WO2016026321A1 - Chargeable aluminum-ion battery and preparation method thereof - Google Patents

Chargeable aluminum-ion battery and preparation method thereof Download PDF

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WO2016026321A1
WO2016026321A1 PCT/CN2015/076947 CN2015076947W WO2016026321A1 WO 2016026321 A1 WO2016026321 A1 WO 2016026321A1 CN 2015076947 W CN2015076947 W CN 2015076947W WO 2016026321 A1 WO2016026321 A1 WO 2016026321A1
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aluminum ion
ion battery
aluminum
positive electrode
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焦树强
孙浩博
王伟
王俊香
刘勇
余智静
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北京科技大学
北京金吕能源科技有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
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    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H—ELECTRICITY
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Abstract

The present invention relates to the field of energy source recycling. Disclosed are a chargeable aluminum-ion battery and preparation method thereof. The battery comprises an anode, a cathode, a liquid aluminum-ion electrolyte, and a diaphragm material; the anode is a graphite structure carbon material; the cathode is high-purity aluminum; and the liquid aluminum-ion electrolyte is a mixture of an anhydrous aluminum chloride and a 3-methylimidazole compound at a molar ratio of 1.1:1 to 1.6:1. The preparation process of the battery comprises: machining the graphite structure carbon material of the anode material into sheets, using an inert metallic foil sheet as a current collector to fix the anode material, and covering the anode material with the diaphragm to serve as the anode; a high-purity aluminum cut sheet serves as a cathode after cleaning thereof; and formulating the liquid aluminum-ion electrolyte comprising freely moving Al3+ ions. The anode, the cathode and the liquid aluminum-ion electrolyte are assembled into a battery in a glovebox. The battery has a high capacity and good circulation stability, and can be used in the fields of electronics, communication and electric vehicles.

Description

一种可充电铝离子电池及其制备方法Rechargeable aluminum ion battery and preparation method thereof 技术领域Technical field
本发明涉及一种可充电铝离子电池及其制备方法，属于能源再利用领域。The invention relates to a rechargeable aluminum ion battery and a preparation method thereof, and belongs to the field of energy reuse.
背景技术Background technique
近年来，随着传统能源的逐渐枯竭，绿色可再生能源备受青睐。其中各种二次电池的研究更是如火如荼。In recent years, with the gradual depletion of traditional energy sources, green renewable energy has been favored. Among them, the research of various secondary batteries is in full swing.
上世纪八十年代提出的锂离子电池因其具有自放电小、比容量高、循环性能好和环境友好等优点，发展十分迅速，现已技术成熟。然而地球上锂资源有限，昂贵的成本及安全隐患限制了锂离子电池的大规模应用。人们亟需设计新型电池体系取代锂离子电池。Lithium-ion batteries proposed in the 1980s have developed rapidly due to their advantages of small self-discharge, high specific capacity, good cycle performance and environmental friendliness. However, limited lithium resources on the earth, expensive costs and safety hazards limit the large-scale application of lithium-ion batteries. There is an urgent need to design new battery systems to replace lithium-ion batteries.
铝元素是地壳中含量最丰富的金属元素，铝成本远远低于锂，基于铝离子嵌入和脱嵌的可充电铝离子电池有望用于大规模储能设备。另外，每一个铝离子携带的电荷是锂离子的三倍，因而，铝离子电池的容量有望得到很大提升。碳材料以其层状结构及优良的导电性可以使铝离子嵌入和脱嵌，且价格低廉、方便加工，成为铝离子电池的合适电极材料。因此，开发比容量较高、价格低廉的铝‐碳可充电电池具有十分重要的理论意义和商业意义。Aluminum is the most abundant metal element in the earth's crust. Aluminum costs far less than lithium. Rechargeable aluminum ion batteries based on aluminum ion intercalation and deintercalation are expected to be used in large-scale energy storage equipment. In addition, each aluminum ion carries three times as much charge as lithium ions, and thus the capacity of the aluminum ion battery is expected to be greatly improved. The carbon material can embed and deintercalate aluminum ions with its layered structure and excellent electrical conductivity, and is inexpensive and convenient to process, and becomes a suitable electrode material for an aluminum ion battery. Therefore, the development of aluminum-carbon rechargeable batteries with higher capacity and lower price has very important theoretical and commercial significance.
发明内容Summary of the invention
本发明要解决的技术问题是，提供一种可取代锂离子电池的新型二次电池，即可充电铝离子电池体系及其制备方法，实现了可充电铝离子电池的高容量充放电，并且循环寿命长。The technical problem to be solved by the present invention is to provide a novel secondary battery, a rechargeable aluminum ion battery system and a preparation method thereof, which can replace the lithium ion battery, realize high-capacity charge and discharge of the rechargeable aluminum ion battery, and circulate long life.
为实现上述目的，本发明采用如下的技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种可充电铝离子电池，其特征在于包含正极、负极、液态铝离子电解液、隔膜材料，其中正极为石墨结构碳材料，负极为高纯铝，液态铝离子电解液由无水氯化铝和3-甲基咪唑类化合物混合而成，其中无水氯化铝和3-甲基咪唑类化合物的摩尔比为1.1:1至1.6:1。A rechargeable aluminum ion battery characterized by comprising a positive electrode, a negative electrode, a liquid aluminum ion electrolyte, and a separator material, wherein the positive electrode is a graphite structure carbon material, the negative electrode is a high purity aluminum, and the liquid aluminum ion electrolyte is made of anhydrous aluminum chloride. It is mixed with a 3-methylimidazole compound in which the molar ratio of anhydrous aluminum chloride to 3-methylimidazole compound is from 1.1:1 to 1.6:1.
所述石墨结构碳材料为石墨、碳纸、碳纤维纸及炭黑等。 The graphite structure carbon material is graphite, carbon paper, carbon fiber paper, carbon black or the like.
所述隔膜材料为具有离子通透性且不与正极和负极反应的聚丙烯微孔隔膜材料、聚乙烯微孔隔膜材料以及玻璃纤维材料中的一种。The separator material is one of a polypropylene microporous membrane material, a polyethylene microporous membrane material, and a glass fiber material having ion permeability and not reacting with the positive electrode and the negative electrode.
所述的3-甲基咪唑类化合物包括1-丁基-3-甲基咪唑氯化物、1-丙基-3-甲基咪唑氯盐、1-乙基-3-甲基咪唑氯化物、1-丁基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑六氟磷酸盐。The 3-methylimidazole compound includes 1-butyl-3-methylimidazolium chloride, 1-propyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate.
所述可充电铝离子电池的制备方法，其特征在于，包括以下的制备步骤：The method for preparing the rechargeable aluminum ion battery is characterized by comprising the following preparation steps:
1)将正极材料石墨结构碳材料加工成片状；1) processing the cathode material graphite structure carbon material into a sheet shape;
2)以惰性金属箔片为集流体将上述正极材料固定，以隔膜包裹作为正极，惰性金属箔片为钼、泡沫镍或金及铂族金属等贵金属；2) fixing the above positive electrode material with an inert metal foil as a current collector, and encapsulating the separator as a positive electrode, and the inert metal foil is a noble metal such as molybdenum, nickel foam or gold and platinum group metal;
3)将高纯铝剪片清洗后作为负极；3) cleaning the high-purity aluminum strip as a negative electrode;
4)配制含有可自由移动的Al3+离子的离子液体作为电池的液态铝离子电解液；4) preparing an ionic liquid containing freely movable Al 3+ ions as a liquid aluminum ion electrolyte of the battery;
5)以上述正极、负极以及液态铝离子电解液，在手套箱中组装电池。5) The battery was assembled in a glove box using the above positive electrode, negative electrode, and liquid aluminum ion electrolyte.
可充电铝离子电池所用壳体结构为玻璃电解池、塑料电解池或塑料电池壳。The housing structure of the rechargeable aluminum ion battery is a glass electrolytic cell, a plastic electrolytic cell or a plastic battery case.
上述步骤2)，固定方式为剪切惰性金属片(钼片、泡沫镍、贵金属等)为集流体，把步骤1)中加工好的碳材料电极片固定在集流体上，作为正极。固定方式包括绑缚、粘连、压制以及槽型固定等物理固定方式。再按正极尺寸剪裁隔膜材料，包在正极片上，固定好。In the above step 2), the fixing method is to shear the inert metal sheet (molybdenum sheet, foamed nickel, precious metal, etc.) as a current collector, and the carbon material electrode sheet processed in the step 1) is fixed on the current collector as a positive electrode. Fixing methods include physical fixation such as binding, adhesion, pressing, and groove fixing. Then cut the diaphragm material according to the positive electrode size, and wrap it on the positive electrode sheet and fix it.
上述步骤3)，负极的清洗方法为，用有机液体，无水乙醇或丙酮，浸泡并超声震荡，干燥后，作为负极。In the above step 3), the negative electrode is cleaned by an organic liquid, anhydrous ethanol or acetone, soaked and ultrasonically shaken, and dried to serve as a negative electrode.
上述步骤4)，液态铝离子电解液应在手套箱中配制，配制后要静置12小时以上。In the above step 4), the liquid aluminum ion electrolyte should be prepared in a glove box and allowed to stand for more than 12 hours after preparation.
本发明使用石墨结构碳材料(石墨、碳纸、碳纤维纸、膨胀石墨以及炭黑等)作为正极，以高纯铝作为负极，构成了一种新型非水系可充电铝离子电池。由于本发明对此种电池正负极、隔膜、电解液等进行了细致的研究、精密的制备、准确的测试，本发明达到了下述特点：提出了一种新型高价离子电池体系，即可充电铝离子电池体系，使可移动电源的种类进一步扩展；由于铝元素储量丰富，价格低廉，大大降低了离子电池的成本；碳材料由于其独特的层状结构、优良的导电性以及低廉的价格，有利于在可充电铝离子电池中的应用；隔膜具有良好的电 绝缘性，电阻低，对电解质离子具有很好的通透性，具有较好的化学稳定性和电化学稳定性，对电解质润湿性好；有一定的机械强度，可选用的品种多；采用离子液体作为可充电铝离子电池的电解质，铝离子电导率高，热稳定性好，电化学窗口较宽，化学稳定性高，与电池体系中的正负极材料、隔膜等基本不发生反应，在较宽的温度范围内保持液态。本发明的可应用于众多领域，如电子工业、通讯产业、电动汽车等。The present invention uses a graphite structure carbon material (graphite, carbon paper, carbon fiber paper, expanded graphite, carbon black, etc.) as a positive electrode, and high-purity aluminum as a negative electrode to constitute a novel non-aqueous rechargeable aluminum ion battery. Since the present invention has carried out detailed research, precise preparation, and accurate testing on the positive and negative electrodes, separators, and electrolytes of the battery, the present invention achieves the following characteristics: a novel high-priced ion battery system is proposed. The rechargeable aluminum ion battery system further expands the types of mobile power supplies; due to the abundant aluminum reserves and low price, the cost of the ion battery is greatly reduced; the carbon material has a unique layer structure, excellent conductivity and low price. Conducive to the application in rechargeable aluminum ion batteries; the diaphragm has good electricity Insulation, low electrical resistance, good permeability to electrolyte ions, good chemical and electrochemical stability, good wettability to electrolytes; certain mechanical strength, many varieties available; As the electrolyte of rechargeable aluminum ion battery, ionic liquid has high conductivity, good thermal stability, wide electrochemical window and high chemical stability. It does not react with positive and negative materials and separators in battery systems. Maintain a liquid state over a wide temperature range. The invention can be applied to many fields, such as the electronics industry, the communication industry, electric vehicles and the like.
附图说明DRAWINGS
图1为实施例1制备的可充电铝离子电池充放电性能测试曲线；1 is a test curve of charge and discharge performance of a rechargeable aluminum ion battery prepared in Example 1;
图2为实施例2制备的可充电铝离子电池的循环性能测试曲线。2 is a cycle performance test curve of the rechargeable aluminum ion battery prepared in Example 2.
具体实施方式detailed description
本发明的可充电铝离子电池结构有圆柱状、方形状、扣式状等多种形状，它们主要包括电池壳体、正极、负极、隔膜以及注入的电解质等。电池壳体可为玻璃制、塑料制及钼制壳体。正极为以钼片固定的石墨结构碳材料(石墨、碳纸、碳纤维纸及炭黑等)，负极为高纯铝。隔膜材料为具有离子通透性且不与正极与负极反应的聚丙烯微孔隔膜材料、聚乙烯微孔隔膜材料以及玻璃纤维材料中的一种。电解质由无水氯化铝和3‐甲基咪唑类化合物(1‐丁基‐3‐甲基咪唑氯化物、1‐丙基‐3‐甲基咪唑氯盐、1‐乙基‐3‐甲基咪唑氯化物、1‐丁基‐3‐甲基咪唑四氟硼酸盐、1‐丁基‐3‐甲基咪唑六氟磷酸盐等)混合而成。The rechargeable aluminum ion battery of the present invention has various shapes such as a cylindrical shape, a square shape, and a buckle shape, and mainly includes a battery case, a positive electrode, a negative electrode, a separator, and an injected electrolyte. The battery case can be made of glass, plastic or molybdenum. The positive electrode is a graphite structural carbon material (graphite, carbon paper, carbon fiber paper, carbon black, etc.) fixed with molybdenum sheets, and the negative electrode is high-purity aluminum. The separator material is one of a polypropylene microporous membrane material, a polyethylene microporous membrane material, and a glass fiber material having ion permeability and not reacting with the positive electrode and the negative electrode. The electrolyte consists of anhydrous aluminum chloride and 3-methylimidazolium compounds (1-butyl-3-methylimidazolium chloride, 1-propyl-3-methylimidazolium chloride, 1-ethyl-3-methyl) A mixture of imidazolium chloride, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, etc.
实施例1：Example 1:
以碳纸作为正极材料。把碳纸在手动压轧机上压平压均匀，剪裁成直径为16mm的圆片，以无水乙醇擦洗干净，在60℃烘箱中烘干2小时。取0.5mm厚的钼箔，剪裁出两片4mm×7mm尺寸的钼片。对其两片钼片打直径1mm的孔。把碳纸置于钼片中间，按钼片上孔洞位置打直径1mm厚的孔。以集流体金属丝把碳纸和钼片绑在一起组成正极。以玻璃纤维滤纸(GF/D,Whatman)包裹碳纸和钼片组成的正极。把高纯铝片在无水乙醇中浸泡3小时，并超声震荡，干燥后，作为负极。将无水氯化铝和1‐乙基‐3‐甲基咪唑氯化物按摩尔比1.3:1在充氩手套箱中混合配制离子液体。之后把正极、负极装到可密封的玻璃电解池中，加入离 子液体后密封，即制成了可充电铝离子电池产品。电池装好12小时后，在0.4‐2.4V范围内进行充放电测试。图1显示了其比容量。Carbon paper was used as the positive electrode material. The carbon paper was pressed flat on a hand-rolling mill, cut into discs having a diameter of 16 mm, scrubbed with absolute ethanol, and dried in an oven at 60 ° C for 2 hours. A 0.5 mm thick molybdenum foil was taken and two pieces of molybdenum sheets of 4 mm x 7 mm size were cut out. A hole of 1 mm in diameter was punched into the two molybdenum sheets. Place the carbon paper in the middle of the molybdenum sheet and punch the hole with a diameter of 1 mm according to the position of the hole on the molybdenum sheet. The carbon paper and the molybdenum sheet are tied together by a current collector wire to form a positive electrode. A positive electrode composed of carbon paper and molybdenum sheets was wrapped with glass fiber filter paper (GF/D, Whatman). The high-purity aluminum sheet was immersed in absolute ethanol for 3 hours, and ultrasonically shaken, and dried to serve as a negative electrode. Anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride were mixed at a molar ratio of 1.3:1 in an argon-filled glove box to prepare an ionic liquid. After that, the positive electrode and the negative electrode are placed in a sealable glass electrolytic cell, and then added. After the sub-liquid is sealed, it is made into a rechargeable aluminum ion battery product. After the battery was installed for 12 hours, the charge and discharge test was performed in the range of 0.4-2.4V. Figure 1 shows its specific capacity.
实施例2：Example 2:
以炭黑作为正极材料。在炭黑中加入少许无水乙醇沾湿，放入20mm直径模具，以15MPa压力压块，在60℃烘箱烘1小时后在真空条件下加热到800℃真空烧结2小时自然冷却。再取0.5mm厚的钼箔，剪裁出两片4mm×7mm尺寸的钼片。对其两片钼片打直径1mm的孔。把炭黑电极片置于钼片中间，按钼片上孔洞位置打直径1mm厚的孔。以集流体金属丝把碳纸和钼片绑在一起组成正极。以玻璃纤维滤纸(GF/D,Whatman)包裹碳纸和钼片组成的正极。把高纯铝片在无水乙醇中浸泡3小时，并超声震荡，干燥后，作为负极。将无水氯化铝和1‐丁基‐3‐甲基咪唑氯化物按摩尔比1.3:1在充氩手套箱中混合配制离子液体。之后把正极、负极装到可密封的玻璃电解池中，加入离子液体后密封，即制成了可充电铝离子电池产品。电池装好12小时后，在0.4‐2.4V范围内进行充放电测试。图2显示了其循环稳定性。 Carbon black was used as the positive electrode material. A small amount of absolute ethanol was added to the carbon black, wetted, placed in a 20 mm diameter mold, pressed at a pressure of 15 MPa, baked in an oven at 60 ° C for 1 hour, and then vacuum-sintered to 800 ° C under vacuum for 2 hours to be naturally cooled. Then take a 0.5 mm thick molybdenum foil and cut two pieces of molybdenum sheets of 4 mm × 7 mm size. A hole of 1 mm in diameter was punched into the two molybdenum sheets. The carbon black electrode sheet was placed in the middle of the molybdenum sheet, and a hole having a diameter of 1 mm was drilled at the position of the hole on the molybdenum sheet. The carbon paper and the molybdenum sheet are tied together by a current collector wire to form a positive electrode. A positive electrode composed of carbon paper and molybdenum sheets was wrapped with glass fiber filter paper (GF/D, Whatman). The high-purity aluminum sheet was immersed in absolute ethanol for 3 hours, and ultrasonically shaken, and dried to serve as a negative electrode. Anhydrous aluminum chloride and 1 -butyl-3-methylimidazolium chloride were mixed in an argon-filled glove box to prepare an ionic liquid at a molar ratio of 1.3:1. After that, the positive electrode and the negative electrode are placed in a sealable glass electrolytic cell, and the ionic liquid is added and sealed, thereby forming a rechargeable aluminum ion battery product. After the battery was installed for 12 hours, the charge and discharge test was performed in the range of 0.4-2.4V. Figure 2 shows its cycle stability.

Claims (9)

  1. 一种可充电铝离子电池，其特征在于包含正极、负极、液态铝离子电解液、隔膜材料，其中正极为石墨结构碳材料，负极为高纯铝，液态铝离子电解液由无水氯化铝和3-甲基咪唑类化合物混合而成，液态铝离子电解液中无水氯化铝和3-甲基咪唑类化合物的摩尔比为1.1:1至1.6:1。A rechargeable aluminum ion battery characterized by comprising a positive electrode, a negative electrode, a liquid aluminum ion electrolyte, and a separator material, wherein the positive electrode is a graphite structure carbon material, the negative electrode is a high purity aluminum, and the liquid aluminum ion electrolyte is made of anhydrous aluminum chloride. The mixture is mixed with a 3-methylimidazole compound, and the molar ratio of anhydrous aluminum chloride to 3-methylimidazole compound in the liquid aluminum ion electrolyte is from 1.1:1 to 1.6:1.
  2. 根据权利要求1所述可充电铝离子电池，其特征在于，石墨结构碳材料为石墨、碳纸、碳纤维纸、膨胀石墨及炭黑。The rechargeable aluminum ion battery according to claim 1, wherein the graphite structured carbon material is graphite, carbon paper, carbon fiber paper, expanded graphite, and carbon black.
  3. 根据权利要求1所述的可充电铝离子电池，其特征在于，所述隔膜材料为具有离子通透性且不与正极和负极反应的聚丙烯微孔隔膜材料、聚乙烯微孔隔膜材料以及玻璃纤维材料中的一种。The rechargeable aluminum ion battery according to claim 1, wherein the separator material is a polypropylene microporous membrane material having ion permeability and not reacting with the positive electrode and the negative electrode, a polyethylene microporous membrane material, and glass. One of the fibrous materials.
  4. 根据权利要求1所述的可充电铝离子电池，其特征在于，所述的3-甲基咪唑类化合物包括1-丁基-3-甲基咪唑氯化物、1-丙基-3-甲基咪唑氯盐、1-乙基-3-甲基咪唑氯化物、1-丁基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑六氟磷酸盐。The rechargeable aluminum ion battery according to claim 1, wherein said 3-methylimidazole compound comprises 1-butyl-3-methylimidazolium chloride, 1-propyl-3-methyl Imidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate.
  5. 如权利要求1所述可充电铝离子电池的制备方法，其特征在于，包括以下的制备步骤：A method of preparing a rechargeable aluminum ion battery according to claim 1, comprising the following steps of preparing:
    1)将正极材料石墨结构碳材料加工成片状；1) processing the cathode material graphite structure carbon material into a sheet shape;
    2)以惰性金属箔片为集流体将上述正极材料固定，以隔膜包裹作为正极，惰性金属箔片为钼、泡沫镍或金及铂族等贵金属；2) fixing the above positive electrode material with an inert metal foil as a current collector, and encapsulating the separator as a positive electrode, and the inert metal foil is a noble metal such as molybdenum, nickel foam or gold and platinum group;
    3)将高纯铝剪片清洗后作为负极；3) cleaning the high-purity aluminum strip as a negative electrode;
    4)配制含有可自由移动的Al3+离子的离子液体作为电池的液态铝离子电解液；4) preparing an ionic liquid containing freely movable Al 3+ ions as a liquid aluminum ion electrolyte of the battery;
    5)以上述正极、负极以及液态铝离子电解液，在手套箱中组装电池。5) The battery was assembled in a glove box using the above positive electrode, negative electrode, and liquid aluminum ion electrolyte.
  6. 如权利要求5所述的可充电铝离子电池的制备方法，其特征在于，可充电铝离子电池所用壳体为玻璃电解池、塑料电解池或塑料电池壳。The method for preparing a rechargeable aluminum ion battery according to claim 5, wherein the housing for the rechargeable aluminum ion battery is a glass electrolytic cell, a plastic electrolytic cell or a plastic battery can.
  7. 如权利要求5所述的可充电铝离子电池的制备方法，其特征在于，所述步骤2)，固定方式为剪切惰性金属片为集流体，把步骤1)中加工好的碳材料电极片固定在集流体上，作为正极；固定方式包括绑缚、粘连、压制以及槽型固定，再按正极尺寸剪裁隔膜材料，包在正极片上，固定好。The method for preparing a rechargeable aluminum ion battery according to claim 5, wherein the step 2) is a method of cutting the inert metal piece into a current collector, and the carbon material electrode piece processed in the step 1) is used. It is fixed on the current collector as the positive electrode; the fixing method includes binding, blocking, pressing and groove fixing, and then the diaphragm material is cut according to the positive electrode size, wrapped on the positive electrode sheet, and fixed.
  8. 如权利要求5所述的可充电铝离子电池的制备方法，其特征在于，所述 步骤3)，负极的清洗方法为，用有机液体，无水乙醇或丙酮，浸泡并超声震荡，干燥。A method of preparing a rechargeable aluminum ion battery according to claim 5, wherein said Step 3), the negative electrode is cleaned by using an organic liquid, absolute ethanol or acetone, soaked and ultrasonically shaken, and dried.
  9. 如权利要求5所述的可充电铝离子电池的制备方法，其特征在于，所述步骤4)，离子液体要在手套箱中配制液态铝离子电解液，配制后要静置12小时以上。 The method for preparing a rechargeable aluminum ion battery according to claim 5, wherein in the step 4), the ionic liquid is prepared by dissolving a liquid aluminum ion electrolyte in a glove box, and is allowed to stand for more than 12 hours after preparation.
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