阅读说明：本技术 一种基于铅笔涂膜正极的铝离子电池及其制备方法 (Aluminum ion battery based on pencil coating positive electrode and preparation method thereof ) 是由 吴亭亭 于江坤 刘艳茹 王磊 于 2021-09-06 设计创作，主要内容包括：本发明涉及铝离子电池领域,公开了一种铅笔涂膜制备电池正极用于铝离子电池的方法。利用激光将钼基底进行粗糙化处理,通过铅笔简单涂覆的方式在其表面成膜,并在薄膜表面滴加微量粘结剂提高稳定性,利用该正极组装铝离子电池,能够稳定循环2000圈,稳定后电池比容量可达100mAh·g～(-1),库伦效率为95％。与传统制备铝离子电池石墨正极方法相比,本发明在保证高容量和高库伦效率的同时,简化了铝离子电池的加工工艺,在未来的实际应用中具有重要价值。(The invention relates to the field of aluminum ion batteries, and discloses a method for preparing a battery anode for an aluminum ion battery by pencil coating. The molybdenum substrate is roughened by laser, a film is formed on the surface of the molybdenum substrate in a mode of simply coating a pencil, a trace amount of binder is dripped on the surface of the film to improve the stability, the aluminum ion battery assembled by the anode can stably circulate 2000 circles, and the specific capacity of the battery after stabilization can reach 100mAh g ‑1 Coulombic efficiency was 95%. Compared with the traditional method for preparing the graphite anode of the aluminum ion battery, the method ensures high capacity and high coulombic efficiencyThe processing technology of the aluminum ion battery is simplified, and the method has important value in future practical application.)

1. The aluminum ion battery based on the pencil coating anode and the preparation method thereof are characterized in that laser roughening and cleaning treatment is carried out on a current collector, pencil scraps are further simply scratched and coated on the surface of the current collector, the loading amount of pencil graphite is increased through the laser treatment of the current collector, and molybdenum sheets scratched and coated by the pencil scraps are subjected to surface modification treatment by using a binder coating method to prepare the anode piece. The aluminum ion battery structure prepared based on the pencil coating positive pole piece comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte, and is finally assembled into the aluminum ion battery.

2. The method for roughening the current collector by using laser as claimed in claim 1, wherein the current collector is cut into a proper size and put under a 30W laser marking machine for roughening, the laser marking distance is 0.01 mm-0.05 mm, and the power is 50% -90%.

3. The current collector cleaning treatment method according to claim 1, wherein the current collector is placed in acetone, ethanol, weak acid and deionized water, and each ultrasonic treatment is carried out for 2-10 min.

4. The pencil shavings of claim 1 derived from HB-12B pencils, wherein the pencil shavings remain on the current collector after the pencil strokes have been applied.

5. The binder of claim 1 wherein the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, and polymethyl methacrylate.

6. The adhesive coating method according to claim 1, wherein the adhesive is coated on the current collector scratched with the pencil shavings and dried overnight in a vacuum oven at 60 ℃.

7. The binder coating amount according to claim 1, wherein the binder is contained in an amount of 0.05 to 40% by weight based on the total weight of the binder and the positive electrode material.

8. The aluminum-ion battery based on a pencil coating positive electrode according to claim 1, characterized in that: the positive pole piece comprises a current collector, a positive active material layer and a binder coating layer, wherein the positive active material layer is coated by a pencil.

9. The aluminum-ion battery based on a pencil coating positive electrode according to claim 1, characterized in that: the negative pole piece comprises a current collector and a negative active material layer, and the negative active material layer can be made of aluminum metal with the purity not less than 90% or an alloy of the aluminum metal and other metals.

10. The aluminum-ion battery based on a pencil coating positive electrode according to claim 1, characterized in that: the diaphragm comprises common diaphragm materials such as a glass fiber diaphragm, a polypropylene diaphragm, a polyethylene diaphragm and the like.

11. The aluminum-ion battery based on a pencil coating positive electrode according to claim 1, characterized in that: the electrolyte comprises imidazole system electrolyte, urea system electrolyte and gel polymer electrolyte.

Technical Field

The invention relates to the field of aluminum ion batteries, in particular to an aluminum ion battery based on a pencil coating positive electrode and a preparation method thereof.

Background

With the increase of energy problems, the use of secondary batteries in electric vehicles is increasing. Since the first battery of the invention, the battery is developed toward high efficiency for portability. The advent of lithium ion batteries until 1991 has created a promise for a variety of portable electronic devices. However, the problems of high cost, poor safety, slow charging rate and the like of the power battery mainly made of the lithium ion battery are gradually highlighted, and the requirements of large-scale energy storage in the future are obviously not met.

Among numerous secondary chemical batteries, aluminum ion batteries have the highest volumetric specific capacity, the theoretical volumetric energy density of which is four times that of lithium ion batteries, and the mass specific capacity of which is second to that of the lithium ion batteries. However, the conventional preparation method of the cathode material is complicated, and the problem of peeling of the electrode material is serious, so that the development of the aluminum ion battery is limited. In view of the above problem, there is a need to develop an aluminum ion battery that is simple to manufacture and has both high capacity and high coulombic efficiency.

Disclosure of Invention

1. The invention aims to provide a simple preparation method of an aluminum ion battery electrode

2. The preparation method of the aluminum ion battery electrode comprises the following steps: and carrying out laser roughening and cleaning treatment on the current collector, further simply scratching and coating pencil scraps on the surface of the current collector, and finally carrying out surface modification treatment on the molybdenum sheet scratched and coated with the pencil scraps by using a binder coating method.

2. The roughening treatment method of the current collector by laser comprises the following steps: cutting the current collector into proper size, and placing the current collector under a 30W laser marking machine for roughening treatment, wherein the laser marking interval is 0.01-0.05 mm, and the power is 50-90%.

3. The current collector cleaning treatment method comprises the following steps: and immersing the current collector into acetone, ethanol, weak acid and deionized water, and carrying out ultrasonic treatment for 2-10 min respectively.

4. The pencil scraps are derived from HB-12B pencils, and pencil graphite can be left on the current collector after the pencil scraps are coated by pencil strokes.

5. The binder used on the surface of the aluminum ion battery comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene and polymethyl methacrylate.

6. The adhesive coating method comprises the following steps: the binder was coated on a current collector scratched with pencil shavings and dried in a vacuum oven at 60 ℃ overnight.

7. The coating amount of the binder is 0.05-40% of the total weight of the binder and the positive electrode material.

8. The positive pole piece comprises a current collector, a positive active material layer and a binder coating layer, wherein the positive active material layer is obtained by adopting a lead stroke coating method.

9. The negative pole piece comprises a current collector and a negative active material layer, and the negative active material layer can be made of aluminum metal with the purity not less than 90% or an alloy of the aluminum metal and other metals.

10. The diaphragm comprises common diaphragm materials such as a glass fiber diaphragm, a polypropylene diaphragm, a polyethylene diaphragm and the like.

11. The electrolyte comprises imidazole system electrolyte, urea system electrolyte and gel polymer electrolyte.

The invention aims to provide an aluminum ion battery based on a pencil coating positive electrode and a preparation method thereof,

the molybdenum substrate is roughened by laser, a film is formed on the surface of the molybdenum substrate in a mode of simply coating by a pencil, and a trace amount of binder is dripped on the surface of the film to improve the stability. Compared with the traditional method for preparing the graphite anode of the aluminum ion battery, the method provided by the invention has the advantages that the high capacity and the high coulombic efficiency are ensured, the processing technology of the aluminum ion battery is simplified, and the method has important value in future practical application.

Drawings

FIG. 1: the long cycle performance curve of the aluminum ion battery assembled in example 1 of the present invention. Wherein: the X axis is the number of cycles, the Y1 axis is the specific discharge capacity (mAh g-1), and the Y2 axis is the coulombic efficiency (%).

FIG. 2: the long cycle performance curve of the aluminum ion battery assembled in example 2 of the present invention. Wherein: the X axis is the number of cycles, the Y1 axis is the specific discharge capacity (mAh g-1), and the Y2 axis is the coulombic efficiency (%).

Detailed Description

In the specific implementation process, the preparation method of the aluminum ion battery electrode comprises the steps of carrying out laser roughening treatment on a current collector and cleaning the surface of the current collector, simply scratching pencil scraps on the surface of the current collector, and further carrying out surface modification treatment on the pencil scraps by using a binder coating method. The aluminum ion battery is directly assembled by using the treated anode, so that the structure and the processing technology of the aluminum ion battery are simplified, and the aluminum ion battery has important value in future practical application.

The present invention will be described in more detail with reference to the following embodiments and the accompanying drawings.

Example 1

In this example, a molybdenum sheet cut to 10cm × 10cm was placed under a 30W laser marker to be roughened, with a laser marking pitch of 0.01mm and a power of 90%. Punching and cutting pole piece into 1cm²The molybdenum sheet is respectively treated by ultrasonic treatment in acetone, ethanol, weak acid and deionized water for 10min, and then dried for standby. And scratching a layer of 8B pencil scraps on the surface of the current collector by using a pencil. Preparing 0.02g/ml polyvinylidene fluoride solution: the two substances, N-methylpyrrolidone and polyvinylidene fluoride, were mixed in a jar by magnetic stirring until there was no white substance in the solution. It should be noted that: after the preparation, the jar is sealed by the sealing compound. Coating the binder on a current collector coated with the pencil scraps, and then putting the current collector into a vacuum drying oven, wherein the drying temperature is 60 ℃ and the drying time is 6 hours; putting the mixture into a glove box while the mixture is hot, and assembling the aluminum ion battery.

In the process of assembling the aluminum ion battery, in the example, the aluminum ion battery is assembled by adopting the ionic liquid with the molar ratio of the anhydrous aluminum trichloride to the 1-ethyl-3-methyl imidazole chloride of 1.3:1 as the electrolyte, the high-purity aluminum foil as the negative electrode and the prepared material as the positive electrode. The prepared aluminum ion battery can be stably circulated for 2000 times, the capacity of more than 100mAh/g is provided, and the coulombic efficiency can reach 95% (figure 1).

Example 2

In this example, a molybdenum sheet cut to 10cm × 10cm was placed under a 30W laser marker to be roughened, with a laser marking pitch of 0.01mm and a power of 90%. Punching and cutting pole piece into 1cm area²The molybdenum sheet is respectively treated by ultrasonic treatment in acetone, ethanol, weak acid and deionized water for 10min, and then dried for standby. Scratching a layer of 8B pencil scraps on the surface of a current collector by using a pencil, and then putting the current collector into a vacuum drying box, wherein the drying temperature is 60 ℃ and the drying time is 6 hours; putting the mixture into a glove box while the mixture is hot, and assembling the aluminum ion battery.

In the process of assembling the aluminum ion battery, in the example, the aluminum ion battery is assembled by adopting the ionic liquid with the molar ratio of the anhydrous aluminum trichloride to the 1-ethyl-3-methyl imidazole chloride of 1.3:1 as the electrolyte, the high-purity aluminum foil as the negative electrode and the prepared material as the positive electrode. The prepared aluminum ion battery can be stably circulated for 2000 times, the capacity of more than 36mAh/g can be provided, and the coulombic efficiency can reach 96% (figure 2).

The above examples are only preferred results of the present invention, and are not intended to limit the present invention, and all equivalent substitutions and modifications based on the principle of the present invention are within the protection scope of the present invention.