CN109980226B - Zinc cathode with polyamide brightener layer and preparation method and application thereof - Google Patents

Zinc cathode with polyamide brightener layer and preparation method and application thereof Download PDF

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CN109980226B
CN109980226B CN201910240468.0A CN201910240468A CN109980226B CN 109980226 B CN109980226 B CN 109980226B CN 201910240468 A CN201910240468 A CN 201910240468A CN 109980226 B CN109980226 B CN 109980226B
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zinc
polyamide
layer
brightener layer
negative electrode
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CN109980226A (en
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崔光磊
赵志明
赵井文
徐红霞
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • 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
    • 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
    • H01M4/08—Processes of 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/244—Zinc electrodes
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of 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
    • H01M4/62—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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • 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

Abstract

The invention relates to a zinc cathode with a polyamide brightener layer, and belongs to the technical field of energy materials. The method is characterized in that polyamide is dissolved in anhydrous formic acid for remodeling, and a solid brightener layer is constructed on the surface of a zinc cathode. The brightener layer can regulate and control the uniform transmission of zinc ions, can prevent the zinc cathode from directly contacting with water system electrolyte and air, inhibits chemical and electrochemical hydrogen evolution in the charging and discharging process, reduces side reactions such as corrosion and passivation of the surface of the zinc cathode, and increases the nucleation density of zinc to promote the uniform deposition of zinc by realizing the effect of the brightener, so that the zinc cathode can effectively carry out deep charging and discharging, and the cycle life of the battery is prolonged.

Description

Zinc cathode with polyamide brightener layer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to a zinc cathode with a polyamide brightener layer, and a preparation method and application thereof.
Background
Currently, lithium ion batteries, lead-acid batteries and nickel-metal hydride batteries occupy most of the market shares, but they are still not perfect. Particularly in the field of electric vehicles, the further development of the batteries is limited by the problems of higher weight, high cost, easy short circuit to cause fire and the like, and the updating and optimization of a battery scientific system are urgently needed. Zinc batteries are battery systems based on metal zinc or zinc alloys as the negative active material, and have a long history of development, such as zinc-air batteries, zinc-manganese alkaline batteries, and the like. The zinc cathode has the advantages of low cost, no toxicity, environmental protection, high biocompatibility and the like, and the mass specific capacity of the zinc cathode reaches 820 mAh/g, and the volume specific capacity of the zinc cathode reaches 5855 mAh/cm3Far higher than that of a lithium metal negative electrode (2061 mAh/cm)3) The application value is extremely high. However, although a zinc-based battery of a neutral aqueous electrolyte has attracted much attention in recent years, its poor cycle performance is a fatal problem. The reason is that the zinc cathode is not thermodynamically stable in aqueous electrolyte and has severe passivation and corrosion phenomenaAnd zinc oxide, zinc hydroxide and the like are easily generated to cover the surface of the zinc cathode, so that the cathode fails. The recharging process (electrochemical galvanization step) is susceptible to strong interference of hydrogen evolution side reactions (especially during low-rate charging), resulting in pulverization of the active zinc layer and low coulombic efficiency during charging; the zinc deposition is uneven, causing dendrites to puncture the membrane. Although a small amount of reports currently report that the traditional water-based electrolyte is replaced by the high-concentrated salt or eutectic electrolyte, the cost of the used salt is very high, which causes the high cost, and the intrinsic advantages of low price, green and safety of the zinc battery are violated. Therefore, it is important to effectively protect the zinc negative electrode so as to suppress a side reaction of zinc with the aqueous electrolyte. The invention is inspired by the fact that the brightener is used as an electrolyte additive in the electroplating industry to enable the zinc plating to be more compact and smooth, a polyamide brightener layer is directly constructed on the surface of a zinc cathode, the side reaction is inhibited, and simultaneously, the deposition density of zinc is increased to obtain a smooth and compact deposition product, so that the key scientific problem existing in a secondary zinc battery system is pertinently solved, and the significance is great.
Disclosure of Invention
The invention aims to inhibit side reaction between a zinc cathode and an electrolyte, and solve the problems of serious zinc dendrite, low coulombic efficiency, poor cycle performance, incapability of deep charge and discharge, poor safety performance and the like caused by uneven deposition of metal zinc. In order to achieve the purpose, the invention adopts the technical scheme that:
a zinc negative electrode having a polyamide brightener layer includes an active material layer and a polyamide brightener layer.
The main components of the polyamide brightener layer are polyamide and metal zinc salt combined with the polyamide or only contain the polyamide, the mass fraction of the polyamide in the brightener layer is 5-100%, the mass fraction of the metal zinc salt combined with the polyamide in the polyamide brightener layer is 0-95%, and the room-temperature ionic conductivity of the polyamide brightener layer is 1 multiplied by 10-8To 9X 10-1 S/cm。
Preferably, in the polyamide brightener layer, the mass fraction of polyamide in the brightener layer is 8% -95%; the mass fraction of the zinc salt combined with the polyamide in the brightener layer is 5-92%.
More preferably, in the polyamide brightener layer, the mass fraction of the polyamide in the brightener layer is 10% -90%; the mass fraction of the zinc salt combined with the polyamide in the brightener layer is 10-90%.
The polyamide brightener layer comprises at least one polyamide, wherein the polyamide is a high molecular polymer containing amido bonds in a repeating unit, the polyamide at least contains one repeating unit, and the repeating unit of the polyamide is selected from chemical formulas 1 or 2,
chemical formula 1:
-NH-R1-NH-CO-R2-CO-
chemical formula 2:
-NH-R3-CO-
R1、R2、R3the groups are independently selected from any divalent group of aliphatic groups, cycloaliphatic groups, benzene-containing aromatic groups, non-benzene aromatic groups, silicon-containing groups, or combinations thereof.
The zinc salt combined with the polyamide in the polyamide brightener layer is one or more of zinc trifluoromethanesulfonate, zinc dicyanamide, bis (trifluoromethanesulfonyl) imide, bis (trifluoroethylsulfonyl) imide, bis (fluorosulfonyl) imide, zinc fluoborate, zinc hexafluorophosphate, zinc sulfate, zinc nitrate, zinc perchlorate and zinc chloride.
Preferably, the metal zinc salt in the polyamide brightener layer is one or more of zinc trifluoromethanesulfonate, bis (trifluoromethanesulfonyl) imide, bis (trifluoroethylsulfonyl) imide, zinc fluoborate, zinc hexafluorophosphate, zinc sulfate, zinc nitrate and zinc perchlorate.
The thickness of the polyamide brightener layer is 1nm-1 mm.
The active material of the zinc negative electrode active material layer is one or more of pure zinc foil, pure zinc sheets, zinc alloy sheets, pure zinc powder, zinc alloy powder, zinc oxide, zinc hydroxide, calcium zincate and zinc stearate.
A method for preparing a zinc negative electrode having a polyamide brightener layer according to claim 1, comprising the steps of:
dissolving one or more polyamides and one or more of the above zinc salts, or only one or more polyamides in anhydrous formic acid, and continuously stirring until a uniform solution is formed; coating the solution on the surface of the zinc cathode with the oxide film removed by adopting a blade coating, spin coating or spraying method; the solvent was thoroughly removed to obtain a uniform polymer brightener layer, and thus a zinc cathode with a polyamide brightener layer was obtained.
The application of a zinc negative electrode with a polyamide brightener layer in a zinc-based battery. The zinc-based battery includes a primary zinc battery and a secondary zinc battery.
The invention has the advantages that:
the zinc cathode with the polyamide brightener layer has the advantages of simple preparation process, high thermal and chemical stability, wide electrochemical window and high ionic conductivity, and can realize the transmission of zinc ions. The method has the greatest characteristics that the polyamide brightener layer is used for carrying out interface coating on the zinc cathode to construct the electrochemically stable brightener layer between the zinc cathode and the electrolyte, so that direct contact between active substance zinc and the body electrolyte can be effectively isolated, the decomposition of the electrolyte in the charging and discharging process is limited to generate gas, the formation of byproducts such as zinc oxide on the surface of the zinc cathode is reduced, the nucleation density of zinc deposition is increased, the uniform deposition of zinc is promoted, the growth of zinc dendrites is inhibited, the zinc battery can be deeply charged and discharged, the cycle life of the battery is prolonged, the operation cost is extremely low, and the application value is huge.
Drawings
FIG. 1 shows a Zn/Zn symmetrical cell assembled by uncoated zinc sheets and a Zn/Zn symmetrical cell assembled by zinc sheets with a polyamide brightener layer provided in example 1 of the present invention in 2M ZnSO4Long cycle profile in aqueous electrolytes.
FIG. 2 shows a Zn/Zn symmetrical cell assembled by uncoated zinc foil and a Zn/Zn symmetrical cell assembled by zinc foil with a polyamide brightener layer provided in example 2 of the present invention at 2M ZnSO4Deep discharge profile in aqueous electrolytes.
FIG. 3 shows MnO provided in example 3 of the present invention in which a zinc sheet having a polyamide brightener layer and an uncoated zinc sheet are respectively assembled as cathodes2The battery is subjected to cyclic voltammetry curve obtained by cyclic voltammetry test at a scanning speed of 1 mV/s.
FIG. 4 shows MnO assembled separately with a zinc sheet having a polyamide brightener layer and an uncoated zinc sheet as negative electrodes provided in example 4 of the present invention2Batteries, charge and discharge curves obtained by charging and discharging at current densities of 2C (1C = 300 mA/g based on the positive electrode active mass), respectively.
FIG. 5 shows MnO assembled separately with a zinc sheet having a polyamide brightener layer and an uncoated zinc sheet as negative electrodes provided in example 5 of the present invention2Batteries, long cycling curves obtained from charging and discharging at current densities of 2C (1C = 300 mA/g based on the active mass of the positive electrode), respectively.
FIG. 6 shows a Zn/Zn symmetric cell assembled by uncoated zinc sheets in 2M ZnSO4Scanning electron micrographs of zinc flakes after 100 hours of cycling in aqueous electrolyte.
FIG. 7 shows a Zn/Zn symmetric cell assembled by zinc sheets with polyamide brightener layers according to example 6 of the present invention at 2M ZnSO4Scanning electron micrographs of zinc flakes after 300 hours of long cycling in aqueous electrolytes.
FIG. 8 shows a Zn/Zn symmetric cell assembled by uncoated zinc sheets and a Zn/Zn symmetric cell assembled by zinc sheets with a polyamide brightener layer provided in example 6 of the present invention at 2M ZnSO4X-ray diffraction spectrum (XRD) patterns of the zinc plate after 100 hours and 300 hours of circulation in the aqueous electrolyte.
FIG. 9 shows uncoated zinc flakes and a 2M ZnSO layer of a zinc flake having a polyamide brightener layer provided in example 7 of the present invention4Graphs of corrosion tests (taverer curves) performed in aqueous solutions.
FIG. 10 shows a V assembly of a zinc powder electrode sheet having a polyamide brightener layer and an uncoated zinc powder electrode sheet as cathodes provided in example 8 of the present invention2O5Batteries, respectively charged and discharged at a current density of 2C (1C = 298 mA/g based on the active mass of the positive electrode)The resulting charge and discharge curve.
FIG. 11 is a V in which a zinc powder electrode sheet having a polyamide brightener layer and an uncoated zinc powder electrode sheet provided in example 9 of the present invention are assembled as cathodes2O5Batteries, long cycling curves obtained from charging and discharging at current densities of 2C (1C = 298 mA/g based on the active mass of the positive electrode), respectively.
Fig. 12 is a schematic diagram of the zinc cathode with polyamide brightener layer provided by the invention for effectively protecting the zinc active material.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples are only for illustrating the present invention, but not for limiting 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 1:1 weighing nylon 6 and zinc trifluoromethanesulfonate, fully mixing and dissolving the nylon 6 and the zinc trifluoromethanesulfonate in anhydrous formic acid, and continuously stirring until a uniform solution is formed. And (4) polishing the zinc sheet to remove an oxide layer on the surface. The solution was then uniformly scraped onto the polished zinc sheet surface with a 100 μm doctor blade. Drying in a vacuum drying oven at 60 ℃ until the anhydrous formic acid on the surface of the zinc sheet is completely volatilized. A zinc sheet with a polyamide brightener layer is obtained. By 2M ZnSO4The water system solution is used as electrolyte, a glass fiber diaphragm is used, and the zinc sheet with the polyamide brightener layer and the uncoated zinc sheet are used as electrodes to respectively assemble the Zn/Zn symmetrical battery. At 0.4 mA/cm2The charge and discharge cycles were carried out at the current density of (1), and the long cycle curve is shown in FIG. 1. It was found that the uncoated zinc sheet assembled symmetric cell failed after 131 hours of cycling, while the zinc sheet assembled symmetric cell with the polyamide brightener layer cycled stably for 2748 hours, with a greatly extended useful life.
Example 2
Weighing nylon 6, zinc trifluoromethanesulfonate and zinc chloride according to the mass ratio of 5:1:1, fully mixing and dissolving the nylon 6, the zinc trifluoromethanesulfonate and the zinc chloride in anhydrous formic acid, and continuously stirring until a uniform solution is formed.And polishing the zinc foil to remove the oxide layer on the surface. The solution was then uniformly scraped onto the polished zinc foil surface with a 100 μm doctor blade. Drying in a vacuum drying oven at 60 ℃ until the anhydrous formic acid on the surface of the zinc foil is completely volatilized. A zinc foil with a polyamide brightener layer is obtained. By 2M ZnSO4The water system solution is used as electrolyte, a glass fiber diaphragm is used, and the zinc foil with the polyamide brightener layer and the uncoated zinc foil are used as electrodes to respectively assemble the Zn/Zn symmetrical battery. At 10 mA/cm2The current density of the battery is measured, and the charge-discharge surface capacity is 10 mAh/cm2The charge and discharge curves are shown in FIG. 2. As a result, it was found that the symmetrical cell assembled with uncoated zinc sheets could not be charged and discharged at a high current density, while the symmetrical cell assembled with zinc foil having a polyamide brightener layer could stably perform a large capacity charge and discharge cycle.
Example 3
According to the mass ratio of 2: 1 weighing nylon 610 and zinc bis (trifluoromethylsulfonyl) imide, fully mixing and dissolving the two in anhydrous formic acid, and continuously stirring until a uniform solution is formed. And (4) polishing the zinc sheet to remove an oxide layer on the surface. And then uniformly spin-coating the solution on the polished surface of the zinc sheet by using a spin coater. Drying in a vacuum drying oven at 60 ℃ until the anhydrous formic acid on the surface of the zinc sheet is completely volatilized. A zinc sheet with a polyamide brightener layer is obtained. By 2M ZnSO4The water system solution is used as electrolyte, a glass fiber diaphragm is used, and MnO is respectively assembled by taking the zinc sheet with the polyamide brightener layer and the zinc sheet without the coating as negative electrodes2The cells were subjected to cyclic voltammetry tests at a scanning rate of 1 mV/s, respectively, and the cyclic voltammetry graph is shown in FIG. 3. The results show that the cyclic voltammetry curves of the full cell assembled by the zinc sheet with the polyamide brightener layer and the full cell assembled by the zinc sheet without coating are basically overlapped, which indicates that the redox behavior in the cell is not changed after the polyamide brightener layer is coated on the zinc cathode in the full cell.
Example 4
A mass of nylon 66 was weighed and dissolved in anhydrous formic acid with constant stirring until a homogeneous solution was formed. And (4) polishing the zinc sheet to remove an oxide layer on the surface. The solution was then homogenized with a 30 μm spatulaAnd uniformly scraping the surface of the polished zinc sheet. Drying in a vacuum drying oven at 60 ℃ until the anhydrous formic acid on the surface of the zinc sheet is completely volatilized. A zinc sheet with a polyamide brightener layer is obtained. By 2M ZnSO4The water system solution is used as electrolyte, a glass fiber diaphragm is used, and MnO is respectively assembled by taking the zinc sheet with the polyamide brightener layer and the zinc sheet without the coating as negative electrodes2The batteries were charged and discharged at a current density of 2C (1C = 300 mA/g based on the positive electrode active mass), and the charge and discharge curves are shown in fig. 4. The results show that the charge and discharge behaviors of the full cell assembled by the zinc sheet with the polyamide brightener layer are similar to those of the full cell assembled by the zinc sheet without the polyamide brightener layer, and the specific discharge capacities are basically the same.
Example 5
According to the mass ratio of 1: 1: 2 weighing nylon 6, nylon 10 and zinc sulfate, fully mixing and dissolving the nylon 6, the nylon 10 and the zinc sulfate in anhydrous formic acid, and continuously stirring until a uniform solution is formed. And (4) polishing the zinc sheet to remove an oxide layer on the surface. The solution was then uniformly scraped onto the polished zinc sheet surface with a 200 μm doctor blade. Drying in a vacuum drying oven at 60 ℃ until the anhydrous formic acid on the surface of the zinc sheet is completely volatilized. A zinc sheet with a polyamide brightener layer is obtained. By 2M ZnSO4The water system solution is used as electrolyte, a glass fiber diaphragm is used, and MnO is respectively assembled by taking the zinc sheet with the polyamide brightener layer and the zinc sheet without the coating as negative electrodes2The batteries were charged and discharged at a current density of 2C (1C = 300 mA/g based on the active mass of the positive electrode), respectively, and the long cycle curves are shown in fig. 5. The results show that the cycle life of the full cell assembled by the zinc sheet with the polyamide brightener layer is remarkably prolonged, the capacity retention rate is 85.8% after 1000 cycles of cycle, and the capacity of the uncoated full cell is less than 20 mAh/g after 240 hours of cycle, which indicates that the effective life of the full cell assembled by the zinc sheet with the polyamide brightener layer is greatly prolonged.
Example 6
Weighing nylon 66, zinc trifluoromethanesulfonate and zinc nitrate according to the mass ratio of 3:1:1, fully mixing and dissolving the nylon 66, the zinc trifluoromethanesulfonate and the zinc nitrate in anhydrous formic acid, and continuously stirring until a uniform solution is formed. And (4) polishing the zinc sheet to remove an oxide layer on the surface. The solution was then scraped with a 150 μm spatulaUniformly scraping the surface of the polished zinc sheet. Drying in a vacuum drying oven at 60 ℃ until the anhydrous formic acid on the surface of the zinc sheet is completely volatilized. A zinc sheet with a polyamide brightener layer is obtained. By 2M ZnSO4The water system solution is used as electrolyte, a glass fiber diaphragm is used, and the zinc sheet with the polyamide brightener layer and the uncoated zinc sheet are used as electrodes to respectively assemble Zn/Zn symmetrical batteries with the concentration of 0.5 mA/cm2The current density of (2) is subjected to charge-discharge cycles. FIG. 6 shows a Zn/Zn symmetrical cell assembled by uncoated zinc sheets in 2M ZnSO4Scanning electron micrographs of zinc flakes after 100 hours of cycling in aqueous electrolyte. FIG. 7 shows the Zn/Zn symmetric cell assembled by zinc sheets with polyamide brightener layer in this example at 2M ZnSO4Scanning electron micrographs of zinc flakes after 300 hours of long cycling in aqueous electrolytes. In comparison, a plurality of byproducts are generated on the surface of the zinc sheet which is not coated after circulation, and the surface of the zinc sheet with the polyamide brightener layer is very flat, smooth and compact. FIG. 8 shows the Zn/Zn symmetrical cell assembled by uncoated zinc sheets and the Zn/Zn symmetrical cell assembled by zinc sheets with polyamide brightener layer in this example at 2M ZnSO4X-ray diffraction spectrum (XRD) patterns of the zinc plate after 100 hours and 300 hours of circulation in the aqueous electrolyte. In contrast, the uncoated zinc sheet showed a hetero-peak of zinc oxide, basic zinc carbonate, etc. after 100 hours of circulation, and the zinc sheet with the polyamide brightener layer in this example showed no other by-products after 300 hours of circulation.
Example 7
3g of nylon 12 was weighed and dissolved in anhydrous formic acid with constant stirring until the nylon was completely dissolved to form a homogeneous solution. And (4) polishing the zinc sheet to remove an oxide layer on the surface. The solution was then uniformly scraped onto the polished zinc sheet surface with a 50 μm doctor blade. Drying in a vacuum drying oven at 60 ℃ until the anhydrous formic acid on the surface of the zinc sheet is completely volatilized. A zinc sheet with a polyamide brightener layer is obtained. For uncoated zinc flakes and the zinc flakes with the polyamide brightener layer in this example, 2M ZnSO4The results of the corrosion tests conducted in the aqueous solution are shown in FIG. 9, and show that the zinc flakes having a polyamide brightener layer in this example are more coated than uncoated zincThe corrosion potential of the sheet is increased by 11.7 mV, and the corrosion current is reduced by 312.1 muA/cm2The protection work is demonstrated to achieve significant effects.
Example 8
According to the mass ratio of 1: 2 weighing nylon 1010 and zinc fluoborate, fully mixing and dissolving the nylon 1010 and the zinc fluoborate in anhydrous formic acid, and continuously stirring until a uniform solution is formed. Mixing zinc powder, activated carbon and 10% polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, grinding for 1 hour, carrying out ultrasonic treatment for 5 hours, scraping a film on the surface of a stainless steel current collector by using a 400-micrometer scraper, and drying the scraped pole piece in an oven at 80 ℃ for 24 hours. The uniform polyamide solution was then uniformly scraped onto the dried pole piece surface with a 50 μm doctor blade. Drying in a vacuum drying oven at 60 ℃ until the anhydrous formic acid of the zinc pole piece is completely volatilized. Obtaining the zinc powder pole piece with the polyamide brightener layer. By 2M ZnSO4The water system solution is used as electrolyte, a glass fiber diaphragm is used, and the zinc powder pole piece with the polyamide brightener layer and the uncoated zinc powder pole piece are respectively assembled with V as cathodes2O5Batteries, each charged and discharged at a current density of 2C (1C = 298 mA/g based on the positive active mass), with charge and discharge curves as shown in fig. 10, illustrate that the charge and discharge behavior of a full battery assembled with a zinc powder negative electrode having a polyamide brightener layer is similar to that of a full battery assembled with an uncoated zinc powder negative electrode, with the specific discharge capacity being substantially the same.
Example 9
According to the mass ratio of 1: 2 weighing nylon 6 and zinc chloride, fully mixing and dissolving the nylon 6 and the zinc chloride in anhydrous formic acid, and continuously stirring until a uniform solution is formed. Mixing zinc powder, activated carbon and 10% polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, grinding for 2 hours, carrying out ultrasonic treatment for 3 hours, scraping a film on the surface of a stainless steel current collector by using a 300-micrometer scraper, and drying the scraped pole piece in an oven at 80 ℃ for 24 hours. The uniform polyamide solution was then uniformly scraped onto the dried pole piece surface with a 100 μm doctor blade. Drying in a vacuum drying oven at 60 ℃ until the anhydrous formic acid of the zinc pole piece is completely volatilized. Obtaining the zinc powder pole piece with the polyamide brightener layer. By 2M ZnSO4The aqueous solution is electrolyteRespectively assembling V by using a glass fiber diaphragm and taking the zinc powder pole piece with the polyamide brightener layer and the zinc powder pole piece without cladding as negative electrodes2O5The batteries were charged and discharged at current densities of 2C (1C = 298 mA/g based on the active mass of the positive electrode), respectively, and long cycle curves are shown in fig. 11. The result shows that the cycle life of the full battery assembled by the zinc powder cathode with the polyamide brightener layer is obviously prolonged, the capacity retention rate is 73.1% after 500 cycles, and the capacity of the full battery assembled by the zinc powder cathode without the coating is less than 30 mAh/g after 300 cycles, which indicates that the effective life of the full battery assembled by the zinc powder cathode with the polyamide brightener layer is greatly prolonged.

Claims (10)

1. A zinc negative electrode having a polyamide brightener layer, characterized by: the zinc negative electrode comprises an active material layer and a polyamide brightener layer, wherein the polyamide brightener layer is positioned on the surface of the active material layer, and the main components of the polyamide brightener layer are polyamide and metal zinc salt combined with the polyamide or only contain the polyamide.
2. The zinc negative electrode having a polyamide brightener layer according to claim 1, wherein the room-temperature ionic conductivity of the polyamide brightener layer is 1 x 10-8To 9X 10-1 S/cm。
3. The zinc negative electrode having a polyamide brightener layer according to claim 1, wherein the mass fraction of the polyamide in the brightener layer is 5 to 100%, and the mass fraction of the metal zinc salt combined with the polyamide in the polyamide brightener layer is 0 to 95%.
4. The zinc negative electrode having a polyamide brightener layer according to claim 1, characterized in that the polyamide brightener layer comprises at least one polyamide, the polyamide is a high molecular polymer comprising amide bonds in the repeating units, the polyamide comprises at least one repeating unit, and the repeating unit of the polyamide is selected from chemical formula 1 or 2,
chemical formula 1:
-NH-R1-NH-CO-R2-CO-
chemical formula 2:
-NH-R3-CO-
R1、R2、R3the groups are independently selected from any divalent group of aliphatic groups, cycloaliphatic groups, benzene-containing aromatic groups, non-benzene aromatic groups, silicon-containing groups, or combinations thereof.
5. The zinc negative electrode with the polyamide brightener layer according to claim 1, wherein the zinc salt combined with the polyamide in the polyamide brightener layer is one or more of zinc trifluoromethanesulfonate, zinc dicyanamide, zinc bis (trifluoromethanesulfonyl) imide, zinc bis (trifluoroethylsulfonyl) imide, zinc bis (fluorosulfonyl) imide, zinc fluoroborate, zinc hexafluorophosphate, zinc sulfate, zinc nitrate, zinc perchlorate, and zinc chloride.
6. The zinc negative electrode having a polyamide brightener layer according to claim 1, wherein the polyamide brightener layer has a thickness of 1nm to 1 mm.
7. The zinc negative electrode having a polyamide brightener layer as claimed in claim 1, wherein the zinc negative electrode active material layer active material is one or more of pure zinc foil, pure zinc sheet, zinc alloy sheet, pure zinc powder, zinc alloy powder, zinc oxide, zinc hydroxide, calcium zincate, and zinc stearate.
8. A method for preparing a zinc negative electrode having a polyamide brightener layer according to claim 1, comprising the steps of:
dissolving one or more polyamides and one or more of the above zinc salts, or only one or more polyamides in anhydrous formic acid, and continuously stirring until a uniform solution is formed; coating the solution on the surface of the zinc cathode with the oxide film removed by adopting a blade coating, spin coating or spraying method; the solvent was thoroughly removed to obtain a uniform polymer brightener layer, and thus a zinc cathode with a polyamide brightener layer was obtained.
9. Use of a zinc negative electrode with a polyamide brightener layer according to claim 1, characterized in that the zinc negative electrode with a polyamide brightener layer is used in the production of zinc-based cells.
10. Use of a zinc negative electrode with a polyamide brightener layer according to claim 9, characterized in that the zinc-based cells comprise primary and secondary zinc cells.
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