CN114824286A - Al-V alloy film substrate material for sodium metal battery and preparation method and application thereof - Google Patents
Al-V alloy film substrate material for sodium metal battery and preparation method and application thereof Download PDFInfo
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- 229910000756 V alloy Inorganic materials 0.000 title claims abstract description 77
- 239000000758 substrate Substances 0.000 title claims abstract description 62
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011888 foil Substances 0.000 claims abstract description 49
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 43
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 28
- 238000004544 sputter deposition Methods 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 238000010849 ion bombardment Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000013077 target material Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 abstract description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 18
- 229910052708 sodium Inorganic materials 0.000 abstract description 18
- 210000001787 dendrite Anatomy 0.000 abstract description 10
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000005684 electric field Effects 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 210000004027 cell Anatomy 0.000 description 16
- HIMLGVIQSDVUJQ-UHFFFAOYSA-N aluminum vanadium Chemical compound [Al].[V] HIMLGVIQSDVUJQ-UHFFFAOYSA-N 0.000 description 14
- 238000004070 electrodeposition Methods 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- VVIHROHFFISGNS-UHFFFAOYSA-K [Al+3].[Cl-].[Cl-].[Cl-].NC(N)=O Chemical compound [Al+3].[Cl-].[Cl-].[Cl-].NC(N)=O VVIHROHFFISGNS-UHFFFAOYSA-K 0.000 description 2
- 239000000956 alloy Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- -1 vanadium pentoxide-aluminum trichloride-urea Chemical compound 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
- H01M4/0426—Sputtering
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses an Al-V alloy film substrate material for a sodium metal battery and a preparation method and application thereof, belonging to the technical field of battery materials. When the Al-V alloy film substrate material of the sodium metal battery is prepared, firstly, the aluminum foil is sequentially cleaned by deionized water and ethanol in an ultrasonic mode, then, the cleaned aluminum foil is placed in magnetron sputtering coating equipment for magnetron sputtering, finally, heat treatment is carried out under certain conditions, and the Al-V alloy film substrate material of the sodium metal battery is obtained after cooling. The Al-V alloy film substrate material prepared by the preparation method not only increases the specific surface area of the material well, but also has a micro-morphology (rod-like) which is beneficial to forming a uniform interface electric field, effectively increases active sites and nucleation sites deposited by sodium ions, induces sodium metal to be uniformly deposited, effectively inhibits the formation of sodium dendrites, and prolongs the service life of a battery.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to an Al-V alloy film substrate material for a sodium metal battery, and a preparation method and application thereof.
Background
With the development of social economy, the demand of human beings on energy is increasing day by day, and the traditional fossil energy is gradually exhausted and a series of environmental problems caused by the fossil energy cannot meet the demand of the development of the human society. Therefore, the development of new renewable energy sources such as solar energy, wind energy, tidal energy, etc. is not slow. However, secondary energy has intermittent and fluctuating properties and is not easy to store, and a new efficient and stable energy storage system needs to be developed. Lithium ion batteries are widely used in the fields of mobile communication, electric vehicles, energy storage and the like due to the advantages of large energy density, long cycle life, wide working temperature range and the like. However, lithium cannot be applied in large scale due to the increasingly scarce lithium resource, uneven distribution and high price, so that a novel energy storage device needs to be developed.
The metal sodium and the metal lithium are located in the same main group in the periodic table of elements, the chemical properties are basically the same, the sodium reserves are rich, the price is low, and the lithium ion battery is replaced to become the best candidate of a new generation of energy storage batteries. The negative electrode material is one of the important components of the sodium ion battery. At present, the anode materials commonly used in the market mainly include carbon-based materials, transition metal oxides, sulfides, and various alloy compounds. Based on the sodium storage mechanism of these negative electrode materials, these negative electrode materials can be classified into three main categories: intercalation-type negative electrode materials, conversion-type and alloy-type negative electrode materials. The theoretical specific capacity of the traditional inserted negative electrode material is lower, and the requirement of the next generation energy storage system on the energy density cannot be met. Although the energy density of the battery can be obviously improved by developing conversion materials and alloy materials, the materials have huge volume change in the sodium storage process, so that electrode materials are easy to pulverize, and the mechanical properties and the electrochemical properties of the materials are seriously influenced. Sodium metal negative electrode is very high in theoretical specific capacity (1166mA h g) -1 ) And a lower electrode potential (-2.714vs. standard hydrogen electrode), which is considered to be one of the most promising sodium ion battery cathodes.
However, the application of sodium metal anodes still faces challenges such as sodium dendrite growth, sodium metal and electrolysisSide reactions between liquids, large volume expansion during charging and discharging, and the like. Among them, the growth of the sodium dendrites can not only generate "dead" sodium and accelerate the side reaction between the sodium metal and the electrolyte, resulting in rapid capacity attenuation, but also may puncture the separator, resulting in serious safety problems such as battery short circuit, even explosion, etc. And Na on the surface of the electrode + Will directly lead to the formation of sodium dendrites, and therefore, it is necessary to study the promotion of Na + And (3) a method for flux uniformity. One of the most common methods is to increase the surface area of the electrode to reduce the local current density, which can be achieved by constructing the current collector in a different configuration. The aluminum foil can be used as a current collector of a negative electrode in a sodium metal battery, and sodium dendrites are easily formed on the aluminum foil due to the uneven distribution of local current. The aluminum collector is modified by a method of forming a layer of aluminum-vanadium alloy on the surface of an aluminum foil, so that the aim of inhibiting the growth of sodium dendrites is fulfilled. The growth restriction effect of the aluminum-vanadium alloy and the solute vanadium is synergistic, so that the grain refinement is realized, the specific surface area of the material is increased, the active sites and nucleation sites of sodium ion deposition are effectively increased, and the material is a sodium metal battery substrate material with great development potential. Therefore, how to prepare the aluminum-vanadium alloy capable of inducing the uniform deposition of the sodium metal has important significance for promoting the application of the aluminum-vanadium alloy in the sodium metal battery.
Through search, no relevant patent about the application of the aluminum-vanadium alloy in the battery exists at present. The commonly used preparation methods of the aluminum vanadium alloy mainly comprise an aluminothermic reduction method and a powder metallurgy method. Such as: the Chinese patent application No. CN201210357559.0 discloses a method for smelting an aluminum-vanadium alloy by an electro-aluminothermic process, and the preparation method of the aluminum-vanadium alloy comprises the steps of uniformly mixing vanadium oxide, a reducing agent aluminum and a slagging constituent, adding the mixture into an electric arc furnace in stages, carrying out aluminothermic reduction reaction in sequence for smelting, and carrying out slag removal, finishing and crushing after the smelting is finished to obtain the aluminum-vanadium alloy. For another example: the Chinese patent application No. 202110808528.1 discloses a method for preparing an aluminum-vanadium alloy by low-temperature electrodeposition, which comprises the following steps: mixing aluminum trichloride and urea, and heating to obtain a Lewis acidic aluminum trichloride-urea ionic liquid; mixing vanadium pentoxide with the aluminum trichloride-urea ionic liquid, and obtaining the vanadium pentoxide-aluminum trichloride-urea ionic liquid after the vanadium pentoxide is dissolved: taking vanadium pentoxide-aluminum trichloride-urea ionic liquid as electrolyte, carrying out electrodeposition under the conditions of voltage of 3.2-3.4V and temperature of 60-90 ℃ until the reaction is finished, and collecting a cathode product to obtain the aluminum-vanadium alloy. The above applications are some methods of preparing Al-V alloys, but none have been applied as a sodium metal battery thin film base material.
Disclosure of Invention
1. Problems to be solved
The invention aims to solve the problem of growth of sodium dendrites, provides an Al-V alloy film substrate material for a sodium metal battery and a preparation method thereof, and realizes uniform deposition and stripping of sodium metal. The aluminum-vanadium alloy is used as a base material of the sodium metal battery film, so that the specific surface area of the material is better increased, the micro-morphology (rod shape) of the aluminum-vanadium alloy is favorable for forming a uniform interface electric field, active sites and nucleation sites for sodium ion deposition are effectively increased, sodium metal is induced to be uniformly deposited, the formation of sodium dendrites is effectively inhibited, and the service life of the battery is prolonged.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a preparation method of an Al-V alloy film substrate material for a sodium metal battery, which comprises the following steps:
(1) fixing a V target at a position corresponding to a target material by adopting a magnetron sputtering method, then placing a pretreated aluminum current collector at a position corresponding to a sample, then pumping the cavity to high vacuum and applying a sputtering power supply, carrying out plasma cleaning on a substrate, and finally carrying out V deposition to obtain a V film material;
(2) and (3) placing the sample (V deposited on the surface of the aluminum foil) subjected to magnetron sputtering in a tube furnace, carrying out heat treatment under certain conditions, and cooling to obtain the Al-V alloy film.
Further, in the step (1), the aluminum current collector has a thickness of 20 μm.
Further, in the step (1), the pretreatment process of the aluminum current collector is as follows: and sequentially placing the current collector in deionized water and ethanol, ultrasonically cleaning for 10min respectively, and then carrying out vacuum drying treatment.
Furthermore, in the step (1), the sputtering power supply is a radio frequency power supply, and the power supply power is 1500W.
Further, in the step (1), the vacuum degree of the high vacuum environment is 1 × 10 -3 ～3×10 -3 Pa。
Further, in the step (1), the V ion bombardment conditions are: the V target power is 120-200W, the working air pressure is 5-10 Pa, and the sputtering time is 5-10 min.
Further, in the step (2), the heat treatment conditions are as follows: in the argon atmosphere, the heating rate is 2-10 ℃/min, the reaction temperature is 400-550 ℃, and the heat preservation time is 2-4 h.
The Al-V alloy film substrate material for the sodium metal battery is prepared by the method, the microscopic appearance of the Al-V alloy film is rod-shaped, and the length of the Al-V alloy film is 100-200 nm.
The invention relates to an application field of an Al-V alloy film substrate material, in particular to a sodium metal battery.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the Al-V alloy film substrate material for the sodium metal battery firstly puts forward that a V film is deposited on the surface of an aluminum current collector, and then the Al-V alloy film substrate with a rod-shaped microscopic appearance is obtained through heat treatment.
(2) The Al-V alloy film substrate material for the sodium metal battery has excellent conductivity and greatly improved stability.
(3) According to the preparation method of the Al-V alloy film substrate material for the sodium metal battery, disclosed by the invention, the specific preparation process and parameters are optimized, and parameters such as sputtering power, pressure intensity, time, annealing temperature and the like are strictly controlled, so that the uniformity of the aluminum-vanadium alloy can be ensured, and the electrochemical performance of the Al-V alloy film for depositing metal sodium is further improved.
(4) According to the Al-V alloy film substrate material for the sodium metal battery, disclosed by the invention, the microscopic morphology of the material is rod-shaped, so that the Al-V alloy substrate is ensured to have a large specific surface area, the infiltration of electrolyte is facilitated, the contact area of the electrolyte and an electrode material is greatly increased, and further more sodium deposition active sites are provided. In addition, the microscopic morphology (rod shape) of the lithium ion battery can improve the distribution of an interface electric field, promote the redistribution of charges, induce the uniform deposition of sodium metal, effectively inhibit the growth of sodium dendrites and prolong the service life of the battery. The preparation method provided by the invention is simple to operate, the raw materials are cheap, and the Al-V alloy film substrate material prepared by the method can be better applied to a sodium metal battery.
Drawings
FIG. 1 is a scanning electron micrograph of a product obtained in example 1 of the present invention;
FIG. 2 is an X-ray diffraction diagram of the product obtained in example 1 of the present invention;
FIG. 3 is a graph of the coulombic efficiency of the product obtained in example 1 of the present invention;
FIG. 4 is a time-voltage curve of constant current charging and discharging of the product obtained in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be further described with reference to the embodiments. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
The preparation method of the Al-V alloy film substrate material for the sodium metal battery comprises the following steps:
(1) selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into 5 multiplied by 4cm foils, and putting the foils into a cavity as sputtering substrates after ultrasonic cleaning by deionized water and ethanol;
(2) the vacuum chamber is vacuumized to reach a vacuum degree of 1 × 10 -3 Pa; then argon is introduced into the chamber, the pressure is adjusted to 100Pa, and therefore the surface of the deposition substrate is cleaned for 10 min.
(3) And starting a cathode V target, setting the power of the V target to be 200W, setting the working air pressure to be 10Pa, setting the sputtering time to be 10min and setting the rotating speed of the substrate to be 5 r/min.
(4) And placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the conditions of heating rate of 5 ℃/min and reaction temperature of 550 ℃ for 2 hours under the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate is cut into a wafer with the diameter of 10mm and used for assembling a button cell, and sodium metal is used as a counter electrode.
(6) And assembling the Al-V alloy membrane electrode after electrochemical deposition into a symmetrical cell.
FIG. 1 is a scanning electron microscope image of the Al-V alloy product obtained in this embodiment, from which it can be seen that the product obtained in this embodiment has a rod-like microstructure and a length of 100 to 200 nm. FIG. 2 is an X-ray diffraction chart of the product obtained in this example, wherein the diffraction peak indexes in the chart are Al and Al 10 V、Al 23 V 4 、V 5 Al 8 . FIG. 3 shows the current density of the product obtained in this example at 1mA cm -2 And (3) a lower coulombic efficiency graph showing stable coulombic efficiency. FIG. 4 shows a symmetrical cell assembled with an Al-V alloy membrane electrode with sodium electrochemically deposited on the product obtained in this example at a current density of 1mA cm -2 The surface capacity is 3mA h cm -2 The time-voltage curve under the condition shows lower deposition overpotential, effectively inhibits the growth of sodium dendrite and improves the stability of deposition/stripping circulation.
Example 2
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into 5 multiplied by 4cm foils, and putting the foils into a cavity as sputtering substrates after ultrasonic cleaning by deionized water and ethanol;
(2) the vacuum chamber is vacuumized to reach a vacuum degree of 1 × 10 -3 Pa; then argon is introduced into the chamber, the pressure is adjusted to 100Pa, and therefore the surface of the deposition substrate is cleaned for 10 min.
(3) And starting a cathode V target, setting the power of the V target to be 120W, setting the working air pressure to be 5Pa, setting the sputtering time to be 10min, and setting the rotating speed of the substrate to be 5 r/min.
(4) And placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the conditions of heating rate of 5 ℃/min and reaction temperature of 550 ℃ for 2 hours under the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate is cut into a wafer with the diameter of 10mm and used for assembling a button cell, and sodium metal is used as a counter electrode.
(6) And assembling the Al-V alloy membrane electrode after electrochemical deposition into a symmetrical cell.
Example 3
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into 5 multiplied by 4cm foils, and putting the foils into a cavity as sputtering substrates after the foils are ultrasonically cleaned by ethanol and deionized water;
(2) the vacuum chamber is vacuumized to reach 2X 10 -3 Pa; then argon is introduced into the chamber, the pressure is adjusted to 100Pa, and therefore the surface of the deposition substrate is cleaned for 10 min.
(3) And starting a cathode V target, setting the power of the V target to be 200W, the working air pressure to be 8Pa, the sputtering time to be 8min and the rotating speed of the substrate to be 5 r/min.
(4) And placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the conditions of heating rate of 10 ℃/min and reaction temperature of 400 ℃ for 4 hours under the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate is cut into a wafer with the diameter of 10mm and used for assembling a button cell, and sodium metal is used as a counter electrode.
(6) And assembling the Al-V alloy membrane electrode after electrochemical deposition into a symmetrical cell.
Example 4
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into 5 multiplied by 4cm foils, and putting the foils into a cavity as sputtering substrates after ultrasonic cleaning by deionized water and ethanol;
(2) the vacuum chamber is vacuumized to reach 2X 10 -3 Pa; then argon is introduced into the chamber, the pressure is adjusted to 100Pa, and therefore the surface of the deposition substrate is cleaned for 10 min.
(3) And starting a cathode V target, setting the power of the V target to be 200W, the working air pressure to be 8Pa, the sputtering time to be 10min and the rotating speed of the substrate to be 5 r/min.
(4) And placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the conditions of heating rate of 10 ℃/min and reaction temperature of 400 ℃ for 4 hours under the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate was cut into a wafer having a diameter of 10mm for assembling a button cell, and sodium metal was used as a counter electrode.
(6) And assembling the Al-V alloy membrane electrode after electrochemical deposition into a symmetrical cell.
Example 5
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into 5 multiplied by 4cm foils, and putting the foils into a cavity as sputtering substrates after ultrasonic cleaning by deionized water and ethanol;
(2) the vacuum chamber is vacuumized to reach a vacuum degree of 3 multiplied by 10 -3 Pa; then argon is introduced into the chamber, the pressure is adjusted to 100Pa, and therefore the surface of the deposition substrate is cleaned for 10 min.
(3) And starting a cathode V target, setting the power of the V target to be 120W, the working air pressure to be 5Pa, the sputtering time to be 10min and the rotating speed of the substrate to be 5 r/min.
(4) And placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the conditions of heating rate of 2 ℃/min and reaction temperature of 400 ℃ for 4 hours under the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate is cut into a wafer with the diameter of 10mm and used for assembling a button cell, and sodium metal is used as a counter electrode.
(6) And assembling the Al-V alloy membrane electrode after electrochemical deposition into a symmetrical cell.
Example 6
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into 5 multiplied by 4cm foils, and putting the foils into a cavity as sputtering substrates after the foils are ultrasonically cleaned by ethanol and deionized water;
(2) the vacuum chamber is vacuumized to reach a vacuum degree of 3 multiplied by 10 -3 Pa; then argon is introduced into the chamber, the air pressure is adjusted to 100Pa, and thenAnd cleaning the surface of the deposition substrate for 10 min.
(3) And starting a cathode V target, setting the power of the V target to be 200W, the working air pressure to be 5Pa, the sputtering time to be 10min and the rotating speed of the substrate to be 5 r/min.
(4) And placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the conditions of heating rate of 2 ℃/min and reaction temperature of 550 ℃ for 2h under the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate is cut into a wafer with the diameter of 10mm and used for assembling a button cell, and sodium metal is used as a counter electrode.
(6) And assembling the Al-V alloy membrane electrode after electrochemical deposition into a symmetrical cell.
Example 7
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into 5 multiplied by 4cm foils, and putting the foils into a cavity as sputtering substrates after ultrasonic cleaning by deionized water and ethanol;
(2) the vacuum chamber is vacuumized to reach a vacuum degree of 1 × 10 -3 Pa; then argon is introduced into the chamber, the pressure is adjusted to 100Pa, and therefore the surface of the deposition substrate is cleaned for 10 min.
(3) And starting a cathode V target, setting the power of the V target to be 120W, setting the working air pressure to be 10Pa, setting the sputtering time to be 10min and setting the rotating speed of the substrate to be 5 r/min.
(4) And placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the conditions of heating rate of 5 ℃/min and reaction temperature of 550 ℃ for 2 hours under the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate is cut into a wafer with the diameter of 10mm and used for assembling a button cell, and sodium metal is used as a counter electrode.
(6) And assembling the Al-V alloy thin film battery subjected to electrochemical deposition into a symmetrical battery.
Example 8
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into a foil piece with the thickness of 5 multiplied by 4cm, and putting the foil piece into a cavity as a sputtering base material after ultrasonic cleaning by deionized water and ethanol;
(2) will be provided withThe vacuum chamber is vacuumized to reach 1 × 10 -3 Pa; then argon is introduced into the chamber, the pressure is adjusted to 100Pa, and therefore the surface of the deposition substrate is cleaned for 10 min.
(3) And starting a cathode V target, setting the power of the V target to be 200W, the working air pressure to be 5Pa, the sputtering time to be 5min and the rotating speed of the substrate to be 5 r/min.
(4) And placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the conditions of heating rate of 5 ℃/min and reaction temperature of 550 ℃ for 2 hours under the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate was cut into a wafer having a diameter of 10mm for assembling a button cell, and sodium metal was used as a counter electrode.
(6) And assembling the Al-V alloy membrane electrode after electrochemical deposition into a symmetrical cell.
The above description is only a few specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
Claims (9)
1. A preparation method of an Al-V alloy film substrate material for a sodium metal battery is characterized by comprising the following steps:
(1) fixing a V target at a position corresponding to a target material by adopting a magnetron sputtering method, then placing a pretreated aluminum current collector at a position corresponding to a sample, then pumping the cavity to high vacuum and applying a sputtering power supply, carrying out plasma cleaning on a substrate, and finally carrying out V deposition to obtain a V film material;
(2) and (3) placing the sample (V deposited on the surface of the aluminum foil) subjected to magnetron sputtering in a tube furnace, carrying out heat treatment under certain conditions, and cooling to obtain the Al-V alloy film.
2. The method for preparing the Al-V alloy thin film substrate material for the sodium metal battery according to claim 1, wherein the method comprises the following steps: in the step (1), the thickness of the aluminum current collector is 20 μm.
3. The method for preparing the Al-V alloy thin film substrate material for the sodium metal battery according to claim 1, wherein the method comprises the following steps: in the step (1), the pretreatment process of the aluminum current collector comprises the following steps: and sequentially placing the current collector in deionized water and ethanol, ultrasonically cleaning for 10min respectively, and then carrying out vacuum drying treatment.
4. The method for preparing the Al-V alloy thin film substrate material for the sodium metal battery according to claim 1, wherein the method comprises the following steps: in the step (1), the sputtering power supply is a radio frequency power supply, and the power supply power is 1500W.
5. The method for preparing the Al-V alloy thin film substrate material for the sodium metal battery according to claim 1, wherein the method comprises the following steps: in the step (1), the vacuum degree of the high vacuum environment is 1 multiplied by 10 -3 ～3×10 -3 Pa。
6. The method for preparing the Al-V alloy thin film substrate material for the sodium metal battery according to claim 1, wherein the method comprises the following steps: in the step (1), the V ion bombardment condition is as follows: v target power is 120-200W, working air pressure is 5-10 Pa, and sputtering time is 5-10 min.
7. The method for preparing the Al-V alloy thin film substrate material for the sodium metal battery according to claim 1, wherein the method comprises the following steps: in the step (2), the heat treatment conditions are as follows: in the argon atmosphere, the heating rate is 2-10 ℃/min, the reaction temperature is 400-550 ℃, and the heat preservation time is 2-4 h.
8. An Al-V alloy thin film base material for a sodium metal battery, prepared by the preparation method of any one of claims 1 to 7, characterized in that: the microscopic morphology of the Al-V alloy film is rod-shaped, and the length of the Al-V alloy film is 100-200 nm.
9. The application of the Al-V alloy film substrate material for the sodium metal battery is characterized in that: the Al-V alloy thin film substrate material according to claim 8, which is used in sodium metal batteries.
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