CN116031356A - Preparation method of zinc anode with large-scale, environment-friendly, rapid preparation and integrated characteristics of polyamide-based ion conductor coating - Google Patents
Preparation method of zinc anode with large-scale, environment-friendly, rapid preparation and integrated characteristics of polyamide-based ion conductor coating Download PDFInfo
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- CN116031356A CN116031356A CN202111250450.2A CN202111250450A CN116031356A CN 116031356 A CN116031356 A CN 116031356A CN 202111250450 A CN202111250450 A CN 202111250450A CN 116031356 A CN116031356 A CN 116031356A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a zinc anode with a polyamide-based coating which has the characteristics of large scale, environmental protection, rapid preparation and integration, and belongs to the energy material technology. The preparation method is characterized in that polyamide gel is coated on the surface of zinc, and then the coating and the metal zinc integrated rapid preparation of rapid conversion from the gel to the solid phase are realized through a coagulating bath. During phase inversion, partial recovery of electrolyte salt and rapid preparation of the internal and external structure differential coating can be achieved; the residual metal salt can reduce the crystallinity of the polyamide polymer coating and play a role in accelerating the transportation of lithium ions/zinc ions in the polymer coating. The coating has special formic nest shapeStructure and surface of the electrode are provided with a plurality of polar functional groups, and electrode surface Zn is regulated and controlled 2+ Flux, slow down zinc dendrites, and also assist in desolvation process, reducing initial zinc nucleation energy; the coating physically prevents the zinc cathode from directly contacting with electrolyte, thereby inhibiting adverse factors such as hydrogen evolution and side reaction when the battery is used, and prolonging the service life of the zinc cathode.
Description
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to a preparation method and application of a zinc anode with a polyamide-based ion conductor coating, wherein the zinc anode has the characteristics of large scale, environment friendliness, rapid preparation and integration.
Background
The energy storage device using the metallic zinc as the negative electrode has the advantages of abundant zinc reserves, high safety, no toxicity and high theoretical specific capacity (820 mAh/g,5851 mAh/cm) 3 ) The advantages of higher hydrogen evolution potential (1.2V), lower equilibrium potential (-0.763V vs. Standard Hydrogen Electrode (SHE)) and the like are considered by researchers to be one of ideal energy storage systems for supplementing organic lithium ion batteries. However, since metallic zinc cathodes are not perfectly flat themselves, the surface has sharp protrusions, and zinc ions are preferentially electrodeposited on these protrusions during discharge and then cause dendrite growth. Dendrite growth can aggravate hydrogen evolution reaction to cause serious corrosion passivation of the surface of the zinc cathode, so that coulomb efficiency is greatly reduced, and an energy storage device fails. Researchers have proposed organic-inorganic coating strategies that effectively extend zinc anode life, and regarding inorganic coating strategies, the inorganic materials employed have poor mechanical properties that do not cushion dendrite growth, and additional binders are added, some of which require expensive instrumentation, which is detrimental to large-scale application of zinc-ion batteries. Regarding the organic coating, researchers prove that some organic high molecular polymers with a large number of polar functional groups on the surfaces have wide application prospects in the aspect of zinc anode protection, however, some coatings are unsuitable for large-scale, environment-friendly and rapid preparation due to the fact that the coating uses highly corrosive chemical agents in the preparation process. Therefore, for the promotion of commercial application of zinc ion batteries, organic polymer coatings which can be prepared in a large scale, environment-friendly, efficient and rapid manner are of great importance for zinc anode protection. The invention is inspired by deep eutectic materials, uses high-concentration metal salt as hydrogen bond donor, polyamide materials as hydrogen bond acceptor, promotes eutectic gelation by dissociating the hydrogen bond among polyamide molecules through high-concentration cations with high Lewis acidity, and successfully constructs a special formic nest-shaped junction on the surface of a zinc negative electrode through a water immersion gel conversion methodThe polyamide-based ion conductor coating containing the micro electrolyte salt regulates and controls the zinc ion flow on the surface of the zinc cathode, slows down the growth of dendrites, and simultaneously filters out the solvated water of the zinc ions layer by layer to achieve the effect of reducing the initial nucleation energy of zinc; the method can block the direct contact between the electrode and the electrolyte on the physical level, inhibit hydrogen evolution, effectively prolong the service life of the zinc cathode, pointedly solve the key problems of dendrite and side reaction existing in the existing energy storage system taking metallic zinc as the cathode, and has great significance for promoting the commercial application of zinc-based energy storage devices.
Disclosure of Invention
The invention aims to physically separate direct contact between the electrode and the electrolyte so as to achieve the ideal effect of inhibiting side reaction between the zinc cathode and the electrolyte; the problem of zinc dendrite growth is solved by regulating and controlling zinc ion flow; the layer-by-layer filtration of solvated water brings about a reduction of the initial zinc nucleation energy. In order to achieve the above purpose, the invention adopts the following technical scheme:
a zinc negative electrode with a polyamide-based ion conductor coating having large-scale, environment-friendly, rapid preparation and integration characteristics comprises an active material layer and a polyamide-based ion conductor coating.
The main components of the polyamide-based ion conductor coating are polyamide-based materials (PA-6, PA-66 and the like) and trace lithium salt or zinc salt which can interact with the polymer. The polyamide accounts for up to 60-90% of the coating by mass, and the lithium salt or zinc salt combined with the polyamide-based polymer accounts for up to 10% of the coating by mass.
The polymer coating comprises at least one polyamide, wherein the polyamide comprises aliphatic polyamide and aromatic polyamide, and one of the polyamide-based ion conductor coating with large-scale, environment-friendly, rapid preparation and integrated characteristics comprises one or more of lithium trifluoromethane sulfonate, lithium bistrifluoromethane sulfonate, lithium chloride, lithium bromide, zinc trifluoromethane sulfonate, zinc bistrifluoromethane sulfonate, zinc chloride and zinc bromide.
The thickness of the polyamide-based polymer coating is 5-50 mu m.
The metal zinc negative electrode active material comprises one or more of pure zinc foil, pure zinc sheet, zinc alloy sheet and flexible zinc negative electrode prepared from pure zinc powder and zinc alloy powder.
The polymer gel is formed without the aid of an organic solvent, which directly allows gel gelation in salt solutions.
The gel formation and gel phase inversion film forming process does not need heating or organic solvent coagulation bath, and water is used as a solvent and a coagulation bath carrier in the process.
The method for preparing a zinc anode with a large-scale, environment-friendly, rapid preparation and integrated polyamide-based ion conductor coating according to claim 1, which comprises the following steps:
dissolving one or more of the above lithium salts or zinc salts and one or more polyamide materials, or only one polyamide in an aqueous solution of the above salts, and placing in a room temperature environment or heating in a forced air oven at a temperature of not higher than 80deg.C until the mixture becomes a homogeneous gel; coating the prepared gel on the surface of the zinc anode by a knife coating method, a spray coating method or a spin coating method; finally, soaking is carried out for a fixed soaking time by a water soaking gel phase conversion method, a large amount of salt is dissolved into water in the soaking process to realize recovery, and the polymer gel is successfully converted into a solid polymer coating containing trace salt and having low crystallinity and high ion conduction property, so that the polymer integrated zinc cathode is obtained.
Use of a zinc anode having a polyamide-based ion conductor coating with large-scale, environmentally friendly, rapid preparation, integrated properties, comprising in a zinc-based battery: lithium-zinc hybrid battery, zinc-manganese battery, secondary zinc ion battery, zinc ion capacitor, lithium-zinc hybrid ion capacitor and zinc-air battery.
The invention has the advantages that:
the zinc cathode of the polyamide ion conductor coating has the advantages of large-scale, environment-friendly, rapid preparation, integration, high thermodynamic and chemical stability and capability of realizing zinc ion transmission. The greatest feature of the present invention is the use of high concentrations of salt to reconstitute polyamide gels having excellent ionic conductivity. The water is also a solvent and a coagulating bath carrier, so that the large-scale recovery of salt and the polyamide coating containing trace salt are used for protecting the water-based zinc cathode, a stable electrode interface is constructed, the direct contact between an electrode and electrolyte is isolated on a physical level, the hydrogen evolution is inhibited, the concentration of hydroxyl ions in the electrolyte is reduced, the generation of byproducts on the surface of the electrode is reduced, and the coulomb efficiency of the battery is improved. Meanwhile, in the phase inversion process of the polyamide gel, the formation of the special formic nest-shaped structure has the functions of space penetration and layer-by-layer filtration of solvated water, and the ideal effect of reducing the initial nucleation energy barrier of zinc is realized. The coating can effectively prolong the cycle life of the zinc cathode, is green, low in cost and large in scale preparation, and has great practical application value.
Drawings
Fig. 1 is a long cycle graph of an uncoated zinc sheet assembled Zn/Zn symmetrical battery and a zinc sheet assembled Zn/Zn symmetrical battery with a polyamide-based ion conductor coating provided in example 1 of the invention in a 2M zinc sulfate aqueous electrolyte.
FIG. 2 is a cyclic voltammogram of a zinc stainless steel half cell assembled from zinc sheets with a polyamide-based ion conductor coating provided in example 1 of the present invention, as measured by cyclic voltammograms at a scan rate of 0.2 mv/s.
Fig. 3 is a graph of corrosion tests (tafel plot) performed in a 2M zinc sulfate aqueous electrolyte of an uncoated zinc sheet assembled Zn/Zn symmetrical battery and a zinc sheet assembled Zn/Zn symmetrical battery with a polyamide-based ion conductor coating provided in example 1 of the present invention.
Fig. 4 is an X-ray diffraction pattern (XRD) of an uncoated zinc sheet assembled Zn/Zn symmetrical battery and a zinc sheet assembled Zn/Zn symmetrical battery with a polyamide-based ion conductor coating provided in example 1 of the present invention after being cycled in a 2M zinc sulfate aqueous electrolyte for 760 hours.
Fig. 5 is a charge-discharge graph of a Zn/AC hybrid capacitor assembled from zinc sheets having a polyamide-based ion conductor coating provided in example 1 of the present invention.
FIG. 6 shows Zn/MnO assembled by a zinc sheet having a polyamide-based ion conductor coating according to example 1 of the present invention 2 Battery charge-discharge curve.
Fig. 7 is a graph of Zn/S battery capacity versus voltage for a zinc sheet assembly with a polyamide-based ion conductor coating provided in example 1 of the present invention.
Fig. 8 is an SEM image of a coating layer with a polyamide-based ion conductor provided in example 1 of the present invention.
FIG. 9 shows the surface state of a Zn/Zn symmetric cell assembled with a polyamide-based ion conductor coated zinc sheet according to example 1 of the present invention after 760 hours of cycling.
Fig. 10 is the coulombic efficiency on LAND of a half cell assembled from a zinc sheet with a polyamide-based ion conductor coating and a copper foil with a polyamide-based ion conductor coating provided in example 1 of the present invention.
Fig. 11 and 12 are zinc sheets having a polyamide-based ion conductor coating formed by the preparation of a polyamide-based ion conductor coating on the surface of a zinc sheet and the water immersion gel conversion according to example 1 of the present invention.
Fig. 13 is a schematic view showing dendrite suppression with a polyamide-based ion conductor coating according to example 1 of the present invention.
Fig. 14 is an SEM image of a polyamide membrane provided in example 2 of the present invention.
FIG. 15 shows the polyamide state at different mass ratios provided in example 5 of the present invention.
Detailed Description
The invention will be described in further detail by way of specific examples. The following examples are only for illustrating the present invention, but are not intended to limit the scope of the present invention, and all technical solutions obtained by equivalent substitution or equivalent transformation fall within the scope of the present invention.
Example 1
According to the mass ratio of 0.5:1:0.3 Polyamide, lithium triflate and water were weighed into a 10 mL clear vial and allowed to stand to gel naturallyThe gelation process may be promoted by auxiliary heating, but the temperature should be ensured not to exceed 80 ℃. The zinc sheet can be used only by ultrasonic cleaning with ethanol. Then the prepared gel is coated on the surface of a zinc sheet by a wet film preparation device with adjustable thickness, the coated zinc sheet cathode is placed in distilled water, the fixed infiltration time is 30 seconds, and finally the moisture is completely removed in a blast drying box at 80 ℃. After drying, a zinc sheet of the polyamide-based ion conductor coating was obtained. A 2M zinc sulfate aqueous solution is used as electrolyte, common filter paper is used as a diaphragm, and a zinc sheet with a polyamide ion conductor coating and an uncoated zinc sheet are used as electrodes to respectively assemble a Zn/Zn symmetrical battery and a Zn/SS half battery; at 0.5mA/cm 2 The long cycle graph is shown in figure 1, and the result shows that the symmetrical battery assembled by uncoated zinc sheets fails after 50 hours of cycle, while the symmetrical battery assembled by zinc sheets with the polyamide-based ion conductor coating stably circulates for 1500 hours, so that the service life of the zinc cathode is effectively prolonged by 30 times; assembled zinc Stainless Steel (SS) half cells were subjected to cyclic voltammetry at a scan rate of 0.2mV/s, as shown in fig. 2, the presence of the polyamide-based ion conductor coating did not affect the redox of zinc. The uncoated zinc sheets and the polyamide-based ion conductor coated zinc sheets of this example were subjected to corrosion testing in a 2M zinc sulfate solution, the results being shown in fig. 3, and the results demonstrate. The corrosion potential of the zinc sheet with the polyamide-based ion conductor coating in this example is increased by 6.91mV compared with that of the uncoated zinc sheet, which indicates that the protective working effect is remarkable. Fig. 4 is an X-ray diffraction (XRD) pattern of zinc sheets after 50 hours and 760 hours, respectively, of an uncoated zinc sheet and a zinc sheet assembled Zn/Zn symmetrical battery with a polyamide-based ion conductor coating in a 2M zinc sulfate electrolyte. In contrast, uncoated zinc sheets were found to have two basic zinc sulfate byproducts on the surface after 50 hours of cycling, whereas zinc sheets with polyamide-based ion conductor coatings in the examples had only one byproduct on the surface after 760 hours of cycling. A Zn/AC hybrid capacitor and a zinc-manganese battery are respectively assembled by taking a 2M aqueous solution as an electrolyte and common filter paper as a diaphragm, taking a zinc sheet with a polyamide-based ion conductor coating as a negative electrode in the embodiment, and the concentration of the Zn/AC hybrid capacitor and the concentration of the zinc-manganese battery are 0.5mA/cm 2 The charge and discharge curves of the Zn/AC hybrid capacitor and the Zn-Mn battery are shown in FIGS. 5 and 6, which illustrate that the coating with the polyamide-based ion conductor effectively prolongs the service life of the Zn/AC hybrid capacitor and the Zn-Mn battery. 2M zinc sulfate added with 5% of simple substance I in mass ratio is taken as electrolyte, filter paper is taken as diaphragm, zinc sheet with polyamide-based ion conductor coating is taken as negative electrode, simple substance sulfur (S) is taken as positive electrode, zn/S battery is assembled, and the ratio of Zn/S battery is 0.5mA/cm 2 The Zn/S battery was charged and discharged at the current density, and the capacity-voltage diagram is shown in fig. 7.
Example 2
Weighing the mass ratio of 0.5:0.3, and anhydrous formic acid in a transparent vial, standing to gel, and heating to promote gelation, wherein the temperature cannot exceed 80 ℃. The method comprises the steps of taking a flat glass plate analog zinc sheet as a substrate, scraping the prepared gel on the surface of the glass plate by a wet film preparation device with adjustable thickness, placing the coated glass plate in distilled water, fixing the soaking time to be 30 seconds, and finally completely removing water in a blast drying box at 80 ℃. After drying, a polyamide film having contrast is obtained.
Example 3
According to the mass ratio of 1:1, polyamide 6 and lithium bis (trifluorosulfonimide) are weighed into a 10 mL transparent small bottle, a proper amount of water is added, and then the mixture is left to stand for natural gelation, and the gelation process can be promoted by auxiliary heating, but the temperature is ensured not to exceed 80 ℃. Then the prepared gel is coated on the surface of the treated zinc sheet by a wet film preparation device with adjustable thickness, the coated zinc sheet cathode is placed in a coagulation bath of distilled water, the fixed infiltration time is 30 seconds, and finally the moisture is completely removed in a blast drying box at 80 ℃. After drying, a zinc sheet of the polyamide-based ion conductor coating was obtained. AC capacitors were assembled separately using a 2M aqueous zinc sulfate solution as the electrolyte, using ordinary filter paper as the separator, and using the coated and uncoated zinc sheets with polyamide-based ion conductor as the electrodes
EXAMPLE 4
Respectively according to the mass ratio of 1:1:0.3, 0.5:1.5:0.3 and 1:0.5:0.3 weighing polyamide, lithium trifluoromethane sulfonate and water, placing in a small bottle, standing to naturally gel, and heating to promote gelation, wherein the temperature is ensured not to exceed 80 ℃.
EXAMPLE 5
Weighing 1 according to the mass ratio: 0.5:0.5:0.3 weighing lithium trifluoromethane sulfonate, zinc trifluoromethane sulfonate, polyamide and water, placing in a small bottle, standing to naturally gel, and heating to promote gelation process, wherein the temperature is ensured not to exceed 80 ℃. Finally, a double salt gel is obtained.
Claims (9)
1. A zinc cathode with a polyamide ion conductor coating with large-scale, environment-friendly, rapid preparation and integrated characteristics is characterized in that: the zinc anode consists of a metallic zinc active material and a polyamide-based coating containing one or more lithium or zinc salts.
2. A zinc anode with a large-scale, environment-friendly, fast-preparing, integrated polyamide-based ion conductor coating according to claim 1, characterized in that the main component of the polyamide coating is a polyamide-based material (PA-6, PA-66, etc.) and a lithium or zinc salt that can interact with the polymer. The polyamide accounts for up to 60-90% of the coating by mass, and the lithium salt or zinc salt combined with the polyamide-based polymer accounts for up to 10% of the coating by mass.
3. The zinc anode with the polyamide-based ion conductor coating having the characteristics of large scale, environmental protection, rapid preparation and integration according to claim 1, wherein the metallic zinc anode active material comprises one or more of pure zinc foil, pure zinc sheet, zinc alloy sheet and flexible zinc anode prepared from pure zinc powder and zinc alloy powder.
4. The zinc anode with large-scale, environmentally friendly, fast-preparing, and integrated polyamide-based ion conductor coating according to claim 1, wherein the salt combined with the polyamide-based polymer coating is one or more of lithium triflate, lithium bis (triflate), lithium chloride, lithium bromide, zinc triflate, zinc bis (triflate), zinc chloride, and zinc bromide.
5. A zinc negative electrode having a large scale, environmentally friendly, fast preparing, integrated polyamide based ion conductor coating according to claim 1, characterized in that the polyamide based polymer coating comprises at least one polyamide comprising aliphatic polyamides, aromatic polyamides and aliphatic-aromatic polyamides.
6. A zinc anode with a large scale, environmentally friendly, fast preparing, integral polyamide based ion conductor coating according to claim 1, characterized in that the polymer gel is formed without the aid of organic solvents, which directly allows gel gelation in salt solutions.
7. A zinc anode with a large scale, environmentally friendly, fast preparing, integral polyamide based ion conductor coating according to claim 1, characterized by gel formation and gel phase inversion film forming process requiring no heating nor organic solvent coagulation bath, water, both as solvent and as coagulation bath in the process.
8. The method for preparing a zinc anode with a large-scale, environment-friendly, rapid preparation and integrated polyamide-based ion conductor coating according to claim 1, which comprises the following steps: dissolving one or more of the above lithium salts or zinc salts and one or more polyamide materials, or only one polyamide in an aqueous solution of the above salts, and placing in a room temperature environment or heating in a forced air oven at a temperature of not higher than 80deg.C until the mixture becomes a homogeneous gel; coating the prepared gel on the surface of the zinc anode by a knife coating method, a spray coating method or a spin coating method; finally, soaking is carried out for a fixed soaking time by a water soaking gel phase conversion method, a large amount of salt is dissolved into water in the soaking process to realize recovery, and the polymer gel is successfully converted into a solid polymer coating containing trace salt and having low crystallinity and high ion conduction property, so that the polymer integrated zinc cathode is obtained.
9. Use of a zinc anode with a large scale, environmentally friendly, fast preparing, integrated polyamide based ion conductor coating according to claim 1, characterized in that the zinc anode with a polyamide based ion conductor coating comprises in a zinc based battery: lithium-zinc hybrid battery, zinc-manganese battery, secondary zinc ion battery, zinc ion capacitor, lithium-zinc hybrid ion capacitor, zinc-sulfur battery, and zinc-air battery.
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| CN202111250450.2A CN116031356A (en) | 2021-10-26 | 2021-10-26 | Preparation method of zinc anode with large-scale, environment-friendly, rapid preparation and integrated characteristics of polyamide-based ion conductor coating |
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| CN202111250450.2A CN116031356A (en) | 2021-10-26 | 2021-10-26 | Preparation method of zinc anode with large-scale, environment-friendly, rapid preparation and integrated characteristics of polyamide-based ion conductor coating |
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