CN117558864A - Zinc metal negative electrode modified by nanoscale copper layer and preparation method thereof - Google Patents
Zinc metal negative electrode modified by nanoscale copper layer and preparation method thereof Download PDFInfo
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- CN117558864A CN117558864A CN202311534480.5A CN202311534480A CN117558864A CN 117558864 A CN117558864 A CN 117558864A CN 202311534480 A CN202311534480 A CN 202311534480A CN 117558864 A CN117558864 A CN 117558864A
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- zinc
- copper layer
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 45
- 239000010949 copper Substances 0.000 title claims abstract description 45
- 239000011701 zinc Substances 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000005498 polishing Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005554 pickling Methods 0.000 claims abstract description 8
- 244000137852 Petrea volubilis Species 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000000428 dust Substances 0.000 claims abstract description 5
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 5
- 231100000719 pollutant Toxicity 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract 2
- 230000006911 nucleation Effects 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 19
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
Classifications
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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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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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- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a zinc metal negative electrode modified by a nanoscale copper layer and a preparation method thereof, the method comprises the following three steps of firstly, placing zinc foil in a mixed solution of ethanol and water, and ultrasonically removing dust and pollutants on the surface of the zinc foil; step two, placing the zinc foil in a dilute acid solution for pickling treatment, and polishing the zinc foil by using sand paper; and thirdly, placing the zinc foil in an evaporator, and then heating copper metal into steam to enable copper steam to be deposited on the surface of the zinc foil. The invention is used for evaporating the nano-scale copper layer on the surface of the zinc metal negative electrode, and has the advantages of simple process, good controllability of the copper layer thickness, short time and the like. The nanoscale copper layer not only has high zinc-philic characteristic, but also promotes uniform nucleation of zinc; and the electrolyte also has the characteristic of high hydrophobicity, and can prevent free water in the electrolyte from directly contacting with the zinc cathode, so that the growth of zinc dendrites and the occurrence of interface side reactions can be effectively inhibited, and the stability and reversibility of the zinc cathode are obviously improved.
Description
Technical Field
The invention belongs to the field of water-based zinc ion batteries, and particularly relates to a zinc metal negative electrode modified by a nanoscale copper layer and a preparation method thereof.
Background
The water-based zinc ion battery has the advantages of no toxicity, high safety, low cost and the like, and is widely considered as a next-generation energy storage device which is expected to replace a lithium ion battery. However, zinc metal cathodes are limited by dendrite growth, hydrogen evolution side reactions and surface passivation, severely hampering the large-scale practical application of aqueous zinc ion batteries.
During zinc ion deposition, the hydrogen evolution reaction potential (-0.296V) of water is higher than the oxidation-reduction potential (-0.76V) of zinc, so that the hydrogen evolution reaction is thermodynamically unavoidable. On the other hand, uncontrolled zinc dendrite growth is caused by non-uniform electric fields and "tip" effects. These side reactions lead to problems of low coulombic efficiency, poor cycle life, and low utilization of the zinc anode of the zinc ion battery. In order to solve the problems, researchers propose to construct a stable protective layer on the surface of a zinc metal negative electrode so as to achieve the aim of inhibiting zinc dendrite growth and interfacial side reaction, thereby improving the performance of a zinc ion battery; however, the thickness of the protective layer constructed at present is in the micron level, so that the ion transmission distance is prolonged, the internal resistance of the battery is increased, and the rate capability of the battery is poor, so that development of a nanoscale protective layer suitable for a zinc metal anode is urgently needed.
Disclosure of Invention
The invention provides a zinc metal negative electrode modified by a nanoscale copper layer and a preparation method thereof, aiming at solving the defects in the prior art.
The technical scheme adopted by the invention specifically comprises the following steps:
step one, placing zinc foil in a mixed solution of ethanol and water, and ultrasonically removing dust and pollutants on the surface of the zinc foil;
step two, placing the zinc foil in a dilute acid solution for pickling treatment, and polishing the zinc foil by using sand paper;
and thirdly, placing the zinc foil in an evaporator, and then heating copper metal into steam to enable copper steam to be deposited on the surface of the zinc foil.
Further, in the first step, the ratio of ethanol to water in the mixed solution is 1:1 to 1:5.
further, in the first step, the ultrasonic time is 10-30 minutes.
Further, in the second step, the dilute acid is hydrochloric acid, sulfuric acid or nitric acid.
Further, in the second step, the concentration of the dilute acid is 0.1 to 1mol L -1 。
Further, in the second step, the pickling treatment time is 10 to 60 minutes.
Further, in the second step, the polishing time is 10-60 minutes.
Further, in the third step, the temperature of heating the copper metal is 400-800 ℃.
Further, in the third step, the thickness of the copper layer deposited on the surface of the zinc foil is 10-100 nanometers.
Compared with the prior art, the method realizes the modification of the nano-scale copper layer on the zinc metal surface through the steps of cleaning, acid washing, vapor plating and the like, has the advantages of simple process, low cost, environmental protection and easy large-scale preparation, and has good development prospect in constructing the zinc metal modification layer by the vapor plating method.
Drawings
FIG. 1 is a flow chart of evaporating a nanoscale copper layer on a zinc metal surface;
FIG. 2 is a scanning electron microscope image of the zinc metal modified by the copper layer in example 1 of the present invention;
FIG. 3 is a cycle test chart of the symmetrical battery in example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of the zinc metal modified by the copper layer in example 2 of the present invention;
Detailed Description
The present invention will be described in detail with reference to the following examples, so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following examples. Fig. 1 is a flow chart of evaporating a nano-scale copper layer on a zinc metal surface, wherein the nano-scale copper layer is modified on the zinc metal surface mainly through steps of cleaning, acid washing, evaporating and the like.
Example 1
In example 1, a nano-scale copper layer was modified on a zinc metal surface using an evaporator, specifically comprising the following three steps:
(1) Placing commercial zinc foil in a mixed solution of ethanol and water in a ratio of 1:1, and performing ultrasonic treatment for 20 minutes to remove dust and pollutants on the surface of the commercial zinc foil;
(2) Placing the cleaned zinc foil in 0.1mol L -1 In dilute sulfuric acid solution, carrying out acid washing treatment for 30 minutes, and then polishing for 20 minutes by using 1000-mesh sand paper and 2000-mesh sand paper;
(3) Placing the zinc foil after pickling and polishing in an evaporator, and then heating copper metal to 500 ℃ to enable copper steam to deposit 50 nanometers on the surface of the zinc foil.
Fig. 2 is a scanning electron microscope image of the zinc metal modified with the copper layer in this example 1, from which it can be seen that the commercial zinc foil, after pickling and polishing, has had the zinc oxide film on the surface removed, but the surface becomes uneven. Copper layers of 50nm are evaporated on the surfaces of the copper layers, and the uneven surface morphology cannot be changed.
FIG. 3 is a Zn// Zn symmetric cell assembled at 1mAcm using a copper layer modified zinc metal electrode -2 、1mAh cm -2 The cyclic graph under the test condition shows that the initial polarization voltage is 44mV, and the polarization voltage is unchanged after 1000 hours of charge-discharge cycle, so that the cyclic graph shows good cyclic stability and reversibility.
Example 2
In example 2, a nano-scale copper layer was modified on the zinc metal surface using an evaporator, specifically comprising the following three steps:
(1) Placing commercial zinc foil in a mixed solution of ethanol and water in a ratio of 1:2, and performing ultrasonic treatment for 30 minutes to remove dust and pollutants on the surface of the commercial zinc foil;
(2) Placing the cleaned zinc foil in 0.5mol L -1 In dilute sulfuric acid solution, carrying out acid washing treatment for 10 minutes, and then polishing for 30 minutes by using 1000-mesh sand paper and 2000-mesh sand paper;
(3) Placing the zinc foil after pickling and polishing in an evaporator, and then heating copper metal to 600 ℃ to enable copper steam to deposit 100 nanometers on the surface of the zinc foil.
Fig. 4 is a scanning electron microscope image of the zinc metal modified with the copper layer in example 1 at a low resolution, from which it can be seen that the surface becomes uneven although the zinc oxide film on the surface is removed after the commercial zinc foil is subjected to acid washing and polishing. Even if a copper layer of 100nm is deposited on the surface, the uneven surface morphology cannot be changed.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (9)
1. The zinc metal negative electrode modified by the nanoscale copper layer and the preparation method thereof are characterized by comprising the following steps:
step one, placing zinc foil in a mixed solution of ethanol and water, and ultrasonically removing dust and pollutants on the surface of the zinc foil;
step two, placing the zinc foil in a dilute acid solution for pickling treatment, and polishing the zinc foil by using sand paper;
and thirdly, placing the zinc foil in an evaporator, and then heating copper metal into steam to enable copper steam to be deposited on the surface of the zinc foil.
2. The zinc metal anode modified by a nanoscale copper layer and the preparation method thereof according to claim 1, wherein in the first step, the ratio of ethanol to water in the mixed solution is 1:1 to 1:5.
3. the zinc metal anode modified by the nanoscale copper layer and the preparation method thereof according to claim 1, wherein in the first step, the ultrasonic time is 10-30 minutes.
4. The zinc metal anode modified by a nanoscale copper layer and the preparation method thereof according to claim 1, wherein in the second step, the dilute acid is hydrochloric acid, sulfuric acid or nitric acid.
5. The zinc metal anode modified by the nanoscale copper layer and the preparation method thereof according to claim 1, wherein in the second step, the pickling treatment time is 10-60 minutes.
6. The nano-scale copper layer modified zinc metal anode and the preparation method thereof according to claim 1, wherein in the second step, the dilute acid concentration is 0.1-1 mol L -1 。
7. The zinc metal anode modified by the nanoscale copper layer and the preparation method thereof according to claim 1, wherein in the second step, polishing time is 10-60 minutes.
8. The zinc metal anode modified by a nanoscale copper layer and the preparation method thereof according to claim 1, wherein in the third step, the temperature for heating the copper metal is 400-800 ℃.
9. The zinc metal negative electrode modified by a nanoscale copper layer and the preparation method thereof according to claim 1, wherein in the third step, the thickness of the copper layer deposited on the surface of the zinc foil is 10-100 nanometers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311534480.5A CN117558864A (en) | 2023-11-16 | 2023-11-16 | Zinc metal negative electrode modified by nanoscale copper layer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311534480.5A CN117558864A (en) | 2023-11-16 | 2023-11-16 | Zinc metal negative electrode modified by nanoscale copper layer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117558864A true CN117558864A (en) | 2024-02-13 |
Family
ID=89822862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311534480.5A Pending CN117558864A (en) | 2023-11-16 | 2023-11-16 | Zinc metal negative electrode modified by nanoscale copper layer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117558864A (en) |
-
2023
- 2023-11-16 CN CN202311534480.5A patent/CN117558864A/en active Pending
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