic solvent and the processing time; the positive electrodes of different loadings can be obtained by controlling the number of dropping or spraying Material
  • the cathode material is an unbonded cathode material, which prevents the electrolyte from reacting with the binder to damage the electrode structure, and the three-dimensional porous network structure of the carbon fiber cloth substrate provides a channel for the rapid migration of ions
  • the aluminum chloride-carbon battery assembled with the positive electrode material as the positive electrode has an average working voltage of 1.5 ⁇ 2.0V, a specific discharge mass capacity of 100 ⁇ 350mAh/g, and a mass specific energy density of 200 ⁇ 650Wh/kg;
  • FIG. 1 is a Raman spectrum of the carbon raw material in Example 1 of the present invention after crushing
  • FIG. 2 is a field emission scanning electron micrograph of the cathode material used in the aluminum chloride-carbon battery in Example 1 of the present invention
  • FIG. 3 shows the cathode material used in the aluminum chloride-carbon battery in Example 1 of the present invention at a scan rate of 0.2 mV/s The cyclic voltammetry curve below;
  • FIG. 4 is a charging and discharging curve diagram of the positive electrode material used in the aluminum chloride-carbon battery in Example 1 of the present invention under the condition of a current density of 100 mA/g; in the figure, ⁇ is charging and Xin is discharging.
  • the ultrasonic power during ultrasonic processing is 100 to 600 W.
  • the carbon fiber cloth used in the embodiment of the present invention is a commercially available product.
  • the carbon fiber cloth used in the embodiment of the present invention is 12.5mg/cm 2 and has a thickness of 0.036cm; before use, the carbon fiber cloth is cut into a square (10-15) mmx (10-15) mm or a circle with a diameter of 10-18 mm shape.
  • the carbon raw materials used in the embodiments of the present invention are all commercially available products with a purity of 99.5 to 99.9%.
  • anhydrous A1C1 3 with a purity of >99% is used for the preparation of the electrolyte, which is directly placed in a glove box under an argon atmosphere for storage.
  • LiCl, LiBr, NaCl, NaBr, EC (ethylene carbonate), THF (tetrahydrofuran), and DCE (1,2-dichloroethane) used in the embodiments of the present invention are commercially available analytical reagents, before use Vacuum dry and place in a glove box under argon atmosphere for storage.
  • EMIC, acetamide, urea, propionamide, and butyramide used in the embodiments of the present invention are all commercially available reagents, which are vacuum dried before use and placed in an argon atmosphere glove box for storage.
  • the conditions of vacuum drying in the embodiment of the present invention are: 60 ⁇ 120°C drying for 12 ⁇ 24 hours, and vacuum degree ⁇ 50Pa.
  • the water and oxygen content in the glove box used in the embodiments of the present invention are both less than 0.1 ppm.
  • the carbon cloth, metal molybdenum, metal tungsten, and metal foil with titanium nitride coating used in the embodiments of the present invention are commercially available products, and surface impurities are removed before use.
  • the purity is 299.9%, and the preparation method of the titanium carbide coating is as described in the literature (Adv. Sci. 2018, 5, 1700712:
  • the flexible current collector is prepared from the abundant elements of the earth for aluminum chloride _ graphite battery).
  • the aluminum chloride-carbon battery in the embodiment of the present invention has a discharge mass specific capacity of 110 to 300 mAh/g under the condition of a current density of 100 to 1000 mA/g.
  • the carbon fiber was placed in ethanol for ultrasonic cleaning for 30 minutes, and then placed in deionized water for ultrasonic Wave cleaning for 30 minutes, after taking it out, place it under vacuum, and dry at 80°C for 24 hours to obtain a pretreated carbon fiber cloth;
  • the carbon raw material is dispersed in an organic solvent, and the carbon raw material in the organic solvent is crushed by ultrasonic treatment and made into a suspension; the carbon raw material is natural graphite; the organic solvent is N-methylpyrrolidone; carbon raw material and organic
  • the mass ratio of the solvent is 1: 100; the Raman spectrum of the obtained carbon raw material is shown in Figure 1; where the ultrasonic treatment time is 0.5h;
  • the method of using the cathode material for the aluminum chloride-carbon battery is:
  • the positive electrode material used for the aluminum chloride-carbon battery is used as the positive electrode, the aluminum foil is used as the negative electrode, and the glass fiber filter paper is used as the separator, and the positive electrode, the negative electrode, the separator and the electrolyte are assembled into an aluminum chloride-carbon battery;
  • - carbon battery further includes a current collector and a soft package shell; current collector is a carbon fiber sheet; electrolyte aluminum chloride-1-ethyl 3 - methylimidazolium chloride; eight electrolyte 1 (: 1 mole percentage of 67 3 %;
  • the Shenzhen Xinweier battery test system was used for constant current charge and discharge test.
  • the charge and discharge curve of the aluminum chloride-carbon battery at a current density of 100mA/g is shown in Figure 4; the charge and discharge cut-off voltage is 0.01 ⁇ 2.45V, the discharge mass specific capacity of the battery is 260mAh/g.
  • the carbon fiber was placed in ethanol for ultrasonic cleaning for 35min, and then placed in deionized water for ultrasonic cleaning for 40min, after being taken out, it was placed under vacuum and dried at 90°C for 22h;
  • the carbon raw material is dispersed in an organic solvent, and the carbon raw material in the organic solvent is pulverized by high shear stirring and made into a suspension; the carbon raw material is porous activated carbon; the organic solvent is anhydrous ethanol; carbon The mass ratio of the raw materials and the organic solvent is 2: 100; the stirring rate of high-shear stirring is lOOOrpm, the time is OJh;
  • the current collector used is metallic molybdenum
  • the electrolyte used is aluminum chloride-1-butyl-3-methylimidazole chloride; the mole percentage of A1C1 3 in the electrolyte is 66%;
  • additives are added to the electrolyte, and the additives account for the total moles of the electrolyte
  • the additive is LiCl
  • the carbon fiber was placed in ethanol for ultrasonic cleaning for 40min, and then placed in deionized water for ultrasonic cleaning for 35min, after being taken out, it was placed under vacuum and dried at 100°C for 20h;
  • the carbon raw material is highly oriented graphite; the organic solvent is dimethylformamide; the mass ratio of the carbon raw material to the organic solvent is 3: 100; the ultrasonic treatment time is 2h;
  • the current collector used is metallic tungsten
  • the electrolyte used is aluminum chloride-triethylamine hydrochloride; A1C1 3 in the electrolyte
  • the mole percentage of is 64%
  • the preparation method is the same as in Example 1, the difference lies in: [0068] (1) The carbon fiber was placed in ethanol for ultrasonic cleaning for 45min, then placed in deionized water for ultrasonic cleaning for 35min, and then placed under vacuum conditions after removal, dried at 110 ° C for 18h;
  • the carbon raw material is dispersed in an organic solvent, and the carbon raw material in the organic solvent is pulverized by high shear stirring and made into a suspension; the carbon raw material is graphitized expanded graphite; the organic solvent is dimethyl Acetamide; the mass ratio of carbon raw material to organic solvent is 4: 100; the stirring rate of high-shear stirring is 1500 rpm, and the time is 1h
  • the current collector used is a metal foil with a titanium nitride coating attached, and the material of the metal foil is nickel metal;
  • the electrolyte used is aluminum chloride-urea; the mole percentage of A1C1 3 in the electrolyte is 62%;
  • additives are added to the electrolyte, and the additives account for the total moles of the electrolyte
  • the additive is NaCl
  • the carbon fiber was placed in ethanol for ultrasonic cleaning for 50min, and then placed in deionized water for ultrasonic cleaning for 60min, after being taken out, it was placed under vacuum and dried at 120°C for 16h;
  • the carbon raw material is porous activated carbon; the organic solvent is dimethyl sulfoxide; the mass ratio of the carbon raw material to the organic solvent is 6: 100; the ultrasonic treatment time is %;
  • the current collector used is a metal foil with titanium nitride coating attached, and the material of the metal foil is rust. steel;
  • the electrolyte used is aluminum chloride-acetamide; the mole percentage of A1C1 3 in the electrolyte is 60%;
  • the carbon fiber was placed in ethanol for ultrasonic cleaning for 55min, and then placed in deionized water for ultrasonic cleaning for 50min, after being taken out, it was placed under vacuum and dried at 130°C for 15h;
  • the carbon raw material is dispersed in an organic solvent, and the carbon raw material in the organic solvent is pulverized by high-shear stirring and made into a suspension; the carbon raw material is highly oriented graphite; the organic solvent is dimethyl ethyl Amide; the mass ratio of carbon raw material and organic solvent is 8: 100; the stirring rate of high-shear stirring is 1800rpm, the time is 4h;
  • the current collector used is a metal foil with a titanium nitride coating attached, and the material of the metal foil is copper;
  • the electrolyte used is aluminum chloride-propionamide; the mole percentage of A1C1 3 in the electrolyte is 57%;
  • the carbon fiber was placed in ethanol for ultrasonic cleaning for 60min, and then placed in deionized water for ultrasonic cleaning for 30min, after being taken out, it was placed under vacuum and dried at 140°C for 14h;
  • the carbon raw material is graphitized expanded graphite; the organic solvent is absolute ethanol; the carbon raw material and the organic solvent The mass ratio is 9: 100; the ultrasonic treatment time is 12 h;
  • the current collector used is a metal foil attached with a titanium nitride coating, wherein the material of the metal foil is metal aluminum;
  • the electrolyte used is aluminum chloride-butyramide; the mole percentage of A1C1 3 in the electrolyte is 54%;
  • the carbon raw material is dispersed in an organic solvent, and the carbon raw material in the organic solvent is pulverized by high-shear stirring and made into a suspension; the carbon raw material is graphitized expanded graphite; the organic solvent is dimethyl Formamide; The mass ratio of carbon raw material to organic solvent is 10: 100; The stirring rate of high-shear stirring is 2000 rpm, and the time is 6 h;
  • the current collector used is a metal foil attached with a titanium nitride coating, and the material of the metal foil is gold metal oxide;
  • the electrolyte used is aluminum chloride-butyramide; the mole percentage of A1C1 3 in the electrolyte is 52%;

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Abstract

用于氯化铝-碳电池的正极材料的制备方法及使用方法，制备方法为：（1）将碳纤维布置于乙醇中超声波清洗，置于水中超声波清洗，在真空条件和80~150℃干燥；（2）将碳原料分散在有机溶剂中，通过超声波处理或高剪切搅拌粉碎并制成悬浊液；（3）将预处理碳纤维布浸泡在悬浊液中；或者将悬浊液滴加或喷涂到预处理碳纤维布表面；取出置于真空条件和80~200℃干燥；使用方法为：采用制得的用于氯化铝-碳电池的正极材料作为正极，将正极、负极、隔膜和电解质组装成氯化铝-碳电池。本发明的方法制备工艺简单、成本低廉，产物性能稳定，可大规模生产

Description

用于氯化铝-碳电池的正极材料的制备方法及使用方法 技术领域
[0001] 本发明属于铝电池技术领域， 特别涉及一种用于氯化铝-碳电池的正极材料的 制备方法及使用方法。
背景技术
[0002] 锂离子电池因其自放电小、 质量比容量高等优点已经获得实际应用， 并且实现 工业化生产； 但是， 锂元素的自然丰度低， 空气中易燃、 易形成枝晶等缺陷限 制了它进一步商业化应用； 铝离子电池的负极材料为金属铝或合金， 铝元素在 自然界储量丰富， 且在空气中稳定存在， 其质量比容量密度可达到 2980mAh/g， 体积比容量密度可达 8040mAh/cm 3。
[0003] 铝离子电池到目前为止还未商品化， 基本上处于实验室研究阶段； CN2015109 02386.X公开了使用改进的 hummers法制备氧化石墨稀， 然后用水合肼还原剂制 备石墨烯正极材料； CN201610390212.4公开了采用化学气相沉积法在泡沫金属 上沉积多层石墨烯， 制备多孔三维石墨烯正极材料； CN201610845761.6公开了 将氧化石墨烯或氧化石墨烯无机盐混合液用静电纺丝设备制备氧化石墨烯布和 还原石墨烯布正极材料； CN201610281036.0公开了将有机碳源和石墨材料加入 溶剂中进行高压溶剂热反应和高温碳化制备正极活性物质， 然后采用涂敷法制 备正极材料； CN201711173282.5公开了化学气相沉积法制备的泡沫石墨粉体与 聚偏氟乙烯分散在设定溶剂中， 得到泡沫石墨浆料、 将泡沫石墨浆料涂覆在基 板上， 干燥处理后， 在基板上形成泡沫石墨碳层、 以及将涂覆有泡沫石墨碳层 的基板浸泡在第一设定溶液中， 待基板溶解后， 对泡沫石墨碳层进行后处理得 到泡沫石墨片正极材料； CN201710641041.2公开了采用冷冻干燥法制备氧化石 墨烯泡沫， 然后化学还原得到石墨烯泡沫， 高温热处理进行热还原得到超高导 石墨烯泡沫正极材料； CN201710685318.1公开了将膨胀石墨经过 2000~3000°C高 温处理后在 1.5~35MPa的压力下压制成膜作为铝离子电池正极。
[0004] 目前， 具有高性能的正极材料的制备方法主要集中在 hummers法、 化学气相沉 积法、 静电纺丝技术制备氧化石墨烯布或还原后石墨烯布； 这些制备方法工艺 复杂、 成本较高、 设备要求高， 阻碍了其商品化的发展。
发明概述
技术问题
问题的解决方案
技术解决方案
[0005] 本发明的目的在于提供一种用于氯化铝-碳电池的正极材料的制备方法及使用 方法， 将粉碎处理后的具有石墨结构的碳材料吸附在碳纤维布上， 将其作为铝 离子电池的正极材料， 简化工艺降低成本的同时， 提高铝电池性能。
[0006] 本发明的用于氯化铝 -碳电池的正极材料的制备方法， 按以下步骤进行：
[0007] 1、 将碳纤维布置于乙醇中进行超声波清洗 30~60min， 然后置于去离子水中进 行超声波清洗 30~60min， 在取出后置于真空条件下， 在 80~150°C干燥 12~24h， 获得预处理碳纤维布；
[0008] 2、 将碳原料分散在有机溶剂中， 通过超声波处理或高剪切搅拌对有机溶剂中 的碳原料进行粉碎并制成悬浊液； 所述的碳原料为天然石墨、 多孔活性炭、 高 取向石墨或石墨化膨胀石墨， 纯度 99.5~99.9% ; 所述的有机溶剂为无水乙醇、 N- 甲基吡咯烷酮、 二甲基甲酰胺、 二甲基乙酰胺或二甲基亚砜； 碳原料与有机溶 剂的质量比为 ( 1~10) : 100；
[0009] 3、 将预处理碳纤维布浸泡在悬浊液中， 然后取出； 或者将悬浊液滴加到预处 理碳纤维布表面； 或者将悬浊液喷涂在预处理碳纤维布表面； 再将表面覆盖有 悬浊液的碳纤维布置于真空条件下， 在 80~200°C干燥 12~24h， 制成用于氯化铝- 碳电池的正极材料。
[0010] 上述的步骤 2中， 超声波处理的时间为 0.5~12 h。
[0011] 上述的步骤 2中， 高剪切搅拌的搅拌速率为 1000~2000rpm， 时间 0.5~6h。
[0012] 上述的用于氯化铝-碳电池的正极材料中， 碳纤维布表面的碳材料的密度为 0.5~ 10 mg/cm 2。
[0013] 本发明的用于氯化铝-碳电池的正极材料的使用方法为：
[0014] 采用用于氯化铝-碳电池的正极材料作为正极， 采用铝箔作为负极， 采用玻璃 纤维滤纸作为隔膜， 将正极、 负极、 隔膜和电解质组装成氯化铝-碳电池。
[0015] 上述的氯化铝-碳电池还包括集流体和软包外壳； 所述的集流体为碳纤维布、 金属钼、 金属钨或附着有氮化钛涂层的金属箔， 其中金属箔的材质选用金属镍 、 不锈钢、 金属铜、 金属招或金属钦。
[0016] 上述的电解质为氯化招 -1-乙基 -3 -甲基氯化咪卩坐、 氯化铝 -1-丁基 -3 -甲基氯化咪 唑、 氯化铝-三乙胺盐酸盐、 氯化铝-尿素、 氯化铝-乙酰胺、 氯化铝 -丙酰胺或氯 化铝-丁酰胺； 电解质中 A1C1 3的摩尔百分比为 52~67%。
[0017] 上述的电解质中添加有添加剂， 添加剂占电解质总摩尔数的
Figure imgf000005_0001
添加剂为
LiCl、 LiBr、 NaCl、 NaBr、 EC （碳酸乙烯酯） 、 THF （四氢呋喃） 或 DCE （1,
2 -二氯乙烷） 。
发明的有益效果
有益效果
[0018] 与现有技术相比， 本发明的方法的优点与有益效果在于：
[0019] 1、 制备过程简单可控， 通过控制碳材料原料与有机溶剂的质量比、 处理时间 可获得不同浓度的活性物质悬浮液； 通过控制滴加或喷涂的次数可以获得不同 负载量的正极材料；
[0020] 2、 正极材料为无粘结正极材料， 避免了电解液与粘结剂发生反应从而破坏电 极结构， 并且碳纤维布基底的三维多孔网状结构为离子的快速迁移提供了通道
[0021] 3、 将该正极材料作为正极组装的氯化铝-碳电池， 平均工作电压为 1.5~2.0V， 放电质量比容量 100~350mAh/g， 质量比能量密度 200~650Wh/kg ;
[0022] 4、 制备工艺简单、 成本低廉， 产物性能稳定， 可大规模生产。
对附图的简要说明
附图说明
[0023] 图 1为本发明实施例 1中碳原料粉碎后的拉曼光谱图；
[0024] 图 2为本发明实施例 1中用于氯化铝-碳电池的正极材料的场发射扫描电子显微 图；
[0025] 图 3为本发明实施例 1中用于氯化铝-碳电池的正极材料在扫描速率 0.2mV/s条件 下的循环伏安曲线图；
[0026] 图 4为本发明实施例 1中用于氯化铝 -碳电池的正极材料在电流密度为 100mA/g条 件下的充放电曲线图； 图中， ■为充电， 馨为放电。
发明实施例
本发明的实施方式
[0027] 本发明实施例中进行超声波处理时的超声波功率为 100~600W。
[0028] 本发明步骤 1和 3中的真空条件为 S200Pa
[0029] 本发明实施例中采用的碳纤维布为市购产品。
[0030] 本发明实施例中采用的碳纤维布的 12.5mg/cm 2， 厚度为 0.036cm; 使用前将碳 纤维布裁剪成 （10~15） mmx （10~15） mm方形或直径 10~ 18mm圆形。
[0031] 本发明实施例中采用的碳原料均为市购产品， 纯度 99.5~99.9%。
[0032] 本发明实施例中配制电解质采用纯度＞99%的无水 A1C1 3， 直接放置于氩气气氛 的手套箱中保存备用。
[0033] 本发明实施例中采用的 LiCl、 LiBr、 NaCl、 NaBr、 EC （碳酸乙烯酯） 、 THF （ 四氢呋喃） 、 DCE （1, 2 -二氯乙烷） 为市购分析纯试剂， 使用前真空干燥并放置 于氩气气氛的手套箱中保存备用。
[0034] 本发明实施例中采用的 EMIC、 乙酰胺、 尿素、 丙酰胺、 丁酰胺均为市购试剂 ， 使用前真空干燥并放置于氩气气氛的手套箱中保存备用。
[0035] 本发明实施例中的真空干燥的条件为： 60~120°C干燥 12~24h， 真空度＜50Pa。
[0036] 本发明实施例中采用的手套箱内水和氧含量均小于 O.lppm。
[0037] 本发明实施例中采用的碳布、 金属钼、 金属钨和附着有氮化钛涂层的金属箔为 市购产品， 使用前除去表面杂质。 纯度为 299.9%， 碳化钛涂层的制备方法如文 献所述（Adv. Sci. 2018, 5, 1700712： 地球丰富的元素制备柔性集流体用于氯化铝 _ 石墨电池）。
[0038] 本发明实施例中的氯化铝-碳电池在电流密度为 100~1000mA/g条件下,放电质量 比容量为 110~300mAh/g。
[0039] 实施例 1
[0040] 将碳纤维布置于乙醇中进行超声波清洗 30min， 然后置于去离子水中进行超声 波清洗 30min， 在取出后置于真空条件下， 在 80°C干燥 24h， 获得预处理碳纤维 布；
[0041] 将碳原料分散在有机溶剂中， 通过超声波处理对有机溶剂中的碳原料进行粉碎 并制成悬浊液； 碳原料为天然石墨； 有机溶剂为 N-甲基吡咯烷酮； 碳原料与有 机溶剂的质量比为 1: 100; 获得的碳原料的拉曼光谱如图 1所示； 其中超声波处理 的时间为 0.5h;
[0042] 将悬浊液喷涂在预处理碳纤维布表面； 再将表面覆盖有悬浊液的碳纤维布置于 真空条件下， 在 80°C干燥 24h， 制成用于氯化铝-碳电池的正极材料； 场发射扫描 电子显微图如图 2所示； 上述的用于氯化铝-碳电池的正极材料中， 碳纤维布表面 的碳材料的密度为 0.5 mg/cm 2; 采用海辰华电化学工作站进行循环伏安测试， 扫 描速率为 0.2mV/s， 循环伏安曲线图如图 3所示；
[0043] 用于氯化铝-碳电池的正极材料的使用方法为：
[0044] 采用用于氯化铝-碳电池的正极材料作为正极， 采用铝箔作为负极， 采用玻璃 纤维滤纸作为隔膜， 将正极、 负极、 隔膜和电解质组装成氯化铝-碳电池； 氯化 铝-碳电池还包括集流体和软包外壳； 集流体为碳纤维布； 电解质为氯化铝 -1-乙 基 -3 -甲基氯化咪唑； 电解质中八1(：1 3的摩尔百分比为 67% ;
[0045] 采用深圳新威尔电池测试系统进行恒电流充放电测试， 氯化铝-碳电池在电流 密度为 100mA/g条件下的充放电曲线如图 4所示； 充放电截止电压为 0.01~2.45V ， 电池的放电质量比容量 260mAh/g。
[0046] 实施例 2
[0047] 制备方法同实施例 1， 不同点在于：
[0048] ( 1) 将碳纤维布置于乙醇中进行超声波清洗 35min， 然后置于去离子水中进行 超声波清洗 40min， 在取出后置于真空条件下， 在 90°C干燥 22h;
[0049] (2) 将碳原料分散在有机溶剂中， 通过高剪切搅拌对有机溶剂中的碳原料进 行粉碎并制成悬浊液； 碳原料为多孔活性炭； 有机溶剂为无水乙醇； 碳原料与 有机溶剂的质量比为 2: 100; 高剪切搅拌的搅拌速率为 lOOOrpm， 时间 OJh;
[0050] (3) 将预处理碳纤维布浸泡在悬浊液中， 然后取出； 将表面覆盖有悬浊液的 碳纤维布置于真空条件下， 在 100°C干燥 20h; 用于氯化铝-碳电池的正极材料中 ， 碳纤维布表面的碳材料的密度为 lmg/cm 2;
[0051] 使用方法同实施例 1， 不同点在于：
[0052] ( 1) 采用的集流体为金属钼；
[0053] (2) 采用的电解质为氯化铝 -1-丁基 -3 -甲基氯化咪唑； 电解质中 A1C1 3的摩尔 百分比为 66% ;
[0054] (3) 电解质中添加有添加剂， 添加剂占电解质总摩尔数的
Figure imgf000008_0001
添加剂为 L iCl；
[0055] (4) 恒电流充放电测试的电流密度为 200mA/g， 电池的放电质量比容量 200m
Ah/go
[0056] 实施例 3
[0057] 制备方法同实施例 1， 不同点在于：
[0058] ( 1) 将碳纤维布置于乙醇中进行超声波清洗 40min， 然后置于去离子水中进行 超声波清洗 35min， 在取出后置于真空条件下， 在 100°C干燥 20h;
[0059] (2) 碳原料为高取向石墨； 有机溶剂为二甲基甲酰胺； 碳原料与有机溶剂的 质量比为 3: 100; 超声波处理的时间为 2h;
[0060] (3) 将悬浊液滴加到预处理碳纤维布表面； 将表面覆盖有悬浊液的碳纤维布 置于真空条件下， 在 120°C干燥 18h; 用于氯化铝-碳电池的正极材料中， 碳纤维 布表面的碳材料的密度为 3mg/cm 2;
[0061] 使用方法同实施例 1， 不同点在于：
[0062] ( 1) 采用的集流体为金属钨；
[0063] (2) 采用的电解质为氯化铝-三乙胺盐酸盐； 电解质中 A1C1 3
的摩尔百分比为 64% ;
[0064] (3) 电解质中添加有添加剂， 添加剂占电解质总摩尔数的
Figure imgf000008_0002
添加剂为 L iBr；
[0065] (4) 恒电流充放电测试的电流密度为 200mA/g， 电池的放电质量比容量 180m
Ah/go
[0066] 实施例 4
[0067] 制备方法同实施例 1， 不同点在于： [0068] ( 1) 将碳纤维布置于乙醇中进行超声波清洗 45min， 然后置于去离子水中进行 超声波清洗 35min， 在取出后置于真空条件下， 在 110°C干燥 18h;
[0069] (2) 将碳原料分散在有机溶剂中， 通过高剪切搅拌对有机溶剂中的碳原料进 行粉碎并制成悬浊液； 碳原料为石墨化膨胀石墨； 有机溶剂为二甲基乙酰胺； 碳原料与有机溶剂的质量比为 4: 100; 高剪切搅拌的搅拌速率为 1500rpm， 时间 lh
[0070] (3) 将预处理碳纤维布浸泡在悬浊液中， 然后取出； 将表面覆盖有悬浊液的 碳纤维布置于真空条件下， 在 140°C干燥 16h; 用于氯化铝-碳电池的正极材料中 ， 碳纤维布表面的碳材料的密度为 4mg/cm 2;
[0071] 使用方法同实施例 1， 不同点在于：
[0072] ( 1) 采用的集流体为附着有氮化钛涂层的金属箔， 其中金属箔的材质选用金 属镍；
[0073] (2) 采用的电解质为氯化铝-尿素； 电解质中 A1C1 3的摩尔百分比为 62%;
[0074] (3) 电解质中添加有添加剂， 添加剂占电解质总摩尔数的
Figure imgf000009_0001
添加剂为 N aCl；
[0075] (4) 恒电流充放电测试的电流密度为 100mA/g， 电池的放电质量比容量 120m
Ah/go
[0076] 实施例 5
[0077] 制备方法同实施例 1， 不同点在于：
[0078] ( 1) 将碳纤维布置于乙醇中进行超声波清洗 50min， 然后置于去离子水中进行 超声波清洗 60min， 在取出后置于真空条件下， 在 120°C干燥 16h;
[0079] (2) 碳原料为多孔活性炭； 有机溶剂为二甲基亚砜； 碳原料与有机溶剂的质 量比为 6: 100; 超声波处理的时间为％;
[0080] (3) 将悬浊液滴加到预处理碳纤维布表面； 将表面覆盖有悬浊液的碳纤维布 置于真空条件下， 在 150°C干燥 15h; 用于氯化铝-碳电池的正极材料中， 碳纤维 布表面的碳材料的密度为 5mg/cm 2;
[0081] 使用方法同实施例 1， 不同点在于：
[0082] ( 1) 采用的集流体为附着有氮化钛涂层的金属箔， 其中金属箔的材质选用锈 钢；
[0083] (2) 釆用的电解质为氯化铝-乙酰胺； 电解质中 A1C1 3的摩尔百分比为 60%;
[0084] (3) 电解质中添加有添加剂， 添加剂占电解质总摩尔数的 1〜 10%， 添加剂为 N aBr；
[0085] (4) 恒电流充放电测试的电流密度为 150mA/g， 电池的放电质量比容量 150m
Ah/go
[0086] 实施例 6
[0087] 制备方法同实施例 1， 不同点在于：
[0088] ( 1) 将碳纤维布置于乙醇中进行超声波清洗 55min， 然后置于去离子水中进行 超声波清洗 50min， 在取出后置于真空条件下， 在 130°C干燥 15h;
[0089] (2) 将碳原料分散在有机溶剂中， 通过高剪切搅拌对有机溶剂中的碳原料进 行粉碎并制成悬浊液； 碳原料为高取向石墨； 有机溶剂为二甲基乙酰胺； 碳原 料与有机溶剂的质量比为 8: 100; 高剪切搅拌的搅拌速率为 1800rpm， 时间 4h;
[0090] (3) 将表面覆盖有悬浊液的碳纤维布置于真空条件下， 在 160°C干燥 14h; 用 于氯化铝-碳电池的正极材料中， 碳纤维布表面的碳材料的密度为 6mg/cm 2;
[0091] 使用方法同实施例 1， 不同点在于：
[0092] ( 1) 采用的集流体为附着有氮化钛涂层的金属箔， 其中金属箔的材质选用金 属铜；
[0093] (2) 采用的电解质为氯化铝-丙酰胺； 电解质中 A1C1 3的摩尔百分比为 57%;
[0094] (3) 电解质中添加有添加剂， 添加剂占电解质总摩尔数的
Figure imgf000010_0001
添加剂为 E
C；
[0095] (4) 恒电流充放电测试的电流密度为 100mA/g， 电池的放电质量比容量 170m
Ah/go
[0096] 实施例 7
[0097] 制备方法同实施例 1， 不同点在于：
[0098] ( 1) 将碳纤维布置于乙醇中进行超声波清洗 60min， 然后置于去离子水中进行 超声波清洗 30min， 在取出后置于真空条件下， 在 140°C干燥 14h;
[0099] (2) 碳原料为石墨化膨胀石墨； 有机溶剂为无水乙醇； 碳原料与有机溶剂的 质量比为 9: 100; 超声波处理的时间为 12 h;
[0100] (3) 将预处理碳纤维布浸泡在悬浊液中， 然后取出； 将表面覆盖有悬浊液的 碳纤维布置于真空条件下， 在 180°C干燥 13h; 用于氯化铝-碳电池的正极材料中 ， 碳纤维布表面的碳材料的密度为 8mg/cm 2;
[0101] 使用方法同实施例 1， 不同点在于：
[0102] ( 1) 采用的集流体为附着有氮化钛涂层的金属箔， 其中金属箔的材质选用金 属铝；
[0103] (2) 采用的电解质为氯化铝-丁酰胺； 电解质中 A1C1 3的摩尔百分比为 54%;
[0104] (3) 电解质中添加有添加剂， 添加剂占电解质总摩尔数的
Figure imgf000011_0001
添加剂为 T
HF；
[0105] (4) 恒电流充放电测试的电流密度为 500mA/g， 电池的放电质量比容量 150m
Ah/go
[0106] 实施例 8
[0107] 制备方法同实施例 1， 不同点在于：
[0108] ( 1) 将碳纤维布置于乙醇中进行超声波清洗 45min， 然后置于去离子水中进行 超声波清洗 45min， 在取出后置于真空条件下， 在 150°C干燥 12h;
[0109] (2) 将碳原料分散在有机溶剂中， 通过高剪切搅拌对有机溶剂中的碳原料进 行粉碎并制成悬浊液； 碳原料为石墨化膨胀石墨； 有机溶剂为二甲基甲酰胺； 碳原料与有机溶剂的质量比为 10: 100; 高剪切搅拌的搅拌速率为 2000rpm， 时间 6 h；
[0110] (3) 将悬浊液滴加到预处理碳纤维布表面； 将表面覆盖有悬浊液的碳纤维布 置于真空条件下， 在 200°C干燥 12h; 用于氯化铝-碳电池的正极材料中， 碳纤维 布表面的碳材料的密度为 10 mg/cm 2;
[0111] 使用方法同实施例 1， 不同点在于：
[0112] ( 1) 采用的集流体为附着有氮化钛涂层的金属箔， 其中金属箔的材质选用金 金属钦；
[0113] (2) 采用的电解质为氯化铝-丁酰胺； 电解质中 A1C1 3的摩尔百分比为 52%;
[0114] (3) 电解质中添加有添加剂， 添加剂占电解质总摩尔数的 添加剂为 D CE；
[0115] (4) 恒电流充放电测试的电流密度为 1000mA/g， 电池的放电质量比容量 110m
Ah/go

Claims

权利要求书 [权利要求 1] 一种用于氯化铝 -碳电池的正极材料的制备方法， 其特征在于按以下 步骤进行：
( 1) 将碳纤维布置于乙醇中进行超声波清洗 30~60min， 然后置于去 离子水中进行超声波清洗 30~60min， 在取出后置于真空条件下， 在 8 0~150°C干燥 12~24h， 获得预处理碳纤维布；
(2) 将碳原料分散在有机溶剂中， 通过超声波处理或高剪切搅拌对 有机溶剂中的碳原料进行粉碎并制成悬浊液； 所述的碳原料为天然石 墨、 多孔活性炭、 高取向石墨或石墨化膨胀石墨， 纯度 99.5~99.9% ; 所述的有机溶剂为无水乙醇、 N-甲基吡咯烷酮、 二甲基甲酰胺、 二甲 基乙酰胺或二甲基亚砜； 碳原料与有机溶剂的质量比为 ( 1~10) : 100
(3) 将预处理碳纤维布浸泡在悬浊液中， 然后取出； 或者将悬浊液 滴加到预处理碳纤维布表面； 或者将悬浊液喷涂在预处理碳纤维布表 面； 再将表面覆盖有悬浊液的碳纤维布置于真空条件下， 在 80~200°C 干燥 12~24h， 制成用于氯化铝-碳电池的正极材料。
[权利要求 2] 根据权利要求 1所述的用于氯化铝-碳电池的正极材料的制备方法， 其 特征在于步骤 (2) 中， 超声波处理的时间为 0.5~12 h。
[权利要求 3] 根据权利要求 1所述的用于氯化铝-碳电池的正极材料的制备方法， 其 特征在于步骤 (2) 中， 高剪切搅拌的搅拌速率为 1000~2000rpm， 时 间 0.5~6h。
[权利要求 4] 根据权利要求 1所述的用于氯化铝-碳电池的正极材料的制备方法， 其 特征在于所述的用于氯化铝-碳电池的正极材料中， 碳纤维布表面的 碳材料的密度为 0.5~10 mg/cm 2。
[权利要求 5] 一种用于氯化铝 -碳电池的正极材料的使用方法， 其特征在于采用权 利要求 1所述的方法制备的用于氯化铝-碳电池的正极材料作为正极， 采用铝箔作为负极， 采用玻璃纤维滤纸作为隔膜， 将正极、 负极、 隔 膜和电解质组装成氯化铝-碳电池。
[权利要求 6] 根据权利要求 5所述的用于氯化铝-碳电池的正极材料的使用方法， 其 特征在于所述的氯化铝-碳电池还包括集流体和软包外壳； 所述的集 流体为碳纤维布、 金属钼、 金属钨或附着有氮化钛涂层的金属箔， 其 中金属箔的材质选用金属镍、 不锈钢、 金属铜、 金属铝或金属钛。
[权利要求 7] 根据权利要求 5所述的用于氯化铝-碳电池的正极材料的使用方法， 其 特征在于所述的电解质为氯化铝 -1-乙基 -3 -甲基氯化咪唑、 氯化铝 -1- 丁基 -3 -甲基氯化咪唑、 氯化铝-三乙胺盐酸盐、 氯化铝-尿素、 氯化铝 -乙酰胺、 氯化铝-丙酰胺或氯化铝-丁酰胺； 电解质中八1（：1 3的摩尔百 分比为 52~67%。
[权利要求 8] 根据权利要求 5所述的用于氯化铝-碳电池的正极材料的使用方法， 其 特征在于所述的电解质中添加有添加剂， 添加剂占电解质总摩尔数的
1-10% , 添加剂为 LiCl、 LiBr、 NaCl、 NaBr、 EC、 THF或 DCE。
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