CN113488607B - Preparation and application of metal zinc cathode with functional nano material modification layer - Google Patents

Preparation and application of metal zinc cathode with functional nano material modification layer Download PDF

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CN113488607B
CN113488607B CN202110630522.XA CN202110630522A CN113488607B CN 113488607 B CN113488607 B CN 113488607B CN 202110630522 A CN202110630522 A CN 202110630522A CN 113488607 B CN113488607 B CN 113488607B
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zinc
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CN113488607A (en
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董留兵
李扬
谢仕寅
周煜钧
李许
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Jinan University
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    • H01—ELECTRIC ELEMENTS
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    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
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Abstract

The invention belongs to the technical field of chemical power supplies, and discloses preparation and application of a metal zinc cathode with a functional nano material modification layer. The invention adopts a simple suction filtration method to directly suction filter the functional nano material on the hydrophilic filter membrane to construct the functional nano material modification layer for protecting the metal zinc cathode. The modification layer can regulate and control an electric field or/and an ionic field during dissolution/deposition of zinc ions in the charging and discharging process, and inhibit formation of zinc dendrites, so that the water system zinc-based energy storage system with high stability and long cycle life is realized, and the modification layer has important significance for promoting practical application of the water system zinc-based energy storage system.

Description

Preparation and application of metal zinc cathode with functional nano material modification layer
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to preparation and application of a metal zinc cathode with a functional nano material modification layer.
Background
The rapid development of human society is accompanied by huge consumption of fossil fuels and increasingly serious environmental pollution caused by combustion of fossil fuels, and electrochemical energy storage devices with the advantages of high energy storage/conversion efficiency, environmental protection and the like are increasingly researched. The water system zinc-based energy storage system (comprising a zinc ion battery and a zinc ion hybrid capacitor) is beneficial to improving the energy density of the battery by using the metal zinc cathode of the water system zinc-based energy storage system which has high theoretical specific capacity (820mAh/g) and lower oxidation-reduction potential (-0.762V vs. standard hydrogen electrode), has the excellent performances of rich resources, low price, environmental friendliness, capability of carrying out large-current charge and discharge and the like, and has attracted wide attention in recent years. However, during repeated charge and discharge, zinc dendrite is generated on the surface of zinc due to uneven deposition of zinc ions, and the growth of the zinc dendrite pierces the separator to cause short circuit of the battery, thereby limiting the service life and large-scale application of the metal zinc battery. Therefore, solving zinc dendrites has been the core problem in the research of zinc negative batteries. For example, chinese patent publications CN 108767215A and CN 109713213 a inhibit the growth of zinc dendrites by coating, in-situ depositing or sputtering a protective layer of carbon material on the surface of zinc metal. However, the participation of a binder is often required during the coating process; the thickness uniformity of the protective layer formed by the coating process is difficult to control; and the cracking of the carbon material protective layer and the oxidation of the zinc metal surface are easily caused in the drying and heating process after coating, which leads to the reduction of the inhibiting effect of the process on the zinc dendrite. While in-situ deposition or sputtering methods often require complex physical equipment.
Disclosure of Invention
The invention aims to provide a preparation method of a metal zinc cathode with a functional nano material modification layer, aiming at solving the problem that a metal zinc cathode forms dendrite in the battery circulation process to cause battery short circuit.
The invention also aims to provide the metal zinc cathode with the functional nano material modification layer prepared by the method.
The invention further aims to provide an aqueous zinc-based energy storage system comprising the metal zinc negative electrode with the functional nano material modification layer. The metal zinc cathode is covered by the functional nano material (comprising the carbon nano tube, the zinc oxide, the silicon dioxide and the copper nano wire) modification layer prepared by the suction filtration method, the functional nano material interface modification layer can improve the stability of a contact interface of the metal zinc cathode and an aqueous electrolyte, the growth of zinc dendrites can be effectively inhibited by regulating and controlling an electric field or/and an ion field during the dissolution/deposition of zinc ions, and the cycling stability of the zinc cathode is improved. Has important significance for promoting the practical application of the water system zinc-based energy storage system.
The purpose of the invention is realized by the following scheme:
a preparation method of a metal zinc cathode with a functional nano material modification layer comprises the following steps:
uniformly dispersing the nano material in a solvent, carrying out suction filtration on the solvent to obtain a filter membrane, and drying to obtain the functional nano material modification layer for the stable zinc cathode; the filter membrane is cut into a shape which is not smaller than the size of the metal zinc sheet, and the filter membrane is directly covered on the surface of the metal zinc electrode.
The nano material comprises at least one of carbon nano tubes, zinc oxide, silicon dioxide and copper nano wires;
preferably, when the nanomaterial is a carbon nanotube, the carbon nanotube is a functionalized carbon nanotube or a carbon nanotube aqueous slurry containing an oxygen functional group (including a hydroxyl group and a carboxyl group);
preferably, when the nano material is zinc oxide, the zinc oxide is a porous zinc oxide nano sheet, the pore diameter is 0.5-500nm, and the thickness of the nano sheet is 5-500 nm;
preferably, when the nano material is silicon dioxide, the silicon dioxide is nano silicon dioxide spheres with the diameter of 20-500 nm;
preferably, when the nano material is a copper nanowire, the diameter of the copper nanowire is 5-200nm, and the length of the copper nanowire is 1-50 μm.
The nano material selected by the invention has the characteristics of high specific surface area, porous structure and the like, and can be used as a modification layer to regulate and control the ion field of zinc ions in the charge and discharge processes so as to ensure that the zinc ions are uniformly deposited; the copper nanowire also has the characteristic of high conductivity, the polarization of the electrode can be reduced by taking the copper nanowire as a modification layer, and the electric field and the ion field during the dissolution/deposition of zinc ions are simultaneously regulated and controlled by utilizing the influence of the electrical behavior of the copper nanowire on the dissolution/deposition behavior of the zinc ions and the network channel morphology formed by the nanowire, so that the growth of zinc dendrites is inhibited.
The solvent is water; the dosage of the nano material and the solvent meets the following requirements: the concentration of the nano material in the solvent is 0.01-5mg/mL, preferably 0.05-2 mg/mL;
the filter membrane is a hydrophilic microporous filter membrane, and the aperture is 0.02-2 mu m;
the drying temperature is 25-80 ℃, and the drying time is 2-10 hours;
the load capacity of the nano material on the filter membrane is 0.1-5mg/cm2Preferably 0.2 to 3mg/cm2。
The metal zinc cathode with the functional nano material modification layer is prepared by the method.
An aqueous zinc-based energy storage system comprises the metal zinc negative electrode with the functional nano material modification layer.
From the practical application angle, the invention adopts a simple suction filtration method to directly suction filter the nano material on the filter membrane. The modified zinc ion is used as a modification layer, and the ion field of zinc ions in the charging and discharging process is regulated and controlled by utilizing the shapes of a specific nano material porous structure or a constructed network channel and the like; the electric field of the zinc ions in the charging and discharging process is regulated and controlled by the influence of the self electrical behavior of the nano material on the dissolution/deposition behavior of the zinc ions, so that the aims of uniformly depositing the zinc ions on the surface of zinc metal and inhibiting the growth of zinc dendrites are fulfilled.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the functional nano material modification layer for protecting the metal zinc cathode can regulate and control an electric field or/and an ion field during dissolution/deposition of zinc ions in the charging and discharging process, and inhibit formation of zinc dendrites, so that a water-based zinc-based energy storage system with high stability and long cycle life is realized;
(2) compared with the reported prior art for inhibiting the formation of zinc dendrites, the method adopts a simple suction filtration method to directly suction-filter the functional nano material onto the hydrophilic filter membrane and dry the filter membrane to serve as a modification layer of the metal zinc cathode, has the advantages of simple preparation method and low cost, and is suitable for large-scale production and practical application.
Drawings
FIG. 1 is a scanning electron microscope image of copper nanowires;
fig. 2 is a cross-sectional view of a copper nanowire modification layer;
FIG. 3 is a schematic view of the internal structure of the battery;
FIG. 4 shows the current density at 0.2mA/cm2The cut-off capacity is 0.2mAh/cm2When the copper-containing nanowire modification layer is used, the long cycle curve of the battery is symmetrical;
FIG. 5 is a scanning electron microscope image of a zinc electrode containing a copper nanowire modification layer after 50 hours of cycling;
FIG. 6 is a scanning electron microscope image of a bare zinc electrode after 50 hours of cycling;
FIG. 7 is a graph of rate performance of a symmetric battery containing a copper nanowire modification layer;
FIG. 8 is a transmission electron microscope photograph of silica;
FIG. 9 shows the current density at 0.1mA/cm2The cut-off capacity is 0.5mAh/cm2When the cell is in a long-cycle curve, the cell comprises a silicon dioxide modification layer;
FIG. 10 is a TEM image of carboxylated carbon nanotubes, hydroxylated carbon nanotubes and ordinary carbon nanotubes;
FIG. 11 shows the current density at 0.2mA/cm2The cut-off capacity is 0.2mAh/cm2The long cycle curves of the carboxyl-containing carbon nanotube, the hydroxyl carbon nanotube, the common carbon nanotube modification layer symmetrical battery and the bare zinc symmetrical battery are obtained;
FIG. 12 is a scanning electron microscope photograph of porous zinc oxide nanoplates;
FIG. 13 shows the current density at 0.2m/cm2The cut-off capacity is 0.2mAh/cm2And meanwhile, the long cycle curve of the symmetrical battery containing the porous zinc oxide nanosheet modification layer is shown.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Preparation method of copper nanowire modification layer
(1) 0.17g of CuCl2·2H2O and 0.31g glucose were dissolved in 50mL of deionized water, and then 1.44g of octadecylamine was added to the above mixture and stirred to a uniform pale blue emulsion. It was transferred to an autoclave and heated at 120 ℃ for 6 hours. Naturally cooling to room temperature, and then centrifugally drying to obtain the copper nanowire. The copper nano-particles with the diameter of 30-80nm and the length of 30-50 mu m synthesized by a hydrothermal methodThe line (the micro-morphology is shown in figure 1) is uniformly dispersed into water by magnetic stirring for 30 minutes, and the concentration is 0.2 mg/mL;
(2) filtering the dispersion with a hydrophilic filter membrane (type: Tianjin Jinteng microporous water system filter membrane, diameter 50mm, aperture 0.8 μm), washing with water for three times, and drying at room temperature for 10 hr to obtain copper nanowire with loading of 0.4mg/cm2The loading thickness of the copper nanowire is 18 μm, and the cross-sectional view is shown in fig. 2;
(3) ultrasonically cleaning a commercial zinc sheet, drying the zinc sheet at room temperature, and punching the zinc sheet and the copper nanowire modification layer filter membrane into a circular sheet with the diameter of 10mm by using a sheet punching machine;
(4) in order to study the inhibition effect of the functional nano material modification layer on zinc dendrites, a zinc-zinc symmetrical battery is assembled by facing one side of the material with the copper nanowires to metal zinc, and the schematic diagram of the internal structure of the battery is shown in fig. 3. Wherein the electrolyte is 2mol/L zinc sulfate aqueous electrolyte, and a bare zinc symmetrical battery without a modification layer is taken as a comparative example 1;
(5) at 0.2mA/cm2Current density of 0.2mAh/cm2The constant current charge and discharge curve of the test condition (1) is shown in FIG. 4. The battery with the copper nanowire modification layer still has no short circuit after undergoing a charging and discharging behavior of 500 hours, while the bare zinc symmetrical battery in the comparative example 1, which is not protected by the copper nanowire modification layer, can only complete a normal charging and discharging behavior of 30 hours, and then has a short circuit. For the battery with the copper nanowire modification layer, the zinc surface micro-topography (figure 5) after 50-hour circulation shows that the ion field and the electric field during zinc ion deposition/dissolution in the charging and discharging process are regulated and controlled due to the channels formed by the staggered copper nanowire networks on the modification layer, so that the zinc ion deposition is more uniform, the generation of zinc dendrites and the short circuit problem of the battery are inhibited, and the service life of the battery is obviously prolonged. In contrast, the bare zinc symmetric cell of comparative example 1 showed uneven deposition and dendrites on the zinc surface after 50 hours of cycling (fig. 6).
(6) By adjusting the test conditions of current density and cut-off capacity, a rate performance curve as in fig. 7 was obtained (5 cycles per test condition). It can be seen that the electrochemical performance of the zinc-zinc symmetric battery protected by the copper nanowire modification layer is much higher than that of the bare zinc symmetric battery in comparative example 1 under the conditions of high current density and higher cut-off capacity.
Example 2
Preparation method of nano silicon dioxide modification layer
(1) Adding 4mL of propyl orthosilicate into a mixed solution containing 50mL of ethanol, 10mL of water and 1mL of ammonia water, magnetically stirring at room temperature for 14h, and centrifugally drying the suspension to obtain the nano silicon dioxide spheres. Uniformly dispersing the silica spheres (with the micro-morphology as shown in figure 8) with the diameter of 150nm, which are synthesized by the sol-gel method, into water by magnetic stirring for 30 minutes, wherein the concentration is 0.4 mg/mL;
(2) filtering the dispersion with a hydrophilic filter membrane (type: Tianjin Jinteng microporous water system filter membrane with diameter of 50mm and pore diameter of 0.8 μm), washing with water for three times, and drying at 60 deg.C for 4 hr to obtain nanometer silica with loading of 0.8mg/cm2The functional nano-silica modified layer filter membrane has the loading thickness of the nano-silica of 25 mu m;
(3) ultrasonically cleaning a commercial zinc sheet, drying at room temperature, and punching the zinc sheet and the nano silicon dioxide modified layer filter membrane into a circular sheet with the diameter of 10mm by using a sheet punching machine;
(4) in order to research the inhibition effect of the functional nano material modification layer on zinc dendrite, the zinc-zinc symmetrical battery is assembled by facing one side with the nano silicon dioxide material to metal zinc. Wherein the electrolyte is 2mol/L zinc sulfate aqueous electrolyte, and a bare zinc symmetrical battery without a modification layer is taken as a comparative example 1;
(5) at 0.1mA/cm2Current density of 0.5mAh/cm2The constant current charge and discharge curve of the test condition (2) is shown in FIG. 9. The battery with the nano-silica modified layer still has no short circuit phenomenon after undergoing 500h of charge and discharge behaviors, while the battery without the nano-silica modified layer in the comparative example 1 has no short circuit phenomenonThe protected bare zinc symmetrical battery can only complete normal charging and discharging behaviors for 30 hours, and then a short circuit phenomenon occurs.
Example 3
Preparation method of carbon nano tube modification layer
(1) Uniformly dispersing three different carbon nanotube powders (the micro morphology is shown in figure 10) of a commercial carboxylated carbon nanotube (the diameter is 15-30nm), a commercial hydroxylated carbon nanotube (the diameter is 15-30nm) and a common multi-walled carbon nanotube (the diameter is 8-20nm) which are sold by a vendor as a scientific material station into water by magnetic stirring for 30 minutes, wherein the concentration is 0.25 mg/mL;
(2) filtering the dispersion by suction filtration to hydrophilic filter membrane (type: Tianjin Jinteng microporous water system filter membrane, diameter 50mm, aperture 0.8 μm) with aperture 0.8 μm, washing with water for three times, and drying at 60 deg.C for 4 hr to obtain carbon nanotube with loading of 0.8mg/cm2The functionalized carbon nanotube modified layer filter membrane has the loading thickness of the carbon nanotube of 25 μm;
(3) ultrasonically cleaning a commercial zinc sheet, drying the zinc sheet at room temperature, and punching the zinc sheet and the carbon nano tube modification layer filter membrane into a circular sheet with the diameter of 10mm by using a sheet punching machine;
(4) in order to research the inhibition effect of the functionalized nano material modification layer on zinc dendrites, one side of the material with the carbon nano tube is opposite to metal zinc to assemble a zinc-zinc symmetrical battery. Wherein the electrolyte is 2mol/L zinc sulfate aqueous electrolyte, and a bare zinc symmetrical battery without assembling a carbon nano tube modification layer is taken as a comparative example 1;
(5) at 0.2mA/cm2Current density of 0.2mAh/cm2The cut-off capacity of the bare zinc symmetric cell is taken as a test condition, and constant current charge-discharge curves of different carbon nanotube modification layers and the unprotected bare zinc symmetric cell are shown in fig. 11. The carbon nanotube with oxygen-containing functional groups (including carboxyl and hydroxyl) has better inhibition effect on zinc dendrite than the common carbon nanotube, and the electrochemical performance of the zinc cell with three carbon nanotube modification layers is higher than that of the bare zinc symmetric cell in comparative example 1.
Example 4
Preparation method of porous zinc oxide nanosheet modification layer
(1) Weighing a certain amount of zinc sulfate to prepare a 2mol/L zinc sulfate solution, mixing the zinc sulfate solution with a 1mol/L potassium hydroxide solution according to the volume ratio of 2:3, and then stirring to react to generate basic zinc sulfate. Standing the sample, depositing for a proper time, sucking out excessive water by using a dropper, washing with ultrapure water for three times, repeating the operations, putting the obtained basic zinc sulfate into an oven, drying at 80 ℃, putting into a mini box furnace, sintering for 2 hours at 1000 ℃ in an air atmosphere, and cooling to room temperature. Thus preparing the porous zinc oxide nano-sheet. Uniformly dispersing the synthesized porous zinc oxide nano sheet (the microstructure is shown as figure 12) with the aperture of 5-200nm and the sheet thickness of 200-500nm into water by magnetic stirring for 30 minutes, wherein the concentration is 0.25 mg/mL;
(2) filtering the dispersion by suction filtration to obtain hydrophilic filter membrane (type: Tianjin Jinteng microporous water system filter membrane, diameter 50mm, pore diameter 0.8 μm) with pore diameter of 0.8 μm, washing with water for three times, and drying at 60 deg.C for 4 hr to obtain porous zinc oxide nano-sheet with loading capacity of 1.6mg/cm2The functional porous zinc oxide nano-sheet modification layer filter membrane has the loading thickness of 50 mu m;
(3) ultrasonically cleaning a commercial zinc sheet, drying at room temperature, and punching the zinc sheet and the porous zinc oxide nano sheet modification layer filter membrane into a circular sheet with the diameter of 10mm by using a sheet punching machine;
(4) in order to research the inhibition effect of the functional nano material modification layer on zinc dendrite, one side of the porous zinc oxide nano sheet material is opposite to metal zinc to assemble a zinc-zinc symmetrical battery. Wherein the electrolyte is 2mol/L zinc sulfate aqueous electrolyte, and a bare zinc symmetrical battery without a modification layer is taken as a comparative example 1;
(5) at 0.2mA/cm2Current density of 0.2mAh/cm2The constant current charge and discharge curve of the test condition (2) is shown in FIG. 13. The zinc-zinc symmetric cell with the porous zinc oxide nanosheet modifying layer can still have no short circuit phenomenon after being subjected to charge and discharge behaviors for 300 hours, while the bare zinc symmetric cell which is not protected by the porous zinc oxide nanosheet modifying layer in comparative example 1,normal charge and discharge behavior can only be completed for 30 hours, after which a short circuit phenomenon occurs.
Comparative example 1
(1) Carrying out ultrasonic cleaning on a commercial zinc sheet, drying at room temperature, and punching the zinc sheet into a wafer with the diameter of 10mm by using a sheet punching machine;
(2) and 2mol/L zinc sulfate aqueous electrolyte is used for assembling the zinc foil into a bare zinc symmetrical battery.
(3) At 0.2mA/cm2Current density of 0.2mAh/cm2The constant current charge/discharge curve of the test condition (1) is shown in FIG. 11. The unprotected bare zinc symmetrical battery can only complete normal charging and discharging behaviors for 30 hours, and then a short circuit phenomenon occurs.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (6)

1. A preparation method of a metal zinc cathode with a functional nano material modification layer is characterized by comprising the following steps:
uniformly dispersing the nano material in a solvent, carrying out suction filtration on the solvent to obtain a filter membrane, and drying to obtain a functional nano material modification layer for the metal zinc cathode; cutting the filter membrane into a shape not smaller than the size of the metal zinc sheet, and directly covering the surface of the metal zinc electrode;
the nano material is a copper nanowire, the diameter of the copper nanowire is 5-200nm, and the length of the copper nanowire is 1-50 mu m.
2. The preparation method of the metal zinc anode with the functional nano-material modification layer according to claim 1, characterized in that:
the solvent is water;
the filter membrane is a hydrophilic microporous filter membrane, and the aperture is 0.02-2 mu m.
3. The preparation method of the metal zinc anode with the functional nano-material modification layer according to claim 1, characterized in that:
the load capacity of the nano material on the filter membrane is 0.1-5mg/cm2。
4. The preparation method of the metal zinc anode with the functional nano-material modification layer according to claim 1, characterized in that:
the load capacity of the nano material on the filter membrane is 0.2-3mg/cm2。
5. A metallic zinc anode with a functional nanomaterial modification layer prepared according to the method of any one of claims 1 to 4.
6. An aqueous zinc-based energy storage system comprising the metallic zinc negative electrode of claim 5 having a functional nanomaterial modification layer.
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