CN112643193A - Preparation method of zinc with composite microstructure of zinc-air battery - Google Patents
Preparation method of zinc with composite microstructure of zinc-air battery Download PDFInfo
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- CN112643193A CN112643193A CN202011463128.3A CN202011463128A CN112643193A CN 112643193 A CN112643193 A CN 112643193A CN 202011463128 A CN202011463128 A CN 202011463128A CN 112643193 A CN112643193 A CN 112643193A
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- zinc
- air battery
- sheet
- microstructure
- zinc sheet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/062—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam
- B23K26/0622—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses
- B23K26/0624—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses using ultrashort pulses, i.e. pulses of 1ns or less
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/70—Auxiliary operations or equipment
- B23K26/702—Auxiliary equipment
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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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
- H01M4/06—Electrodes for primary cells
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Plasma & Fusion (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Laser Beam Processing (AREA)
Abstract
A preparation method of zinc with a composite microstructure of a zinc-air battery belongs to the technical field of surface processing. The invention relates to a preparation method of special microstructure zinc for a zinc-air battery, which takes femtosecond laser direct writing as a processing technology to prepare zinc with a composite microstructure under the protection of ethanol isolated from air and is used for a zinc-air battery cathode material. The microstructure zinc sheet disclosed by the invention has abundant surface micro-morphology, and the discharge performance of the zinc-air battery is improved in the working process of the zinc-air battery.
Description
Technical Field
The invention relates to a preparation method of special microstructure zinc for a zinc-air battery, which takes femtosecond laser direct writing as a processing technology to prepare zinc with a composite microstructure under the protection of ethanol isolated from air and is used for a zinc-air battery cathode material. The invention provides a new method for researching a zinc-air battery cathode, and belongs to the technical field of surface processing.
Background
With the continuous breakthrough of the laser technology, the laser processing technology is no longer a rare processing means, and is widely applied to different fields of medical cosmetology, aerospace, transportation, environmental energy and the like in recent years. Due to the advantages of ultrashort pulse, higher peak power and higher energy of the femtosecond laser, the corresponding femtosecond laser processing has the characteristics of cold processing (very low heat effect), flat processing edge (no hot melt zone), high processing precision and capability of realizing micro-nano scale processing. The processing of metals can be controlled on the micron scale, while the induced microstructure can change the inherent physicochemical properties of the metal. As a relatively active metal in a metal activity sequence, the processing of a zinc sheet by using femtosecond laser is accompanied by heat effect. The femtosecond laser direct writing zinc sheet is a material reduction processing technology, and the properties in application can be changed by the generated special microstructure. The zinc-air battery is an important classification in rechargeable energy supply batteries, and the negative active material in the working electrode is a metal zinc simple substance. According to the working principle, the reaction of zinc is the dissolution-deposition process of zinc, which corresponds to the discharge-charge process of the battery. From this, it is understood that the phase and structure of the zinc negative electrode may affect the charge and discharge performance of the zinc-air battery. In various researches on a zinc negative electrode in a rechargeable zinc-air battery, the researches mainly focus on coating layers, additives and alloying, and the influence of a microstructure on the charge and discharge of the zinc-air battery is relatively little. Therefore, the invention obtains the special microstructure by directly writing the zinc cathode of the zinc-air battery by utilizing the femtosecond processing technology.
Disclosure of Invention
The invention relates to a special microstructure of a zinc cathode of a zinc-air battery, which is obtained by using a femtosecond laser processing technology.
The technical scheme of the invention is as follows:
the preparation method of the composite microstructure zinc sheet comprises the following steps:
(1) polishing an analytically pure zinc sheet by using 500-plus-1500-mesh sand paper, removing a zinc oxide layer on the surface, and cleaning by using ethanol to remove zinc oxide particles;
(2) placing the zinc sheet cleaned in the step (1) in a strip-shaped flat-bottom magnetic boat, and adding a protective liquid;
(3) placing the magnetic boat in the step (2) on a two-dimensional processing displacement table, and adjusting the moving speed of the displacement table to be 1-10 mm/s;
(4) performing laser direct writing on a zinc sheet in the magnetic boat by using femtosecond laser, wherein the laser wavelength is 800nm, the pulse width is 100fs, the repetition frequency is 1-100kHz, and the power is set to be 0.2-0.5W;
(5) and after the processing is finished, taking out the zinc sheet from the liquid and drying the zinc sheet to obtain the zinc sheet with the composite microstructure.
Preferably, the sand paper described in step (1) is 1500 mesh;
preferably according to the invention, the liquid described in step (2) is ethanol;
preferably, according to the invention, the movement speed described in step (3) is 5 mm/s;
preferably, according to the invention, the laser frequency described in step (4) is 100kHz and the power setting is 0.3W.
The microstructure zinc sheet in the step (5) is applied as a negative electrode of a zinc-air battery, and the specific application method is as follows:
the microstructure zinc sheet is used as a negative electrode, the Pt/C compound is used as a positive electrode catalyst, and 6M KOH solution is used as electrolyte to form the zinc-air battery.
The microstructure zinc sheet disclosed by the invention has abundant surface micro-morphology, and the discharge performance of the zinc-air battery is improved in the working process of the zinc-air battery. At 2mA cm-2The first discharge time was 80 minutes and the second discharge time was 63 minutes at the current density of (1), indicating that the discharge capacity of the zinc-air battery was greatly improved.
Drawings
FIG. 1 is a schematic illustration of laser machining of examples 1, 2, 3, 4 of the present invention.
FIG. 2 is a scanning electron micrograph of a zinc plate according to example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of a zinc plate according to example 2 of the present invention.
FIG. 4 is a scanning electron micrograph of a zinc plate according to example 3 of the present invention.
FIG. 5 is a scanning electron micrograph of a zinc plate according to example 4 of the present invention.
FIG. 6 is a test chart of a charge-discharge cycle according to an embodiment of the present invention.
FIG. 7 is a scanning electron microscope photograph of a zinc sheet according to a preferred embodiment of the present invention.
Detailed Description
The present invention will be further described with reference to the following detailed description of embodiments thereof, but not limited thereto, in conjunction with the accompanying drawings.
Example 1
(1) Polishing an analytically pure zinc sheet by 1500-mesh abrasive paper, removing a zinc oxide layer on the surface, and cleaning by using ethanol to remove zinc oxide particles;
(2) placing the zinc sheet cleaned in the step (1) in a strip-shaped flat-bottom magnetic boat, and adding an ethanol protective solution;
(3) placing the magnetic boat in the step (2) on a two-dimensional processing displacement table, and adjusting the moving speed of the displacement table to be 5 mm/s;
(4) performing laser direct writing on a zinc sheet in the magnetic boat by using femtosecond laser, wherein the laser frequency is 100kHz, and the power is set to be 0.2W;
(5) and after the processing is finished, taking out the zinc sheet from the liquid and drying the zinc sheet to obtain the zinc sheet with the composite microstructure.
The first discharge time of the zinc sheet assembled battery processed in this example was 53 minutes and the second discharge time was 17 minutes.
Example 2
(1) Polishing an analytically pure zinc sheet by using 500-mesh abrasive paper, removing a zinc oxide layer on the surface, and cleaning by using ethanol to remove zinc oxide particles;
(2) placing the zinc sheet cleaned in the step (1) in a strip-shaped flat-bottom magnetic boat, and adding an ethanol protective solution;
(3) placing the magnetic boat in the step (2) on a two-dimensional processing displacement table, and adjusting the moving speed of the displacement table to be 2 mm/s;
(4) performing laser direct writing on a zinc sheet in the magnetic boat by using femtosecond laser, wherein the laser frequency is 50kHz, and the power is set to be 0.25W;
(5) and after the processing is finished, taking out the zinc sheet from the liquid and drying the zinc sheet to obtain the zinc sheet with the composite microstructure.
The first discharge time of the zinc sheet assembled battery processed in this example was 55 minutes and the second discharge time was 23 minutes.
Example 3
(1) Polishing an analytically pure zinc sheet by using 500-mesh abrasive paper, removing a zinc oxide layer on the surface, and cleaning by using ethanol to remove zinc oxide particles;
(2) placing the zinc sheet cleaned in the step (1) in a strip-shaped flat-bottom magnetic boat, and adding a protective liquid;
(3) placing the magnetic boat in the step (2) on a two-dimensional processing displacement table, and adjusting the moving speed of the displacement table to be 2 mm/s;
(4) performing laser direct writing on a zinc sheet in the magnetic boat by using femtosecond laser, wherein the laser frequency is 100kHz, and the power is set to be 0.2W;
(5) and after the processing is finished, taking out the zinc sheet from the liquid and drying the zinc sheet to obtain the zinc sheet with the composite microstructure.
The first discharge time of the zinc sheet assembled battery processed in this example was 45 minutes and the second discharge time was 22 minutes.
Example 4
(1) Polishing an analytically pure zinc sheet by using 500-mesh abrasive paper, removing a zinc oxide layer on the surface, and cleaning by using ethanol to remove zinc oxide particles;
(2) placing the zinc sheet cleaned in the step (1) in a strip-shaped flat-bottom magnetic boat, and adding a protective liquid;
(3) placing the magnetic boat in the step (2) on a two-dimensional processing displacement table, and adjusting the moving speed of the displacement table to be 2 mm/s;
(4) performing laser direct writing on a zinc sheet in the magnetic boat by using femtosecond laser, wherein the laser frequency is 50kHz, and the power is set to be 0.3W;
(5) and after the processing is finished, taking out the zinc sheet from the liquid and drying the zinc sheet to obtain the zinc sheet with the composite microstructure.
The first discharge time of the zinc sheet assembled battery processed in this example was 55 minutes and the second discharge time was 37 minutes.
Claims (5)
1. A preparation method of zinc with a composite microstructure of a zinc-air battery is characterized by comprising the following steps:
(1) polishing an analytically pure zinc sheet by using 500-plus-1500-mesh sand paper, removing a zinc oxide layer on the surface, and cleaning by using ethanol to remove zinc oxide particles;
(2) placing the zinc sheet cleaned in the step (1) in a strip-shaped flat-bottom magnetic boat, and adding ethanol;
(3) placing the magnetic boat in the step (2) on a two-dimensional processing displacement table, and adjusting the moving speed of the displacement table to be 1-10 mm/s;
(4) performing laser direct writing on a zinc sheet in the magnetic boat by using femtosecond laser, wherein the laser wavelength is 800nm, the pulse width is 100fs, the repetition frequency is 1-100kHz, and the power is set to be 0.2-0.5W;
(5) and after the processing is finished, taking out the zinc sheet from the liquid and drying the zinc sheet to obtain the zinc sheet with the composite microstructure.
2. The method of claim 1, wherein: the sand paper described in step (1) is 1500 mesh.
3. The method of claim 1, wherein: the moving speed described in the step (3) is 5 mm/s.
4. The method of claim 1, wherein: the laser frequency described in step (4) was 100kHz and the power setting was 0.3W.
5. The application of the zinc with the composite microstructure of the zinc-air battery is characterized in that:
a zinc-air battery is formed by taking zinc with a composite microstructure as a negative electrode, a Pt/C composite as a positive electrode catalyst and 6M KOH solution as electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011463128.3A CN112643193A (en) | 2020-12-11 | 2020-12-11 | Preparation method of zinc with composite microstructure of zinc-air battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011463128.3A CN112643193A (en) | 2020-12-11 | 2020-12-11 | Preparation method of zinc with composite microstructure of zinc-air battery |
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| Publication Number | Publication Date |
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| CN112643193A true CN112643193A (en) | 2021-04-13 |
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| CN202011463128.3A Pending CN112643193A (en) | 2020-12-11 | 2020-12-11 | Preparation method of zinc with composite microstructure of zinc-air battery |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306794A (en) * | 2011-08-31 | 2012-01-04 | 上海尧豫实业有限公司 | Zinc electrode of zinc-air battery |
| KR20130023732A (en) * | 2011-08-29 | 2013-03-08 | 한국과학기술원 | Apparatus and method for nanoscale laser sintering of metal nanoparticles |
| US20130084504A1 (en) * | 2011-09-30 | 2013-04-04 | Michael Edward Badding | Micromachined electrolyte sheet |
| CN104947016A (en) * | 2015-05-28 | 2015-09-30 | 湖北工业大学 | Method for preparing zinc alloy super-hydrophobic and self-cleaning surface by using ultra-short pulse laser |
| CN105921887A (en) * | 2016-05-25 | 2016-09-07 | 武汉虹拓新技术有限责任公司 | Device and method for manufacturing three-dimensional structure battery based on ultrafast laser |
| CN106575786A (en) * | 2014-08-29 | 2017-04-19 | 夏普株式会社 | Air cathode battery using zinc slurry anode with carbon additives |
| CN109175708A (en) * | 2018-10-29 | 2019-01-11 | 北京航空航天大学 | A kind of method of metal surface micro-patterning |
| CN109249136A (en) * | 2018-09-28 | 2019-01-22 | 江苏理工学院 | A kind of laser and the compound method for preparing super-hydrophobic zinc alloy surface of acid solution |
-
2020
- 2020-12-11 CN CN202011463128.3A patent/CN112643193A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130023732A (en) * | 2011-08-29 | 2013-03-08 | 한국과학기술원 | Apparatus and method for nanoscale laser sintering of metal nanoparticles |
| CN102306794A (en) * | 2011-08-31 | 2012-01-04 | 上海尧豫实业有限公司 | Zinc electrode of zinc-air battery |
| US20130084504A1 (en) * | 2011-09-30 | 2013-04-04 | Michael Edward Badding | Micromachined electrolyte sheet |
| CN106575786A (en) * | 2014-08-29 | 2017-04-19 | 夏普株式会社 | Air cathode battery using zinc slurry anode with carbon additives |
| CN104947016A (en) * | 2015-05-28 | 2015-09-30 | 湖北工业大学 | Method for preparing zinc alloy super-hydrophobic and self-cleaning surface by using ultra-short pulse laser |
| CN105921887A (en) * | 2016-05-25 | 2016-09-07 | 武汉虹拓新技术有限责任公司 | Device and method for manufacturing three-dimensional structure battery based on ultrafast laser |
| CN109249136A (en) * | 2018-09-28 | 2019-01-22 | 江苏理工学院 | A kind of laser and the compound method for preparing super-hydrophobic zinc alloy surface of acid solution |
| CN109175708A (en) * | 2018-10-29 | 2019-01-11 | 北京航空航天大学 | A kind of method of metal surface micro-patterning |
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Application publication date: 20210413 |