CN114566608A - Silver-zinc alloy coating with zinc sheet as substrate and preparation method thereof - Google Patents
Silver-zinc alloy coating with zinc sheet as substrate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silver-zinc alloy coating taking a zinc sheet as a substrate and a preparation method thereof, belonging to the field of secondary zinc batteries. The coating is composed of a silver-zinc alloy layer with the thickness of 400-3000 nm, which covers the surface of the zinc sheet, wherein the atomic ratio of zinc to silver in the silver-zinc alloy layer is 0.2-5.0. The silver particles provide nucleation cores and form a cluster-like silver-zinc alloy coating together with the zinc particles. The preparation method comprises the steps of firstly polishing and ultrasonically cleaning a zinc sheet to remove zinc oxide and oil stains, and fully drying; placing a zinc sheet in a chamber of a plasma sputtering apparatus; introducing argon as protective gas; and (3) carrying out plasma sputtering on the zinc sheet by using a silver target to obtain a silver-zinc alloy coating on the surface of the zinc sheet. The vertical crystal face of the silver-zinc alloy coating is highly matched with the vertical crystal face of zinc, so that the nucleation of zinc can be uniform, the growth of zinc can be regulated, the horizontal deposition of zinc is finally promoted, the occurrence of dendritic crystal puncture danger is reduced, and the secondary zinc battery with long service life and high performance is realized.
Description
Technical Field
The invention belongs to the field of novel battery energy storage, and particularly relates to a silver-zinc alloy coating taking a zinc sheet as a substrate and a preparation method thereof.
Background
Secondary zinc batteries have been rapidly developed in recent years due to their advantages of high safety, low cost, etc., and have become a powerful candidate for large-scale energy storage batteries in the late lithium battery age. The Chinese patent in 9 months in 2020 definitely proposes the targets of 'carbon peak reaching' in 2030 years and 'carbon neutralization' in 2060 years, at this time, new energy power generation including photovoltaic and wind power is developed in an explosive manner, and a power grid side and a user side energy storage power station matched with the new energy power generation are necessary. The lithium iron phosphate battery which is commonly used as an energy storage battery at present is far better than the lead-acid battery in energy density, but the safety and the cost of the lithium iron phosphate battery are greatly improved compared with the lead-acid battery. In the large-scale construction and operation of electrochemical energy storage power stations in China since 2018, a plurality of energy storage power stations have fire or explosion accidents, so that large economic loss is caused, and the development of the industry is hindered. The secondary zinc battery adopts the water-based electrolyte, so that the secondary zinc battery has intrinsic safety and no thermal runaway risk. Due to the abundant reserves of zinc and water resources, the cost of zinc batteries is much lower than that of lithium batteries. And the energy density of the secondary zinc battery is higher than that of the lead-acid battery. In the future, secondary zinc batteries will play an important role in the fields of energy storage and the like.
However, at present, the zinc dendrite problem of the zinc metal cathode is still a difficult problem which troubles the industrialization of the zinc ion battery. Because the crystal plane orientation of the surface of the metallic zinc cathode is rich, the deposition of zinc is inclined to the crystal planes of zinc (101), (100) and the like with a larger included angle with the electrode, which is a favorable process in thermodynamics, and uneven dendritic zinc deposition is caused under the repeated uneven nucleation and vertical growth. The growth of zinc dendrites can puncture the soft separator and cause micro-short circuits, and although not causing thermal runaway problems, can greatly reduce the battery life, resulting in a typical zinc symmetric battery at 1mA/cm2And 1mAh/cm2The operation can be carried out for about 100 hours under the condition. Coating chemistry is currently a solution suitable for large-scale applications, but finding an ideal coating that achieves a high lattice match with horizontally deposited zinc is difficult.
Therefore, a zinc negative electrode having a silver-zinc alloy coating layer, which realizes a long-life, high-performance secondary zinc battery by a high vertical lattice matching effect, has been devised in view of the above problems. The vertical crystal face of the silver-zinc alloy coating is highly matched with the vertical crystal face of zinc, so that the nucleation of zinc can be uniform, the growth of zinc can be regulated and controlled, and the zinc water can be promoted finallyFlat deposition and reduced dendrite penetration risk. The obtained silver alloy coated zinc electrode has a current density of 1mA/cm2、2mA/cm2And 4mA/cm2Under the three test conditions, the electrode life was improved by 10.37 times on average compared to the untreated zinc cathode. Compared with other two heavy metal zinc alloy coatings, namely gold zinc alloy and copper zinc alloy, the service life of the battery is prolonged to be higher, namely 2.71 times of that of the battery and 2.98 times of that of the battery. Compared with other coating patents, the electrolyte used by the technology has low concentration, large working current density of the electrode and more ideal service life.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a silver-zinc alloy coating taking a zinc sheet as a substrate and a preparation method thereof.
In order to solve the technical problem of the invention, the adopted technical scheme is as follows:
a preparation method of a silver-zinc alloy coating taking a zinc sheet as a substrate comprises the following steps:
1) polishing, ultrasonically cleaning a zinc sheet, and drying;
2) placing a zinc sheet in a chamber of a plasma sputtering apparatus;
3) opening a vacuum pump to pump the chamber until the vacuum degree is less than or equal to 30Pa, and introducing argon as protective gas to stabilize the vacuum degree at 5-25 Pa;
4) setting sputtering time and sputtering current, carrying out plasma sputtering on the zinc sheet by using a silver target, and obtaining a silver-zinc alloy coating on the surface of the zinc sheet, wherein the sputtering time is 3-40 minutes, and the sputtering current is 5-40 mA.
Further, the polishing refers to polishing by using sand paper, a file, a blade and an agate knife with any meshes, the ultrasonic cleaning is ultrasonic cleaning by using ethanol and/or water, the drying is to dry the zinc sheet in a drying oven or a vacuum oven, and the drying temperature is 50-100 ℃.
Further, the plasma sputtering apparatus refers to an apparatus capable of performing plasma treatment on the surface of the zinc electrode, and includes a magnetron sputtering apparatus, an ion sputtering apparatus, a plasma surface treatment apparatus, and a plasma sputtering apparatus. The chamber can be sealed, when the chamber is used, the internal air needs to be exhausted, the plasma sputtering refers to that the silver target and the zinc sheet are respectively arranged on a cathode and an anode, the anode is grounded, negative high voltage is applied, the cathode emits electrons, electrons bombard argon gas to generate cascade ionization to form plasma, the ions bombard the cathode target at high energy, when the energy of the ions is higher than the binding energy of target atoms, silver atoms or silver atom clusters are separated from the target, fall on the surface of a zinc electrode and form a thin silver-zinc alloy layer, and the zinc-silver atomic ratio can be adjusted according to the sputtering current and the vacuum degree of different equipment.
Preferably, during sputtering, the vacuum degree is stabilized at 5-20 Pa by adjusting the flow of argon; the sputtering current is 12 mA-17 mA, and the sputtering time is 10 minutes-30 minutes.
Further, the argon gas is high-purity argon gas with the purity of more than or equal to 99.99%, and the silver target is a high-purity silver target with the purity of more than or equal to 99.99%.
The silver-zinc alloy coating prepared by the preparation method and taking the zinc sheet as the substrate has the thickness of 400-3000 nm, the average diameter of silver-zinc cluster particles in the silver-zinc alloy coating is 200-1000 nm, and the zinc-silver atomic ratio of the silver-zinc alloy coating is 0.2-5.0, preferably 0.6-3.9. The silver particles provide nucleation cores and form a cluster-shaped silver-zinc alloy coating together with the zinc particles; the silver particles become fluffy when the zinc-silver atomic ratio is increased, the silver particles are compact blocks when the zinc-silver atomic ratio is about 0.6-0.8, the silver particles are porous when the zinc-silver atomic ratio is about 1.7-3.3, and the silver particles are cotton when the zinc-silver atomic ratio reaches 3.9; the content of the zinc particles increases along with the increase of the atomic ratio of the zinc and the silver, and the zinc particles are flaky or cotton-shaped.
The silver-zinc alloy coating taking the zinc sheet as the substrate is applied as the negative electrode of the zinc battery.
Further, a vanadium dioxide (B) electrode is used as a positive electrode, glass fiber is used as a diaphragm, and 1mol/L zinc sulfate solution is used as electrolyte to assemble the zinc battery.
Compared with the prior art, the beneficial effects are that:
firstly, the performance and the service life of the zinc ion battery are greatly improved. At a current density of 1mA/cm2、2mA/cm2And 4mA/cm2Under the three test conditions, the electrode life was improved by 10.37 times on average compared to the untreated zinc cathode. Compared with other two heavy metal zinc alloy coatings, namely gold zinc alloy and copper zinc alloy, the service life of the battery is prolonged to be higher, namely 2.71 times and 2.98 times of that of the battery. Compared with other coating patents, the electrolyte used by the technology has low concentration, large working current density of the electrode and longer service life. The silver-zinc alloy coating is derived from a unique vertical crystal face matching mechanism of the silver-zinc alloy coating, the vertical crystal face of the silver-zinc alloy coating is highly matched with the vertical crystal face of zinc, the nucleation of zinc can be uniform, the growth of zinc can be regulated and controlled, the horizontal deposition of zinc is finally promoted, and the occurrence of dendritic crystal puncture danger is reduced.
Secondly, the preparation method is simple, scientific and effective. The silver-zinc alloy coating is obtained by firstly polishing and ultrasonically cleaning a zinc sheet to remove zinc oxide and oil stains, fully drying, then placing the zinc sheet in a chamber of a plasma sputtering instrument, introducing argon as protective gas, and performing plasma sputtering on the zinc sheet by using a silver target on the surface of the zinc sheet, wherein the target is not required to be heated during sputtering. The sputtering parameters resulted in an ideal zinc-silver alloy ratio of 3. The preparation method is simple to operate and low in cost, is an ideal coating for realizing high lattice matching with horizontally deposited zinc, plays a key role in inhibiting the growth of zinc dendrites, benefits from the high maturity of a plasma etching technology, and can realize large-scale application.
Drawings
FIG. 1 is a surface topography of a silver-zinc alloy coating and SEM made in example 1;
FIG. 2 is an SEM image of surface zinc deposition morphology after cycling for a blank zinc electrode and a symmetrical cell with a silver-zinc alloy coated zinc electrode;
FIG. 3 is an XRD pattern of a gold zinc alloy coated zinc electrode with pure zinc;
FIG. 4 is an XRD pattern of a copper zinc alloy coated zinc electrode with pure zinc;
FIG. 5 is an SEM image showing the thickness of the silver-zinc alloy coating of example 1;
FIG. 6 is an EDS elemental spectrum (zinc to silver atomic ratio 2.8) of example 1;
fig. 7 is an XRD spectrum of a blank zinc electrode and a zinc electrode with a silver-zinc alloy coating;
fig. 8 is a life performance of zinc negative electrodes and pure zinc negative electrodes with silver-zinc alloy, gold-zinc alloy and copper-zinc alloy coatings with two silver-zinc alloy ratios at different current densities and area capacities;
FIG. 9 is a working principle diagram of the dense deposition of zinc on a silver-zinc alloy based on vertical lattice matching;
FIG. 10 is a surface morphology of a silver-zinc alloy coating with a zinc sheet as a substrate, wherein the atomic ratio of zinc to silver is 0.6;
FIG. 11 is a surface morphology of a silver-zinc alloy coating with a zinc sheet as a substrate, with an atomic ratio of zinc to silver of 0.8;
FIG. 12 is a surface appearance of a silver-zinc alloy coating with a zinc sheet as a substrate, wherein the atomic ratio of zinc to silver is 1.7;
FIG. 13 is a surface morphology of a silver-zinc alloy coating with a zinc sheet as a substrate, with an atomic ratio of zinc to silver of 3.9;
FIG. 14 is a graph comparing the long cycle performance of a full cell assembled with a blank zinc electrode and a silver-zinc alloy coated zinc electrode as the negative electrode and vanadium dioxide (B) as the positive electrode, respectively.
Detailed Description
The present invention will be further described below by way of comparative examples and examples with reference to the accompanying drawings.
Comparative example 1
And preparing a pure zinc electrode, and testing and characterizing the battery as a blank sample.
A0.2 mm thick sheet of pure zinc (purchased from national chemical) was polished with 1000 mesh sandpaper to remove oil stains and zinc oxide layer on the surface, then ultrasonically cleaned with ethanol (ultrasonic frequency 40kHz, power 300W, time 5 minutes), and cut into pieces of 12mm in diameter and about 1.13cm in area using an electrode microtome2The wafer of (1) was cleaned again with ethanol by ultrasonic cleaning (ultrasonic frequency 40kHz, power 300W, time 5 minutes), and then dried in a vacuum oven at 80 ℃ for 1 hour.
Step 2, assembling the zinc symmetrical battery
The blank zinc electrodes were assembled into CR2016 type (cell diameter 20.0mm, thickness 1.6 mm) symmetric cells for cycling stability testing. Each part of the battery sequentially comprises a positive electrode shell, a pure zinc sheet, a diaphragm, a pure zinc sheet, a stainless steel gasket (with the diameter of 16mm and the thickness of 500 mu m) and a negative electrode shell, and the sealing pressure is about 50 kilograms per cubic centimeter. The battery needs to be left standing at room temperature for not less than 4 hours before use. The separator was a glass fiber (produced by Whatman, 110mm in diameter, cut into a circular piece 19mm in diameter) for use. The electrolyte is 1mol/L (or 1M) zinc sulfate solution, 100 mu L of electrolyte is added into each battery, and the electrolyte is added after a diaphragm is placed. The preparation method of the 1M zinc sulfate electrolyte comprises the following steps of mixing ZnSO4∙7H2O (analytically pure, purchased from national pharmaceutical chemicals) was dissolved in pure water in a mass ratio of about 11.5024: 34.9556.
Step 3, zinc symmetrical battery test
The symmetric cell long cycle test was performed in an incubator maintained at 25 ℃ to eliminate the effects of ambient temperature. The battery test uses a battery test system of Wuhan blue electricity. The test parameters are set as constant current charging and constant current discharging, and the current density based on the electrode area is 1mA/cm2The area capacity is 1mAh/cm2. Under the test conditions, the service life of the pure zinc electrode symmetric battery is about 93 hours, and the service life of the pure zinc electrode is short. In addition, at 2mA/cm for two other groups of larger test currents2、1mAh/cm2The service life of the pure zinc symmetrical battery is 112 hours under the condition of 4mA/cm2、2mAh/cm2The pure zinc symmetric cell under the conditions had a life of 82 hours.
Step 4, observing the dendrite on the surface of the zinc symmetrical battery
And observing the surface appearance of the dead pure zinc electrode after 93 hours by adopting a Zeiss focused dual-ion-beam Scanning Electron Microscope (SEM). After prolonged zinc deposition and stripping, zinc dendrites up to tens of microns in size appear on the surface of the zinc-bearing electrode, as shown in the left panel of fig. 2, which have penetrated the membrane, and are linear in the left panel of fig. 2, a glass fiber membrane. The appearance of zinc dendrites on the pure zinc cathode can easily cause short circuit of the battery, and is the main reason for short service life of the zinc ion battery.
Comparative example 2
And the alloy is a gold-zinc alloy obtained by sputtering the heavy metal element plasma.
Same as comparative example 1, step 1.
Step 2, loading a pure zinc wafer into a plasma sputtering instrument
A plurality of pure zinc wafers (determined by the area of a stage of a plasma sputtering instrument, wherein no more than 10 pure zinc wafers can be placed) are uniformly placed on the stage of the plasma sputtering instrument (the used plasma sputtering instruments are all called three-target plasma sputtering instruments, the model is VTC-16-3HD, is purchased from Shenyang Kejing, and has the output direct current voltage of 1.68 kV), and the plasma sputtering is carried out at room temperature without heating a target material.
Step 3, cleaning the cavity of the plasma sputtering instrument
Closing a cover of the plasma sputtering instrument, opening a vacuum pump, pumping the chamber to high vacuum (the vacuum degree is less than or equal to 30 Pa), introducing high-purity argon (more than or equal to 99.99%) as protective gas, adjusting the gas inlet rate to enable the vacuum degree to be stable at 5Pa, and performing sputtering after lasting for 5 minutes.
Step 4, argon plasma sputtering
Selecting a gold target as a sputtering target (purchased from Shenyang Kejing, the purity is more than or equal to 99.99%), setting the sputtering time to be 5 minutes, starting sputtering, adjusting the sputtering current to 10mA, carrying out plasma sputtering on a zinc electrode, waiting for about 3 minutes after the sputtering is finished, starting the sputtering again, and repeating the steps until the total sputtering time is 30 minutes. Turning off the vacuum pump, turning on the plasma sputtering apparatus, obtaining a gold coating (marked as gold-zinc alloy coating zinc electrode) on the surface of the zinc sheet, and testing the gold-zinc alloy through X-ray diffraction (XRD), specifically referring to FIG. 3, and as can be seen from FIG. 3, the existence of AuZn3The alloy phase is considered to have a zinc-gold atomic ratio of 3.
Step 5, assembling the symmetrical battery with the gold-zinc alloy coating zinc electrode
And assembling the gold-zinc alloy coated zinc electrode into a CR2016 type symmetrical battery to perform a cycle stability test. The cell was assembled as in step 2 of comparative example 1 except that the pure zinc sheet of comparative example 1 was replaced with a gold-zinc alloy coated zinc electrode.
Step 6, testing the symmetric battery with the gold-zinc alloy coating zinc electrode
And assembling the gold-zinc alloy coated zinc electrode into a symmetrical battery for cycle test. In an incubator at 25 ℃. The battery test uses a battery test system of Wuhan blue electricity. The test shows that the current density of the gold-zinc alloy coated zinc electrode is 1mA/cm2And the area capacity is 1mAh/cm2Under the conditions of (1) was effectively circulated for 423 hours.
Comparative example 3
And the copper-zinc alloy is obtained by sputtering the heavy metal element plasma.
The steps 1 and 2 are the same as the comparative example 2,
step 3, cleaning the cavity of the plasma sputtering instrument
Closing a cover of the plasma sputtering instrument, opening a vacuum pump, pumping the chamber to high vacuum (the vacuum degree is less than or equal to 30 Pa), introducing high-purity argon (more than or equal to 99.99%) serving as protective gas, adjusting the gas inlet rate to enable the vacuum degree to be stabilized at 10Pa, and sputtering after 5 minutes.
Step 4, argon plasma sputtering
Selecting a copper target (purchased from Shenyang Kejing, the purity is more than or equal to 99.99%) as a sputtering target material, setting the sputtering time to be 5 minutes, starting sputtering, adjusting the sputtering current to be 20mA, carrying out plasma sputtering on a zinc electrode, waiting for about 3 minutes after the sputtering is finished, starting the sputtering again, and repeating the steps until the total sputtering time is 30 minutes. Turning off the vacuum pump, turning on the plasma sputtering apparatus, obtaining copper coating (marked as copper-zinc alloy coating zinc electrode) on the surface of the zinc sheet, and testing by X-ray diffraction (XRD) to obtain copper-zinc alloy, as shown in figure 4, and as shown in figure 4, CuZn exists5The alloy phase is considered to have a zinc-copper atomic ratio of 5.
Cell Assembly and testing As in comparative example 2, copper-Zinc alloy coated Zinc electrodes were tested at a current density of 1mA/cm2And the area capacity is 1mAh/cm2Can be effectively circulated for 385 hours under the condition of (1).
Comparative example 4
The pure zinc electrode and the vanadium dioxide (B) anode form a zinc ion full battery
As in comparative example 1.
Step 2, preparation of vanadium dioxide (B) anode
References Ding J, Du Z, Gu L, et al2+ intercalation and deintercalation in vanadium dioxide[J]Advanced Materials, 2018, 30(26): 1800762. specifically, 1.2 g V was added to ultrapure water (40 mL)2O5(purity 99%, purchased from Western reagent) and 1.8 g H2C2O4·2H2O (purity 99.8%, purchased from national medicine) and the above mixture was then reacted for 60 minutes at 75 ℃ under magnetic stirring to give a dark blue dispersion. The dispersion was then transferred to a 50mL autoclave lined with Teflon and held at 180 ℃ for 180 minutes. After complete cooling, the reaction was removed and the precipitated product was collected using a high speed centrifuge. Centrifuge speed was 8000 rpm for 5 minutes. Centrifugation was repeated and washed with ultrapure water until the supernatant in the centrifuge tube was almost transparent. VO obtained by centrifugation2(B) The blocks were dried in an oven at 50 ℃ for 6 hours, then ground into a powder and dried for 12 hours to obtain VO2(B) And (3) powder. VO (vacuum vapor volume)2(B) The positive plate is prepared by a rolling film method without a current collector so as to increase the loading capacity of the active material. VO (vacuum vapor volume)2(B) The positive plate is composed of VO with the mass ratio of 6:2:22(B) Carbon black and PTFE. First 140 mg of VO2(B) The powder and 46.6 mg of carbon black powder were dry-milled for 5 minutes, then an appropriate amount of isopropanol and 77.7 mg of a 60wt% aqueous PTFE solution (PTFE mass: 46.6 mg) were added, and wet-milling was continued in a fume hood until a paste was formed. Next, the mixture was rolled into a sheet using a roll press. While rolling, isopropanol was continuously added to maintain the viscosity of the PTFE. The long pieces were sliced using a microtome at a certain humidity. They were cut into circular pieces (about 1.13cm in area) of 12mm in diameter2) And then dried in an oven at 60 ℃ for 8 h and weighed for later use. VO in positive plate2(B) The loading was about 3.7g/cm2。
Step 3, pure zinc full cell assembly
Mixing blank zinc electrode and VO2(B) The electrodes were assembled into a CR2016 type (cell diameter 20.0mm, thickness 1.6 mm) full cell. The whole battery is assembled by a positive electrode shell, a stainless steel mesh (400 meshes, diameter 12 mm), a positive electrode plate, a diaphragm, a negative electrode plate, a gasket and a negative electrode shell. The sealing pressure is approximately 50 kilograms per cubic centimeter. The battery needs to be left standing at room temperature for not less than 4 hours before use. The membrane is a glass fibre (produced by Whatman, 110mm in diameter, cut into 19mm disks for use). The electrolyte is 1mol/L (or 1M) zinc sulfate solution, 100 mu L of electrolyte is added into each battery, and the electrolyte is added after a diaphragm is placed.
Step 4, testing pure zinc full cell
The full cell test was performed in an incubator (25 ℃) to eliminate the influence of ambient temperature. The battery test uses a battery test system of Wuhan blue electricity. The current density was 500 mA/g. The initial specific discharge capacity was 62.5mAh/g, the 5 th cycle reached a maximum of 189.8mAh/g, and then showed a downward trend, short circuit death after about 90 cycles, and the capacity dropped to 110 mAh/g.
Example 1
And (3) preparing and characterizing the silver-zinc alloy coating zinc electrode.
A0.2 mm thick pure zinc plate (purchased from national chemical) was polished with 1000-mesh sandpaper to remove surface oil stains and a zinc oxide layer, then the plate was ultrasonically cleaned with ethanol, and cut into pieces having a diameter of 12mm and an area of about 1.13cm using an electrode slicer2The wafer of (1) was ultrasonically cleaned again with ethanol and then placed in a vacuum oven at 80 ℃ to dry for 1 hour.
Step 2, loading a pure zinc wafer into a plasma sputtering instrument
A plurality of pure zinc wafers (which are determined by the area of a stage of a plasma sputtering instrument, and not more than 10 pure zinc wafers can be placed in the stage) are uniformly placed on the stage of the plasma sputtering instrument (the used plasma sputtering instruments are all called three-target plasma sputtering instruments, the model is VTC-16-3HD, and is purchased from Shenyang Kejing), and the plasma sputtering is different from the magnetron sputtering in that the sputtering is carried out at room temperature, the target material is not required to be heated, and the energy is saved.
Step 3, cleaning the cavity of the plasma sputtering instrument
Closing a cover of the plasma sputtering instrument, opening a vacuum pump, pumping the chamber to high vacuum (the vacuum degree is less than or equal to 30 Pa), introducing high-purity argon (more than or equal to 99.99%) serving as protective gas, adjusting the gas inlet rate to enable the vacuum degree to be stable at 5Pa, and sputtering after 5 minutes.
Step 4, argon plasma sputtering
Selecting a silver target as a sputtering target material (purchased from Shenyang Kejing, the purity is more than or equal to 99.99%), setting the sputtering time to be 5 minutes, starting sputtering, adjusting the sputtering current to be 15mA, carrying out plasma sputtering on a zinc electrode, waiting for about 3 minutes after the sputtering is finished, starting the sputtering again, and setting the total sputtering time to be 30 minutes. Turning off the vacuum pump and turning on the plasma sputtering apparatus, a gray coating can be obtained on the surface of the zinc sheet, as shown in FIG. 1.
Step 5, the shape of the silver-zinc alloy and the atomic ratio of zinc to silver
The surface morphology of the silver-zinc alloy coated zinc electrode obtained by observation of a scanning electron microscope is shown in figure 1, the silver-zinc alloy cluster particles are of a porous structure, and each cluster particle comprises white point-like and gray sheet-like substances which are a place with high silver content locally and a place with high zinc content locally. The thickness of the silver-zinc alloy coating was measured to be about 570 nm (as shown in fig. 5), and the cluster particle diameter in the silver-zinc alloy coating was about 500 nm. As shown in fig. 6, X-ray energy spectrum analysis (EDS) showed 2.8 atomic ratio of zinc and silver, and X-ray photoelectron spectrum analysis (XPS) showed 4.9 atomic ratio of zinc and silver. The reason for the lower Ag ratio in the XPS test results compared to the EDS results should be the presence of additional zinc flakes, which are present in the silver-zinc alloy layer or the zinc substrate. Here and hereafter, the atomic ratio of zinc to silver as determined by EDS is used as a reference.
Step 6, the unique vertical crystal face structure of the silver-zinc alloy
The zinc electrode coated with a zinc-silver alloy ratio of 2.8 and the pure zinc electrode were characterized using XRD, and the results are shown in fig. 7Shown in the figure. From FIG. 7, it can be seen that when the ratio of Zn to Ag is about 2.8, the Ag-Zn alloy has a crystal face AgZn with a predominance3(002) The crystal plane is parallel to the substrate and the direction of the crystal plane is the normal direction, i.e. perpendicular to the substrate, which leads to a kind of AgZn-based3(002) And the vertical crystal face of Zn (002) to promote the ordered planar deposition of Zn.
Example 2
Half-cell performance test of silver-zinc alloy coated zinc electrode and action mechanism of silver-zinc alloy
The silver-zinc alloy coated zinc electrode prepared in example 1 was assembled into a symmetrical cell and tested under the same conditions as in step 2 of comparative example 1. The test conditions were divided into three groups, each of which was (1) a current density of 1mA/cm2The area capacity is 1mAh/cm2(ii) a (2) The current density is 2mA/cm2The area capacity is 1mAh/cm2(ii) a (3) The current density is 4mA/cm2The area capacity is 2mAh/cm2。
Step 2, the test result is compared with the pure zinc symmetrical battery in the comparative example 1
The test results of the symmetrical battery with the silver-zinc alloy coated zinc electrode under three conditions are shown in fig. 8, and the service life of the battery respectively reaches (1) 1150 hours; (2) 1360 hours; (3) 540 hours. Compared with the pure zinc electrode of comparative example 1, the service life of the battery is obviously prolonged, and under the three test conditions, the service life of the silver-zinc alloy coated zinc electrode is prolonged to 12.37 times, 12.14 times and 6.59 times of the service life of the pure zinc symmetrical battery in sequence. The average lifting is 10.37 times. This is a good indication that coating the zinc electrode with silver-zinc alloy can greatly improve the cycle life of the battery.
Step 3, comparing the test result with the symmetric batteries of the gold-zinc alloy coated zinc electrode and the copper-zinc alloy coated zinc electrode in the comparative examples 2 and 3
The assembly and test conditions of the silver-zinc alloy coated zinc symmetrical battery, the gold-zinc alloy coated zinc symmetrical battery and the copper-zinc alloy coated zinc symmetrical battery are the same, wherein the electrolyte is 1M ZnSO4The current density of the battery test is 1mA/cm2The area capacity is 1mAh/cm2And the test results show that the service lives of the silver-zinc alloy coated zinc symmetrical battery, the gold-zinc alloy coated zinc symmetrical battery and the copper-zinc alloy coated zinc symmetrical battery respectively reach 1150 hours, 423 hours and 385 hours as shown in fig. 8. Compared with the pure zinc electrode battery of the comparative example 1, the service life of the pure zinc electrode battery is improved to 12.37 times, 4.55 times and 4.14 times of the service life of the pure zinc symmetrical battery in sequence. This shows that only the silver-zinc alloy coating in the heavy metal zinc alloy coating can improve the service life of the zinc battery most obviously.
Step 4, observing the surface appearance of the zinc electrode with the silver-zinc alloy coating after long-term circulation by using SEM
After 1150 hours of circulation, the surface morphology of the silver-zinc alloy coated zinc electrode is shown on the right of fig. 2, and it can be seen that zinc is densely deposited on the silver-zinc alloy coating without obvious dendrites. Compared with the pure zinc electrode which is cycled under the same conditions in the left figure, the deposition of the zinc is obviously more smooth and ordered, which shows that the silver-zinc alloy coating can realize the compact deposition of the zinc.
Step 5, illustrating the action mechanism of the silver-zinc alloy coating in the zinc ion battery
Fig. 9 is a schematic diagram of deposition of zinc on silver-zinc alloy, and shows that matching effect between crystal faces of zinc (002) and silver-zinc alloy (002) promotes ordered growth (or deposition) of zinc on silver-zinc alloy coating in two directions, one is lamellar growth in vertical direction, and the other is epitaxial growth in horizontal direction. This results in dense zinc deposition, which greatly reduces the generation of zinc dendrites, thereby extending the electrode life.
Example 3
And (3) preparing and characterizing the silver-zinc alloy coating zinc electrode.
Step 3, cleaning the cavity of the plasma sputtering instrument
Closing a cover of the plasma sputtering instrument, opening a vacuum pump, pumping the chamber to high vacuum (the vacuum degree is less than or equal to 30 Pa), introducing high-purity argon (more than or equal to 99.99%) as protective gas, adjusting the gas inlet rate to enable the vacuum degree to be stable at 6 Pa, and performing sputtering after lasting for 5 minutes.
Step 4, argon plasma sputtering
Selecting a silver target as a sputtering target material (purchased from Shenyang Kejing, the purity is more than or equal to 99.99%), setting the sputtering time to be 5 minutes, starting sputtering, adjusting the sputtering current to 17mA, carrying out plasma sputtering on a zinc electrode, waiting for about 3 minutes after the sputtering is finished, starting the sputtering again, and setting the total sputtering time to be 30 minutes. The vacuum pump is closed, the plasma sputtering instrument is turned on, a white coating can be obtained on the surface of the zinc sheet, the surface appearance of the electrode after amplification is shown as the left side of a graph 10 (accelerating voltage EHT =5 kV), the silver-zinc alloy cluster particles are compact blocks, the silver-zinc alloy cluster particles are silver-zinc alloy through an EDS test, and the atomic ratio of zinc to silver is 0.6 (the right side of the graph 10). The average grain diameter is about 441nm and the calculated thickness of the silver-zinc alloy layer is about 441-882 nm (calculated according to the thickness of about 1-2 times the grain diameter) by using grain diameter distribution calculation software. The reason why the atomic ratio of zinc and silver is low is that the sputtering current is large, the vacuum degree is large, and the sputtering time is long, so that compact silver particles quickly appear on the formed silver-zinc alloy coating, and the continuous growth of the zinc-silver alloy coating is prevented, so that a relatively thin silver-zinc alloy layer is formed on the zinc sheet, and a silver particle layer is formed on the silver-zinc alloy layer.
Step 5, testing the performance of the symmetrical battery (or half battery) with the silver-zinc alloy coating zinc electrode
The silver-zinc alloy coated zinc electrode was assembled into a symmetrical cell for testing, the cell assembly conditions were the same as in step 2 of comparative example 1. The test condition was that the current density was 2mA/cm2The area capacity is 1mAh/cm2。
Step 6, the test result is compared with the pure zinc symmetrical battery in the comparative example 1
The results of the tests on symmetrical cells with a zinc electrode coated with a silver-zinc alloy (zinc-silver ratio of about 0.6) are shown in fig. 8, and the life of the cells reaches 932 hours. The pure zinc electrode cell of comparative example 1 had a lifetime of 112 hours under the same conditions. By comparison, the service life of the battery is obviously prolonged, and the service life of the silver-zinc alloy coated zinc electrode is prolonged to 8.32 times of that of a pure zinc symmetrical battery. This is a good indication that coating the zinc electrode with silver-zinc alloy can greatly improve the cycle life of the battery even if the proportion of silver on the surface of the silver-zinc alloy is increased.
Example 4
And (3) preparing and characterizing the silver-zinc alloy coating zinc electrode.
Step 3, cleaning the cavity of the plasma sputtering instrument
Closing a cover of the plasma sputtering instrument, opening a vacuum pump, pumping the chamber to high vacuum (the vacuum degree is less than or equal to 30 Pa), introducing high-purity argon (more than or equal to 99.99%) as protective gas, adjusting the gas inlet rate to enable the vacuum degree to be stable at 20Pa, and performing sputtering after lasting for 5 minutes.
Step 4, argon plasma sputtering
Selecting a silver target as a sputtering target material (purchased from Shenyang Kejing, the purity is more than or equal to 99.99%), setting the sputtering time to be 5 minutes, starting sputtering, adjusting the sputtering current to be 17mA, carrying out plasma sputtering on the zinc electrode, waiting for about 3 minutes after the sputtering is finished, starting the sputtering again, and setting the total sputtering time to be 15 minutes. Turning off the vacuum pump, turning on the plasma sputtering apparatus, obtaining a white coating on the surface of the zinc sheet, wherein the amplified electrode surface morphology is as shown in fig. 11 left (acceleration voltage EHT =5 kV), the silver-zinc alloy cluster particles are compact blocks, the silver-zinc alloy cluster particles are silver-zinc alloy by EDS test and have a zinc-silver atomic ratio of 0.8 (fig. 11 right), and the average particle size is about 380nm, and the calculated thickness value of the silver-zinc alloy layer is about 380-760 nm (calculated according to the thickness being about 1-2 times the particle size).
Example 5
And (3) preparing and characterizing the silver-zinc alloy coating zinc electrode.
Step 3, cleaning the cavity of the plasma sputtering instrument
Closing a cover of the plasma sputtering instrument, opening a vacuum pump, pumping the chamber to high vacuum (the vacuum degree is less than or equal to 30 Pa), introducing high-purity argon (more than or equal to 99.99%) as protective gas, adjusting the gas inlet rate to enable the vacuum degree to be stable at 18Pa, and performing sputtering after lasting for 5 minutes.
Step 4, argon plasma sputtering
Selecting a silver target as a sputtering target (purchased from Shenyang Kejing, the purity is more than or equal to 99.99%), setting the sputtering time to be 5 minutes, starting sputtering, adjusting the sputtering current to be 15mA, carrying out plasma sputtering on a zinc electrode, waiting for about 3 minutes after the sputtering is finished, starting the sputtering again, and setting the total sputtering time to be 10 minutes. Turning off the vacuum pump, turning on the plasma sputtering apparatus, a gray coating can be obtained on the surface of the zinc sheet, the enlarged electrode surface morphology is as shown in fig. 12 left (acceleration voltage EHT =5 kV), the silver-zinc alloy cluster particles are porous, and are silver-zinc alloy through EDS test, and the zinc-silver atomic ratio is 1.7 (fig. 12 right). The average grain diameter is 642nm, and the calculated thickness of the silver-zinc alloy layer is about 642-1284 nm (calculated according to the thickness of about 1-2 times of the grain diameter) by using grain diameter distribution calculation software.
Example 6
And (3) preparing and characterizing the silver-zinc alloy coating zinc electrode.
Step 3, cleaning the cavity of the plasma sputtering instrument
Closing a cover of the plasma sputtering instrument, opening a vacuum pump, pumping the chamber to high vacuum (the vacuum degree is less than or equal to 30 Pa), introducing high-purity argon (more than or equal to 99.99%) as protective gas, adjusting the gas inlet rate to enable the vacuum degree to be stable at 10Pa, and performing sputtering after lasting for 5 minutes.
Step 4, argon plasma sputtering
Selecting a silver target as a sputtering target (purchased from Shenyang Kejing, the purity is more than or equal to 99.99%), setting the sputtering time to be 5 minutes, starting sputtering, adjusting the sputtering current to be 12mA, carrying out plasma sputtering on a zinc electrode, waiting for about 3 minutes after the sputtering is finished, starting the sputtering again, and setting the total sputtering time to be 10 minutes. And (3) turning off the vacuum pump, turning on the plasma sputtering instrument, so as to obtain a gray black coating on the surface of the zinc sheet, wherein the amplified electrode surface morphology is shown on the left of fig. 13 (acceleration voltage EHT =20 kV), the silver-zinc alloy cluster particles are cotton-shaped, and are silver-zinc alloy through EDS test, and the atomic ratio of zinc to silver is 3.9 (on the right of fig. 13). The average grain diameter is 572nm, and the calculated thickness of the silver-zinc alloy layer is about 572-1144 nm (calculated according to the thickness of about 1-2 times of the grain diameter) by using grain diameter distribution calculation software.
Example 7
Zinc ion full battery performance of zinc cathode with silver-zinc alloy coating and vanadium dioxide (B) anode
Step 2, the preparation of the vanadium dioxide (B) positive electrode is the same as that of comparative example 4.
And 3, assembling the silver-zinc alloy coated zinc cathode and the vanadium dioxide (B) anode full cell.
Same as comparative example 4, step 3.
Step 4, silver-zinc alloy coated zinc cathode and vanadium dioxide (B) anode full battery test
The full cell test was performed in an incubator (25 ℃) to eliminate the influence of ambient temperature. The battery test uses a battery test system of Wuhan blue electricity. The current density was 500 mA/g.
Step 5, comparing the performances of the pure zinc cathode and the vanadium dioxide (B) full battery in the comparative example 4
The silver-zinc alloy coated zinc electrode is used as a negative electrode, vanadium dioxide (B) is used as a positive electrode to be assembled into a full battery, the zinc is used as a negative electrode, the performance of the full battery with the vanadium dioxide (B) as the positive electrode is compared and analyzed, and as a result, as shown in fig. 14, compared with the full battery with the pure zinc negative electrode, after about 90 cycles, the battery is suddenly short-circuited and dies, and the capacity is reduced to about 110mAh/g, the initial discharge specific capacity of the zinc negative electrode battery with the silver-zinc alloy coating is 161.1mAh/g, the 65 th cycle reaches the maximum value and is 207.8mAh/g, and then the initial discharge specific capacity is continuously reduced, the capacity of the 90 th cycle is 204.9mAh/g, the capacity of the 172 th cycle reaches 189.2mAh/g, the 500 th cycle is 132.9mAh/g, and the 700 th cycle is 108.5mAh/g, which shows that the silver alloy coating can improve the cycle life of the zinc full battery.
Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. This disclosure is intended to cover any variations, uses, or adaptations of the disclosure following, in general, the principles of the disclosure and including such departures from the present disclosure as come within known or customary practice within the art to which the disclosure pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention, and the scope of the present invention is defined by the appended claims, and all changes that come within the meaning and range of equivalency of the specification are therefore intended to be embraced therein.
Claims (8)
1. A preparation method of a silver-zinc alloy coating taking a zinc sheet as a substrate is characterized by comprising the following steps:
1) polishing, ultrasonically cleaning a zinc sheet, and drying;
2) placing a zinc sheet in a chamber of a plasma sputtering apparatus;
3) opening a vacuum pump to pump the chamber until the vacuum degree is less than or equal to 30Pa, and introducing argon as protective gas to stabilize the vacuum degree at 5-25 Pa;
4) setting sputtering time and sputtering current, carrying out plasma sputtering on the zinc sheet by using a silver target, and obtaining a silver-zinc alloy coating on the surface of the zinc sheet, wherein the sputtering time is 3-40 minutes, and the sputtering current is 5-40 mA.
2. The method for preparing the silver-zinc alloy coating taking the zinc sheet as the substrate according to claim 1, wherein the grinding is carried out by adopting any number of sand paper, file, blade and agate, the ultrasonic cleaning is ultrasonic cleaning by using ethanol and/or water, the drying is carried out by drying the zinc sheet in a drying oven or a vacuum oven, and the drying temperature is 50-100 ℃.
3. The method for preparing a zinc sheet-based silver-zinc alloy coating according to claim 1, wherein the argon gas is a high-purity argon gas with a purity of 99.99% or more, and the silver target is a high-purity silver target with a purity of 99.99% or more.
4. The method for preparing the silver-zinc alloy coating taking the zinc sheet as the substrate according to claim 1, wherein during sputtering, the vacuum degree is stabilized at 5Pa to 20Pa, the sputtering current is 12mA to 17mA, and the sputtering time is 10 minutes to 30 minutes.
5. The silver-zinc alloy coating with zinc plate as the substrate prepared by the preparation method of any one of claims 1 to 4, wherein the thickness of the silver-zinc alloy coating is 400 to 3000nm, the average diameter of silver-zinc cluster particles in the silver-zinc alloy coating is 200 to 1000nm, and the atomic ratio of zinc and silver of the silver-zinc alloy coating is 0.2 to 5.0.
6. The zinc sheet-based silver-zinc alloy coating according to claim 5, wherein the atomic ratio of zinc to silver in the silver-zinc alloy coating is 0.6 to 3.9.
7. Use of a zinc sheet-based silver-zinc alloy coating as defined in claim 5 or 6 as a negative electrode in a zinc cell.
8. The use of claim 7, wherein a zinc battery is assembled with a vanadium dioxide (B) electrode as the positive electrode, glass fibers as the separator, and 1mol/L zinc sulfate solution as the electrolyte.
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| CN115233157A (en) * | 2022-06-14 | 2022-10-25 | 沈阳大学 | Method for preparing copper film on surface of zinc and zinc alloy through magnetron sputtering |
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