CN116914143A - Preparation method of long-cycle zinc ion battery negative electrode beta-PVDF coating - Google Patents
Preparation method of long-cycle zinc ion battery negative electrode beta-PVDF coating Download PDFInfo
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- CN116914143A CN116914143A CN202310910320.XA CN202310910320A CN116914143A CN 116914143 A CN116914143 A CN 116914143A CN 202310910320 A CN202310910320 A CN 202310910320A CN 116914143 A CN116914143 A CN 116914143A
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 71
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 71
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 238000000576 coating method Methods 0.000 title claims abstract description 38
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000011701 zinc Substances 0.000 claims abstract description 49
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 45
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010146 3D printing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
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- 238000005516 engineering process Methods 0.000 claims abstract description 7
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- 238000007639 printing Methods 0.000 claims description 9
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- 239000012535 impurity Substances 0.000 claims description 3
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- 210000003477 cochlea Anatomy 0.000 claims description 2
- 230000008021 deposition Effects 0.000 abstract description 5
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- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
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- 150000003751 zinc Chemical class 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
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- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
-
- 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
-
- 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
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of zinc ion battery materials, in particular to a preparation method of a long-cycle zinc ion battery negative electrode beta-PVDF coating. The preparation method specifically comprises the following steps: cleaning a polished zinc metal sheet, drying for standby, adding polyvinylidene fluoride into an N-methyl pyrrolidone organic solvent, stirring uniformly to obtain a mixed solution, adding acetone into the mixed solution, and mixing uniformly to obtain ink; then constructing a beta-PVDF coating on the surface of the zinc metal sheet by using the ink through a 3D printing technology, and finally drying the zinc metal sheet constructed with the beta-PVDF coating to obtain a long-cycle secondary zinc battery negative beta-PVDF coating; wherein the polyvinylidene fluoride has the following model: PVDF-SOLEF5130, N-methylpyrrolidone concentration: 99.5% and an optimal addition ratio of polyvinylidene fluoride to N-methylpyrrolidone of 0.12:1, a step of; the phase of PVDF is changed by the shearing force generated during direct-writing 3D printing, and the uniform deposition of zinc ions on the surface of the beta-PVDF coating is ensured, so that the zinc ion battery has long cycle life.
Description
Technical Field
The invention relates to the technical field of zinc ion battery materials, in particular to a preparation method of a long-cycle zinc ion battery negative electrode beta-PVDF coating.
Background
Today's economy and technology are rapidly advancing, and the society is increasingly dependent on available energy. Traditional primary energy reserves of natural gas, coal, petroleum and the like are gradually exhausted, and the greenhouse effect is deepened and the environmental problem is remarkable due to direct combustion of fossil fuel. Therefore, new energy systems such as solar energy, wind energy, geothermal energy and tidal energy have been widely studied. However, these new energy sources have the disadvantages of greater volatility and inability to continuously generate electricity compared to fossil energy sources, limiting their use on a large scale for a long period of time. Therefore, the development of efficient energy storage systems is a need to address new energy applications and human social developments. The most fundamental criteria for developing an ideal large energy storage system are low cost, high reliability, good safety, environmental friendliness, high efficiency, long cycle life and high energy density.
Lithium ion batteries have been receiving attention since the commercialization development, and are dominant in the application of secondary batteries for nearly 30 years due to their high energy density and long cycle life. However, the use of flammable organic electrolytes for lithium ion batteries has serious problems of environmental pollution and poor safety, and lithium is severely in shortage of supply. Thus, aqueous zinc ion batteries are a powerful competitor for future large-scale electrical energy storage applications by virtue of cost effectiveness, environmental friendliness, safety and competitive energy density. Despite the great potential of zinc metal anodes, their poor rechargeability has prevented practical large-scale applications to some extent due to insufficient dendrite formation and deposition/stripping coulombic efficiency. Since zinc has very high mechanical properties, its young's modulus is much higher than that of lithium and sodium, which means that zinc dendrites, once formed on a large scale, can easily penetrate through the separator to grow, leading to failure of the battery. Dendrite formation, low deposition/stripping coulombic efficiency and poor cycling stability of zinc cathodes remain an obstacle to the use of zinc cathodes.
Therefore, optimizing the material and structural design of zinc cathodes is very critical. In recent years, along with the continuous breakthrough of related technologies in the field of nano materials, researchers propose a plurality of new methods for inhibiting the growth of zinc dendrites so as to expect to stabilize a metal zinc anode, improve the reversible use efficiency of active zinc and further improve the long-period cycle life of a battery, thereby obtaining an efficient and safe energy storage system with high energy density. The zinc negative electrode system without dendrite and high stability is constructed, and the development of a safe and efficient metal zinc negative electrode which is stable in the working process is of great significance to the construction of a new energy storage system.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a zinc ion battery with a beta-PVDF coating on a negative electrode and a preparation method thereof, wherein the phase of PVDF is changed through the shearing force generated during direct-writing 3D printing, so that the crystalline phase of the PVDF is converted from alpha phase to beta phase, thereby having higher dielectric property, ensuring that zinc ions are uniformly deposited on the surface of the beta-PVDF coating, and further enabling the zinc ion battery to have long cycle life.
A preparation method of a long-cycle zinc ion battery negative electrode beta-PVDF coating comprises the following specific steps: cleaning a polished zinc metal sheet, drying for standby, adding polyvinylidene fluoride into an N-methyl pyrrolidone organic solvent, stirring uniformly to obtain a mixed solution, adding acetone into the mixed solution, and mixing uniformly to obtain yellowish ink; printing ink on the surface of a zinc metal sheet through a 3D printing technology to construct a beta-PVDF coating, and finally drying the zinc metal sheet constructed with the beta-PVDF coating to obtain a long-cycle secondary zinc battery negative beta-PVDF coating;
wherein the polyvinylidene fluoride has the following model: PVDF-SOLEF5130, N-methylpyrrolidone concentration: 99.5% of polyvinylidene fluoride and N-methyl pyrrolidone, wherein the optimal adding ratio is as follows: 0.12:1.
preferably, the zinc foil has a size of 1cm in diameter and 0.05mm in thickness.
Preferably, when the zinc metal sheet is polished, 2000-mesh sand paper, 5000-mesh sand paper and 8000-mesh sand paper are sequentially used for polishing, so that an oxide layer on the surface of the zinc metal sheet is removed.
Preferably, the polished zinc metal sheet is sequentially ultrasonically cleaned by deionized water, absolute ethyl alcohol and acetone solution to remove oil stains and impurities on the surface of the zinc foil; wherein the concentration of the absolute ethyl alcohol is 99.5 percent, and the concentration of the acetone solution is 99.5 percent.
Preferably, the mass fraction of the acetone solution added to the mixed solution is 10%; the addition ratio of the mixed solution to the acetone solution is as follows: the acetone content is 10% of the mass of the N-methylpyrrolidone solution.
Preferably, the 3D printing technology adopts a direct-writing 3D printer, the inner diameter of a needle head selected by the direct-writing 3D printer is 0.15mm, the set pressure value is 6.5bar, and the moving speed during printing is 5mm/s.
Preferably, the thickness of the beta-PVDF coating printed by the direct-writing 3D printer is 0.1-0.5 mm.
Preferably, the drying conditions of the zinc foil built with a beta-PVDF coating are: vacuum condition, drying temperature is: the drying time at 40 ℃ is as follows: and 12h.
Preferably, a long-cycle battery comprises a zinc-ion battery anode with a beta-PVDF coating attached, prepared by the method described above.
Preferably, the long-cycle battery can be used in the fields of artificial cochlea, intelligent watch and electric automobile.
The invention has the beneficial effects that:
according to the beta-PVDF coating modified zinc cathode disclosed by the invention, the ink prepared from the PVDF polymer is coated on the surface of the zinc foil in a direct-writing 3D printing mode to protect the zinc cathode. The PVDF coating-protected zinc cathode has the advantages that by virtue of good mechanical toughness and improved dielectric property of beta-PVDF, corrosion resistance of the zinc cathode can be improved, and side reactions such as hydrogen evolution corrosion and the like can be inhibited in the charge and discharge process, so that the regulation and control capability of zinc ions in deposition/stripping is improved, zinc dendrite generation is reduced, the cycle charge and discharge time of a zinc ion battery is greatly prolonged, and the service life of the zinc ion battery is far longer than that of an unprotected zinc cathode under the same current density. Meanwhile, the method can be popularized to a plurality of other similar polymer coating protection zinc cathodes, and the preparation method is simple and can be used for mass production.
Drawings
In order to more clearly illustrate the embodiments of the present disclosure or the prior art, the drawings that are required for the description of the embodiments or the prior art will be briefly described, and it will be apparent to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is an XRD pattern of the direct write 3D printed beta-PVDF coated zinc foil of the present invention, before and after;
FIG. 2 is an SEM image of the invention before and after direct write 3D printing of a beta-PVDF coated zinc foil;
FIG. 3 shows that the direct-write 3D printed beta-PVDF coated zinc foil front-back symmetric battery of the invention is 1mAcm -2 、1mAhcm -2 The following cycle performance graph.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The invention is further described in detail by means of specific embodiments:
the preparation method of the polymer coating modified zinc cathode comprises the following steps:
s1, firstly, polishing commercial zinc foil (with purity of 99.995% and thickness of 0.05 mm) with 2000-mesh, 5000-mesh and 8000-mesh sand paper in sequence, then carrying out ultrasonic cleaning with deionized water, absolute ethyl alcohol and acetone solution to obtain clean zinc foil for later use, wherein the absolute ethyl alcohol and acetone solution used are chemical purity, the ultrasonic time of the zinc foil with deionized water, ethanol and acetone is generally 10-60 min, the ultrasonic time is selected in the experiment, the ultrasonic temperature is kept at about 25 ℃, the ultrasonic time is placed in a vacuum drying oven for drying for 6h after the ultrasonic time is ended, the temperature is set to 80 ℃, and finally the clean zinc foil is obtained;
s2, adding polyvinylidene fluoride (PVDF) into an N-methyl pyrrolidone (NMP) organic solvent, and stirring in a sealed container until the PVDF is completely dissolved to obtain a yellowish transparent colloidal solution, wherein the mass fraction of the PVDF polymer is 6%;
s3, adding an acetone organic solution into the colloidal solution in the step S2, wherein the mass fraction of the acetone solution is 10%. Ultrasonic treatment is carried out for 1 hour at room temperature, and the mixture is stood for one night so that acetone is fully dissolved in the colloidal solution;
s4, printing the colloidal solution obtained in the step S3 on the cleaned metal zinc foil through a direct-writing type 3D printer, wherein the inner diameter of a needle head selected for 3D printing is 0.15mm, the set pressure value is 6.5bar, the printing moving speed is 5mm/S, and the printing of the polymer coating is under the room temperature condition without adding any external condition. And (3) carrying out vacuum drying on the printed and coated modified zinc negative electrode plate, and cutting the electrode to obtain the modified zinc negative electrode plate with a proper size and coated with a polymer coating with the thickness of 0.01-0.05 mm, wherein the vacuum drying temperature is 40 ℃, and the vacuum drying time is 12 hours.
Example 2
Analogously to example 1, except that in step S2 polyvinylidene fluoride (PVDF) was added to N-methylpyrrolidone (NMP) organic solvent and stirred in a sealed vessel until completely dissolved, a yellowish transparent gum-like solution was obtained, the mass fraction of PVDF polymer being 12%.
Example 3
Analogously to example 1, except that in step S2 polyvinylidene fluoride (PVDF) was added to N-methylpyrrolidone (NMP) organic solvent and stirred in a sealed vessel until completely dissolved, a yellowish transparent colloidal solution was obtained, the mass fraction of PVDF polymer being 18%.
The testing method comprises the following steps:
(1) Coating characterization
XRD crystal structure and SEM morphology structure comparison are carried out on the zinc cathode before and after the PVDF polymer is printed and coated, and figure 1 is an XRD diagram of the zinc cathode before and after the PVDF polymer is coated. As can be seen from XRD patterns, there are two characteristic peaks at about 18.4 DEG and 20.6 DEG, corresponding to the (020) diffraction peak of the alpha-PVDF and the (110) diffraction peak of the beta-PVDF, respectively, and the intensity of the (110) diffraction peak of the beta-PVDF is higher than that of the (020) diffraction peak of the alpha-PVDF. The characteristic diffraction peaks of the beta-phase (110) crystal surface of PVDF by 3D printing are sharper compared to bare zinc-zinc foil, and the shear force of surface 3D printing enhances the beta-phase content in PVDF coating. FIG. 2 (a) shows a zinc foil before printing PVDF polymer, which has a smooth surface and no obvious corrosive pits and other impurities, and FIG. 2 (b-d) shows a dense film on the surface of the zinc foil after printing PVDF polymer in examples 1-3, respectively.
(2) Electrochemical testing
Assembly of Zn// Zn symmetrical cells: and cutting the zinc foil decorated by the 3D printing PVDF polymer coating and the zinc foil which is not printed with the PVDF polymer coating, and then using the zinc foil and the zinc foil as the anode and the cathode of the symmetrical battery, and respectively installing the zinc foil and the zinc foil into a button battery, namely, arranging two identical cathodes in the button battery. Wherein the model of the button cell shell is CR2032, and the electrolyte is 2MZnSO 4 The diaphragm is made of glass fiber, the model is Whatman GF/D, the diameter of the cut electrode plate is 1cm, the purity of the used zinc foil is 99.995%, the thickness is 0.05mm, and the assembly is completed in air.
Constant current charge and discharge test of Zn// Zn symmetrical battery: testing the assembled symmetrical battery in a New Wei battery test system, wherein the zinc cathode of the 3D printing PVDF polymer coating and the pure zinc cathode of the unprinted PVDF polymer coating are 1mAcm -2 Charge-discharge current density and 1mAhcm -2 Constant current charge and discharge tests are carried out under the specific capacity of the charge and discharge area, and the test results are shown in figure 3.
As can be seen from FIG. 3, the charge and discharge are performedThe current density is 1mAcm -2 And a specific charge/discharge area capacity of 1mAhcm -2 And the symmetric battery cycle life of the 3D printing PVDF polymer coated zinc cathode with the content of 12% (embodiment II) can reach 600 hours, and the pure zinc cathode and the PVDF polymer with the content of 6% (embodiment I) and 18% (embodiment III) respectively have short circuits at about 50 hours, 290 hours and 300 hours. The stability of the zinc cathode after the coating is added can be better proved by the test of cyclic charge and discharge under high current, and the zinc cathode with the PVDF polymer content of 12 percent (the second embodiment) coating is more stable. The enhancement of the circulation stability means that the ion migration rate of zinc is accelerated in the deposition/stripping process, and is mainly attributed to the fact that the beta-PVDF coating is more beneficial to promoting zinc ion transmission, inhibiting zinc dendrite from generating, reducing side reactions such as hydrogen evolution corrosion and the like occurring between the zinc dendrite and electrolyte, and prolonging the circulation life of the battery.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. The preparation method of the long-cycle zinc ion battery negative electrode beta-PVDF coating is characterized by specifically comprising the following steps: cleaning a polished zinc metal sheet, drying for standby, adding polyvinylidene fluoride into an N-methyl pyrrolidone organic solvent, stirring uniformly to obtain a mixed solution, adding acetone into the mixed solution, and mixing uniformly to obtain yellowish ink; printing ink on the surface of a zinc metal sheet through a 3D printing technology to construct a beta-PVDF coating, and finally drying the zinc metal sheet constructed with the beta-PVDF coating to obtain a long-cycle secondary zinc battery negative beta-PVDF coating;
wherein the polyvinylidene fluoride has the following model: PVDF-SOLEF5130, N-methylpyrrolidone concentration: 99.5% of polyvinylidene fluoride and N-methyl pyrrolidone, wherein the optimal adding ratio is as follows: 0.12:1.
2. the method of claim 1, wherein the zinc foil has a size of 1cm in diameter and 0.05mm in thickness.
3. The preparation method according to claim 1, wherein the zinc metal sheet is polished by sequentially polishing with 2000 mesh sand paper, 5000 mesh sand paper and 8000 mesh sand paper to remove the oxide layer on the zinc metal surface.
4. The preparation method of claim 1, wherein the polished zinc foil is sequentially ultrasonically cleaned by deionized water, absolute ethyl alcohol and acetone solution to remove oil stains and impurities on the surface of the zinc foil; wherein the concentration of the absolute ethyl alcohol is 99.5 percent, and the concentration of the acetone solution is 99.5 percent.
5. The preparation method according to claim 1, wherein the mass fraction of the acetone solution added to the mixed solution is 10%; the addition ratio of the mixed solution to the acetone solution is as follows: the acetone content is 10% of the mass of the N-methylpyrrolidone solution.
6. The preparation method according to claim 1, wherein the 3D printing technology adopts a direct-writing 3D printer, the internal diameter of a needle head selected by the direct-writing 3D printer is 0.15mm, the set pressure value is 6.5bar, and the moving speed during printing is 5mm/s.
7. The method of claim 6, wherein the thickness of the beta-PVDF coating printed by the direct write 3D printer is 0.1mm to 0.5mm.
8. The method of claim 1, wherein the drying conditions of the zinc foil with the β -PVDF coating are: vacuum condition, drying temperature is: the drying time at 40 ℃ is as follows: and 12h.
9. A long-cycle battery comprising a zinc-ion battery anode having a β -PVDF coating attached, prepared according to the method of any one of claims 1-8.
10. The long-cycle battery according to claim 9 can be used in the fields of artificial cochlea, smart watch and electric automobile.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310910320.XA CN116914143A (en) | 2023-07-24 | 2023-07-24 | Preparation method of long-cycle zinc ion battery negative electrode beta-PVDF coating |
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| CN202310910320.XA CN116914143A (en) | 2023-07-24 | 2023-07-24 | Preparation method of long-cycle zinc ion battery negative electrode beta-PVDF coating |
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| CN202310910320.XA Pending CN116914143A (en) | 2023-07-24 | 2023-07-24 | Preparation method of long-cycle zinc ion battery negative electrode beta-PVDF coating |
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