阅读说明：本技术 一种图案化超轻柔性自支撑锌电极的制备方法及其应用 (Preparation method and application of patterned ultralight flexible self-supporting zinc electrode ) 是由 张冠华 李金昊 段辉高 胡晋 于 2020-06-12 设计创作，主要内容包括：本发明公开了一种图案化超轻柔性自支撑锌电极的制备方法及其应用,本发明具有环境友好、可定制图案、无需添加导电剂和粘结剂、超轻超薄、能自支撑和力学性能优良的优点。相比于现有的柔性锌离子电池负极,本发明所得柔性电极由可定制图案化的单层锌网格组成,集流体和活性材料均为锌金属,电极的孔状间隙能有效抑制充放电过程中锌沉积引起的体积膨胀和枝晶生长,也有利于电解液的渗透。所制备的柔性电极能够承受反复弯曲而不发生断裂,且电化学性能基本保持不变,能够直接剪裁用于装配电池,便于锌离子电池的外形设计和组装。(The invention discloses a preparation method and application of a patterned ultralight flexible self-supporting zinc electrode. Compared with the conventional flexible zinc ion battery cathode, the flexible electrode obtained by the invention consists of the single-layer zinc grid which can be customized and patterned, the current collector and the active material are zinc metal, and the porous gaps of the electrode can effectively inhibit the volume expansion and dendritic crystal growth caused by zinc deposition in the charging and discharging processes and are also beneficial to the permeation of electrolyte. The prepared flexible electrode can bear repeated bending without breaking, the electrochemical performance is basically kept unchanged, and the flexible electrode can be directly cut for assembling a battery, so that the appearance design and the assembly of the zinc ion battery are facilitated.)

1. The preparation method and the application of the patterned ultralight flexible self-supporting zinc electrode are characterized in that the obtained ultralight flexible electrode is composed of a customizable patterned single-layer zinc grid, the thickness of the electrode is in a micron level, a current collector and an active material are both zinc metal, and the preparation method comprises the following steps:

(1) sequentially placing the planar conductive film in ethanol and deionized water for ultrasonic cleaning;

(2) spin-coating a photoresist on the substrate obtained in the step (1);

(3) placing the substrate obtained in the step (2) on a constant temperature plate for drying glue;

(4) carrying out patterning exposure on the photoresist on the substrate obtained in the step (3), and cleaning for a certain time by using a sodium hydroxide solution to prepare a hard template;

(5) dissolving zinc sulfate heptahydrate, sodium sulfate and boric acid in deionized water to prepare electroplating solution;

(6) placing the hard template obtained in the step (4) in the electroplating solution obtained in the step (5) for electroplating for a certain time to prepare a zinc plate;

(7) and (4) placing the zinc plate obtained in the step (6) in a sodium hydroxide solution to obtain the patterned ultralight flexible self-supporting zinc electrode.

2. The method for preparing the patterned ultra-light flexible self-supporting zinc electrode according to claim 1, wherein the method comprises the following steps: and (2) in the step (1), the planar conductive film is an ITO (indium tin oxide), AZO (aluminum-doped zinc oxide) or graphite plate.

3. The method for preparing the patterned ultra-light flexible self-supporting zinc electrode according to claim 1, wherein the method comprises the following steps: the photoresist in the step (2) is a Ruizhong photoresist.

4. The method for preparing the patterned ultra-light flexible self-supporting zinc electrode according to claim 1, wherein the method comprises the following steps: in the step (2), the spin coater sequentially performs spin coating for a certain time at one or more rotation speeds, wherein the spin coating rotation speed range is 500-3000rpm, and the spin coating time is 10-120 s.

5. The method for preparing the patterned ultra-light flexible self-supporting zinc electrode according to claim 1, wherein the method comprises the following steps: and (3) drying the glue of the thermostatic plate at one or more temperatures for a certain time in sequence, wherein the glue drying temperature range is 50-100 ℃, and the glue drying time is 5-90 min.

6. The method for preparing the patterned ultra-light flexible self-supporting zinc electrode according to claim 1, wherein the method comprises the following steps: the patterning exposure time in the step (4) is 5-100s, the concentration of the used sodium hydroxide solution is 0.1% -2%, and the cleaning time is 10-100 s.

7. The method for preparing the patterned ultra-light flexible self-supporting zinc electrode according to claim 1, wherein the method comprises the following steps: the components of the electroplating solution in the step (5) are 5-20 wt% of zinc sulfate heptahydrate, 10-20 wt% of sodium sulfate, 0.1-1 wt% of boric acid solution and 59-84.9 wt% of deionized water.

8. The method for preparing the patterned ultra-light flexible self-supporting zinc electrode according to claim 1, wherein the method comprises the following steps: the electroplating mode in the step (6) can be constant current or constant voltage, and the constant current density range is 0.5-50mA cm^-2The constant voltage range is 0.5-3V, and the electroplating time is 5-30 min.

9. The method for preparing the patterned ultra-light flexible self-supporting zinc electrode according to claim 1, wherein the method comprises the following steps: in the step (6), the mass fraction of the sodium hydroxide solution is 2-10 wt%, and the soaking time is 1-5 min.

10. Use of the patterned ultra-light flexible self-supporting zinc electrode prepared by the method of claims 1-9 as a negative electrode of a zinc-ion battery.

Technical Field

The invention relates to the field of electrode preparation, in particular to a preparation method and application of an electrode.

Background

With the rapid development of wearable electronic technology, higher requirements are put on the lightness, flexibility, biosafety and cycle life of energy supply devices. The rechargeable aqueous zinc ion battery has the advantages of low cost, high operation safety, environmental friendliness and the like, and has obvious potential in application of wearable devices. The zinc metal is an ideal cathode of the water system zinc ion battery due to high theoretical capacity, relatively low oxidation-reduction potential, low cost, good electrochemical stability in water and the like.

At present, a current collector and an active material heterostructure are mostly adopted for a zinc cathode, the current collector is manufactured by photoetching, selective melting and other modes, most materials are carbon-based materials, copper, stainless steel nets and the like, and then zinc metal is plated on the current collector in electrochemical deposition and other modes to serve as an active material. The cycle life of the device is limited by dendritic growth, corrosion, uneven zinc deposition/stripping and the like in the charging and discharging processes of the conventional flexible zinc cathode. The current collector and the active material heterostructure adopted by the existing zinc cathode also greatly increase the quality of the device. Therefore, it is necessary to develop an ultra-light flexible self-supporting zinc negative electrode capable of effectively inhibiting the growth of dendrites.

Disclosure of Invention

Aiming at the problems, the invention aims to provide a simple, convenient and feasible method for preparing an ultra-light flexible self-supporting zinc negative electrode with customizable and patterned patterns, so as to reduce the quality of a zinc ion battery device and inhibit the growth of zinc dendrites, thereby improving the electrochemical performance of the zinc ion battery device

The technical scheme adopted by the invention for solving the technical problems is as follows:

(1) placing the low-dimensional conductive material in ethanol and deionized water in sequence for ultrasonic cleaning;

(2) spin-coating a photoresist on the substrate obtained in the step (1);

(3) placing the substrate obtained in the step (2) on a constant temperature plate for drying glue;

(4) carrying out patterning exposure on the photoresist on the substrate obtained in the step (3), and cleaning for a certain time by using a sodium hydroxide solution to prepare a hard template;

(5) dissolving zinc sulfate heptahydrate, sodium sulfate and boric acid in deionized water to prepare electroplating solution;

(6) placing the hard template obtained in the step (4) in the electroplating solution obtained in the step (5) for electroplating for a certain time to prepare a zinc plate;

(7) and (4) placing the zinc plate obtained in the step (6) in a sodium hydroxide solution to obtain the patterned ultralight flexible self-supporting zinc electrode.

The patterned ultralight flexible self-supporting zinc electrode prepared by the preparation method.

The patterned ultralight flexible self-supporting zinc electrode is applied as a negative electrode of a zinc ion battery.

The invention has the following beneficial effects: compared with the prior art, the invention has the advantages of environmental protection, customizable patterns, no need of adding conductive agent and binder, ultralight and ultrathin property, self-support and excellent mechanical property. The flexible electrode obtained by the invention is composed of a single-layer zinc grid which can be customized and patterned, the current collector and the active material are both zinc metal, and the porous gaps of the electrode inhibit the volume expansion and dendritic crystal growth caused by zinc deposition in the charging and discharging processes, and are also beneficial to the permeation of electrolyte. The obtained flexible electrode can bear repeated bending without fracture, and the electrochemical performance is basically kept unchanged. The obtained flexible electrode can be directly cut for assembling the battery, so that the appearance design and the assembly of the zinc ion battery are facilitated.

Drawings

FIG. 1 optical microscope photograph of patterned ultra-light flexible self-supporting zinc electrode prepared in example 1 of the present invention.

Fig. 2 flexible curl test photographs of patterned ultra-light flexible self-supporting zinc electrodes prepared in example 1 of the present invention.

Fig. 3 is a scanning electron micrograph of the patterned ultra-light flexible self-supporting zinc electrode prepared in example 1 of the present invention.

Fig. 4X-ray diffraction pattern of patterned ultra-light flexible self-supporting zinc electrode prepared in example 1 of the present invention.

Fig. 5 is a symmetrical cell overpotential curve for an ultra-light flexible self-supporting zinc electrode prepared in example 1 of the present invention.

Fig. 6 is a device showing a view when the electrode prepared in example 1 of the present invention is used as a negative electrode of a zinc ion battery.

Detailed Description

The following describes embodiments of the present invention with reference to specific examples.