CN114824286B - 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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- CN114824286B CN114824286B CN202210496870.7A CN202210496870A CN114824286B CN 114824286 B CN114824286 B CN 114824286B CN 202210496870 A CN202210496870 A CN 202210496870A CN 114824286 B CN114824286 B CN 114824286B
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- 229910000756 V alloy Inorganic materials 0.000 title claims abstract description 75
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000000758 substrate Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 57
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000151 deposition Methods 0.000 claims abstract description 19
- 230000008021 deposition Effects 0.000 claims abstract description 19
- 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
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 27
- 238000004544 sputter deposition Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 238000010849 ion bombardment 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
- 239000011888 foil Substances 0.000 abstract description 53
- 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
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 5
- 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
- 230000002349 favourable 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 35
- 239000002184 metal Substances 0.000 description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- HIMLGVIQSDVUJQ-UHFFFAOYSA-N aluminum vanadium Chemical compound [Al].[V] HIMLGVIQSDVUJQ-UHFFFAOYSA-N 0.000 description 13
- 238000004070 electrodeposition Methods 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 239000010405 anode material Substances 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
- 230000001965 increasing effect Effects 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 239000000956 alloy Chemical class 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 vanadium pentoxide-aluminum trichloride-urea Chemical compound 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 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
- 229910045601 alloy Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 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
- 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
- 230000009286 beneficial effect Effects 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
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 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
- 230000004907 flux Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000004663 powder metallurgy Methods 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
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000009466 transformation Effects 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
Classifications
-
- 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
Abstract
The invention discloses an Al-V alloy film base material for a sodium metal battery, and a preparation method and application thereof, and belongs to the technical field of battery materials. When the Al-V alloy film base material of the sodium metal battery is prepared, firstly, the aluminum foil is sequentially ultrasonically cleaned by deionized water and ethanol, then, the cleaned aluminum foil is placed in magnetron sputtering coating equipment for magnetron sputtering, finally, heat treatment is carried out under a certain condition, and the Al-V alloy film base material of the sodium metal battery is obtained after cooling. The Al-V alloy film substrate material obtained by the preparation method not only increases the specific surface area of the material well, but also has a microcosmic appearance (rod shape) which is favorable for forming a uniform interface electric field, effectively increases active sites and nucleation sites for sodium ion deposition, induces sodium metal to be deposited uniformly, effectively inhibits the formation of sodium dendrites, and prolongs the service life of the battery.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to an Al-V alloy film base 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 for energy is growing, and the traditional fossil energy is gradually exhausted and a series of environmental problems brought by the fossil energy are not satisfied. Therefore, the development of new renewable energy sources such as solar energy, wind energy, tidal energy, etc. is not satisfactory. However, secondary energy has intermittent and fluctuating properties, is not easy to store, and needs to develop a new, efficient and stable energy storage system. The lithium ion battery is widely applied to the fields of mobile communication, electric automobiles, energy storage and the like due to the advantages of high energy density, long cycle life, wide working temperature range and the like. However, lithium resources are increasingly scarce, unevenly distributed and expensive, which makes it impossible to apply them on a large scale, and therefore, development of novel energy storage devices is required.
The metal sodium and the metal lithium are in the same main group in the periodic table of elements, have basically the same chemical property, are rich in sodium reserves and low in price, and are the best candidates for replacing lithium ion batteries to become the next generation energy storage batteries. The negative electrode material is one of the important components of sodium ion batteries. Currently, the anode materials commonly used in the market mainly comprise carbon-based materials, transition metal oxides, sulfides and various alloy compounds. Based on the sodium storage mechanism of these anode materials, these anode materials can be divided into three major categories: intercalation type negative electrode material, transformation type negative electrode material and alloy type negative electrode material. The theoretical specific capacity of the traditional intercalation anode material is lower, and the energy density requirement of the next generation energy storage system cannot be met. While the energy density of the battery can be obviously improved by developing the conversion material and the alloy material, the material can generate huge volume change in the sodium storage process, so that the electrode material is easy to pulverize, and the mechanical property and the electrochemical property of the material are seriously influenced. Sodium metal negative electrode due to its extremely high theoretical specific capacity (1166 mA h g) -1 ) And a lower electrode potential (-2.714 vs. standard hydrogen electrode) are considered to be one of the most promising cathodes for sodium ion batteries.
However, the use of sodium metal anodes still faces challenges such as the growth of sodium dendrites, side reactions between sodium metal and electrolyte, large volume expansion during charge and discharge, and the like. The growth of sodium dendrites not only can produce "dead" sodium and accelerate side reactions between sodium metal and electrolyte, resulting in rapid decay of capacity, but also can puncture the separator, resulting in serious safety problems such as short circuit, even explosion, of the battery. And Na on the electrode surface + The non-uniform distribution of (a) will directly lead to the formation of sodium dendrites, and thus the promotion of Na needs to be studied + 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 current collectors of different structures. 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 uneven distribution of local current. The patent is to use aluminum foilThe aluminum current collector is modified by a method of forming a layer of aluminum-vanadium alloy on the surface, so that the purpose of inhibiting the growth of sodium dendrite is achieved. The growth limiting effect of the aluminum-vanadium alloy and solute vanadium is synergistic, so that grain refinement is realized, the specific surface area of the material is increased, active sites and nucleation sites for 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 uniform deposition of sodium metal has important significance for promoting the application of the aluminum-vanadium alloy in sodium metal batteries.
Related patents on the application of aluminum-vanadium alloys in batteries have not been searched at present. The preparation methods of the common aluminum-vanadium alloy mainly comprise an aluminothermic reduction method and a powder metallurgy method. Such as: the application with the Chinese patent application number of CN201210357559.0 discloses a method for smelting 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, aluminum serving as a reducing agent and a slag forming agent, adding the mixture into an electric arc furnace in stages, sequentially carrying out aluminothermic reduction reaction for smelting, and removing slag and finishing and crushing after smelting is finished to obtain the aluminum-vanadium alloy. Another example is: the application of Chinese patent application No. 202110808528.1 discloses a method for preparing aluminum-vanadium alloy by low-temperature electrodeposition, which comprises the following steps: mixing aluminum trichloride with urea, and heating to obtain aluminum trichloride-urea ionic liquid with Lewis acidity; mixing vanadium pentoxide with aluminum trichloride-urea ionic liquid, and obtaining the vanadium pentoxide-aluminum trichloride-urea ionic liquid after the vanadium pentoxide is dissolved: and taking vanadium pentoxide-aluminum trichloride-urea ionic liquid as electrolyte, electrodepositing at the voltage of 3.2-3.4V and the 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 are applied as a sodium metal battery film base material.
Disclosure of Invention
1. Problems to be solved
The invention aims to solve the problem of growth of sodium dendrites, and provides an Al-V alloy film substrate material for sodium metal batteries and a preparation method thereof, which realize uniform deposition and stripping of sodium metal. As the film base material of the sodium metal battery, the aluminum-vanadium alloy not only increases the specific surface area of the material well, but also has microscopic morphology (rod shape) which is favorable for forming a uniform interface electric field, thereby effectively increasing active sites and nucleation sites for sodium ion deposition, inducing sodium metal to be deposited uniformly, effectively inhibiting the formation of sodium dendrite and prolonging the service life of the battery.
2. Technical proposal
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 base 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, placing a pretreated aluminum current collector at a position corresponding to a sample, pumping the cavity to high vacuum, applying a sputtering power supply, cleaning a substrate by plasma, and finally performing V deposition to obtain a V film material;
(2) And (3) placing a sample (V is deposited on the surface of an aluminum foil) subjected to magnetron sputtering in a tubular furnace, performing heat treatment under certain conditions, and cooling to obtain the Al-V alloy film.
Further, in the step (1), the thickness of the aluminum current collector is 20 μm.
Further, in the step (1), the pretreatment process of the aluminum current collector is as follows: and sequentially placing the current collectors in deionized water and ethanol, ultrasonically cleaning for 10min respectively, and then carrying out vacuum drying treatment.
Further, 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 power of the V target 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: argon atmosphere, heating speed of 2-10 ℃/min, reaction temperature of 400-550 ℃ and heat preservation time of 2-4 h.
The Al-V alloy film base material for the sodium metal battery is prepared by the method, and the microscopic morphology of the Al-V alloy film is in a rod shape, and the length of the Al-V alloy film is 100-200nm.
The application field of the Al-V alloy film substrate material is a sodium metal battery.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the Al-V alloy film substrate material for the sodium metal battery, a V film is deposited on the surface of an aluminum current collector for the first time, and then the Al-V alloy film substrate with a bar-shaped microstructure is obtained through heat treatment.
(2) The Al-V alloy film base 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 base material for the sodium metal battery, the specific preparation process and parameters are optimally designed, and the parameters such as sputtering power, pressure intensity, time and annealing temperature are strictly controlled, so that the uniformity of the aluminum-vanadium alloy can be ensured, and the electrochemical performance of the deposited metal sodium of the Al-V alloy film is further improved.
(4) According to the Al-V alloy film substrate material for the sodium metal battery, the microcosmic appearance of the material is in a rod shape, so that the Al-V alloy substrate is ensured to have a large specific surface area, electrolyte infiltration is facilitated, the contact area of the electrolyte and an electrode material is greatly increased, and more sodium deposition active sites are further provided. In addition, the microcosmic appearance (rod shape) can improve the interfacial electric field distribution, promote charge redistribution, induce uniform deposition of sodium metal, effectively inhibit growth of sodium dendrite and prolong the service life of the battery. The preparation method disclosed by the invention is simple to operate, the raw materials are cheap, and the prepared Al-V alloy film substrate material can be well applied to sodium metal batteries.
Drawings
FIG. 1 is a scanning electron microscope image of the product obtained in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of the product obtained in example 1 of the present invention;
FIG. 3 is a graph showing the coulombic efficiency of the product of example 1 of the present invention;
FIG. 4 is a time-voltage plot of constant current charge and discharge of the product obtained in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described by combining the embodiments. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
The preparation method of the Al-V alloy film base 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 a foil with the thickness of 5 multiplied by 4cm, ultrasonically cleaning the metal aluminum foil with deionized water and ethanol, and putting the metal aluminum foil serving as a sputtering substrate into a chamber;
(2) Vacuum is pumped in the vacuum chamber, and the vacuum degree reaches 1 multiplied by 10 -3 Pa; then argon is introduced into the chamber, and the air pressure is regulated to 100Pa, so that the surface of the deposition substrate is cleaned for 10min.
(3) Starting a cathode Vtarget, setting the power of the Vtarget 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 5r/min.
(4) And (3) placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the condition that the temperature rising rate is 5 ℃/min and the reaction temperature is 550 ℃ and the heat preservation is carried out for 2 hours in the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate was cut into a wafer with a diameter of 10mm, which was used to assemble a button cell with sodium metal as a counter electrode.
(6) And assembling the Al-V alloy film electrode after electrochemical deposition into a symmetrical battery.
FIG. 1 is a scanning electron microscope image of the Al-V alloy product obtained in this example, from which it can be seen that the product obtained in this exampleThe microstructure of the material is in a rod shape, and the length of the material is 100-200nm. FIG. 2 is an X-ray diffraction chart of the product obtained in this example, wherein the diffraction peak index in the chart is Al, al 10 V、Al 23 V 4 、V 5 Al 8 . FIG. 3 shows the product obtained in this example at a current density of 1mA cm -2 The coulombic efficiency plot below shows stable coulombic efficiency. FIG. 4 shows an Al-V alloy thin film electrode assembled symmetrical cell after electrochemical deposition of sodium in 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 graph under the condition shows lower deposition overpotential, effectively inhibits the growth of sodium dendrite and improves the stability of deposition/stripping cycle.
Example 2
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into a foil with the thickness of 5 multiplied by 4cm, ultrasonically cleaning the metal aluminum foil with deionized water and ethanol, and putting the metal aluminum foil serving as a sputtering substrate into a chamber;
(2) Vacuum is pumped in the vacuum chamber, and the vacuum degree reaches 1 multiplied by 10 -3 Pa; then argon is introduced into the chamber, and the air pressure is regulated to 100Pa, so that the surface of the deposition substrate is cleaned for 10min.
(3) Starting a cathode Vtarget, setting the power of the Vtarget to 120W, the working air pressure to 5Pa, the sputtering time to 10min, and the substrate rotating speed to 5r/min.
(4) And (3) placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the condition that the temperature rising rate is 5 ℃/min and the reaction temperature is 550 ℃ and the heat preservation is carried out for 2 hours in the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate was cut into a wafer with a diameter of 10mm, which was used to assemble a button cell with sodium metal as a counter electrode.
(6) And assembling the Al-V alloy film electrode after electrochemical deposition into a symmetrical battery.
Example 3
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into a foil with the thickness of 5 multiplied by 4cm, ultrasonically cleaning the metal aluminum foil with ethanol and deionized water, and putting the metal aluminum foil serving as a sputtering substrate into a chamber;
(2) The vacuum chamber is evacuated to a vacuum level,vacuum degree reaches 2X 10 -3 Pa; then argon is introduced into the chamber, and the air pressure is regulated to 100Pa, so that the surface of the deposition substrate is cleaned for 10min.
(3) Starting a cathode Vtarget, setting the power of the Vtarget to be 200W, setting the working air pressure to be 8Pa, setting the sputtering time to be 8min, and setting the rotating speed of the substrate to be 5r/min.
(4) And (3) placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the condition that the temperature rising rate is 10 ℃/min and the reaction temperature is 400 ℃ and the temperature is kept for 4 hours in the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate was cut into a wafer with a diameter of 10mm, which was used to assemble a button cell with sodium metal as a counter electrode.
(6) And assembling the Al-V alloy film electrode after electrochemical deposition into a symmetrical battery.
Example 4
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into a foil with the thickness of 5 multiplied by 4cm, ultrasonically cleaning the metal aluminum foil with deionized water and ethanol, and putting the metal aluminum foil serving as a sputtering substrate into a chamber;
(2) Vacuum is pumped in the vacuum chamber, and the vacuum degree reaches 2 multiplied by 10 -3 Pa; then argon is introduced into the chamber, and the air pressure is regulated to 100Pa, so that the surface of the deposition substrate is cleaned for 10min.
(3) Starting a cathode Vtarget, setting the power of the Vtarget to be 200W, setting the working air pressure to be 8Pa, setting the sputtering time to be 10min, and setting the rotating speed of the substrate to be 5r/min.
(4) And (3) placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the condition that the temperature rising rate is 10 ℃/min and the reaction temperature is 400 ℃ and the temperature is kept for 4 hours in the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate was cut into a wafer with a diameter of 10mm, which was used to assemble a button cell with sodium metal as a counter electrode.
(6) And assembling the Al-V alloy film electrode after electrochemical deposition into a symmetrical battery.
Example 5
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into a foil with the thickness of 5 multiplied by 4cm, ultrasonically cleaning the metal aluminum foil with deionized water and ethanol, and putting the metal aluminum foil serving as a sputtering substrate into a chamber;
(2) Vacuum is pumped in the vacuum chamber, and the vacuum degree reaches 3 multiplied by 10 -3 Pa; then argon is introduced into the chamber, and the air pressure is regulated to 100Pa, so that the surface of the deposition substrate is cleaned for 10min.
(3) Starting a cathode Vtarget, setting the power of the Vtarget to 120W, the working air pressure to 5Pa, the sputtering time to 10min, and the substrate rotating speed to 5r/min.
(4) And (3) placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the condition that the temperature rising rate is 2 ℃/min and the reaction temperature is 400 ℃ and the temperature is kept for 4 hours in the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate was cut into a wafer with a diameter of 10mm, which was used to assemble a button cell with sodium metal as a counter electrode.
(6) And assembling the Al-V alloy film electrode after electrochemical deposition into a symmetrical battery.
Example 6
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into a foil with the thickness of 5 multiplied by 4cm, ultrasonically cleaning the metal aluminum foil with ethanol and deionized water, and putting the metal aluminum foil serving as a sputtering substrate into a chamber;
(2) Vacuum is pumped in the vacuum chamber, and the vacuum degree reaches 3 multiplied by 10 -3 Pa; then argon is introduced into the chamber, and the air pressure is regulated to 100Pa, so that the surface of the deposition substrate is cleaned for 10min.
(3) Starting a cathode Vtarget, setting the power of the Vtarget to be 200W, 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 5r/min.
(4) And (3) placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the condition that the temperature rising rate is 2 ℃/min and the reaction temperature is 550 ℃ and the heat preservation is carried out for 2 hours in the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate was cut into a wafer with a diameter of 10mm, which was used to assemble a button cell with sodium metal as a counter electrode.
(6) And assembling the Al-V alloy film electrode after electrochemical deposition into a symmetrical battery.
Example 7
(1) Selecting a metal aluminum foil with the thickness of 20 mu m, cutting the metal aluminum foil into a foil with the thickness of 5 multiplied by 4cm, ultrasonically cleaning the metal aluminum foil with deionized water and ethanol, and putting the metal aluminum foil serving as a sputtering substrate into a chamber;
(2) Vacuum is pumped in the vacuum chamber, and the vacuum degree reaches 1 multiplied by 10 -3 Pa; then argon is introduced into the chamber, and the air pressure is regulated to 100Pa, so that the surface of the deposition substrate is cleaned for 10min.
(3) Starting a cathode Vtarget, setting the power of the Vtarget to 120W, the working air pressure to 10Pa, the sputtering time to 10min, and the substrate rotating speed to 5r/min.
(4) And (3) placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the condition that the temperature rising rate is 5 ℃/min and the reaction temperature is 550 ℃ and the heat preservation is carried out for 2 hours in the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate was cut into a wafer with a diameter of 10mm, which was used to assemble a button cell with sodium metal as a counter electrode.
(6) And assembling the Al-V alloy film battery after 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 with the thickness of 5 multiplied by 4cm, ultrasonically cleaning the metal aluminum foil with deionized water and ethanol, and putting the metal aluminum foil serving as a sputtering substrate into a chamber;
(2) Vacuum is pumped in the vacuum chamber, and the vacuum degree reaches 1 multiplied by 10 -3 Pa; then argon is introduced into the chamber, and the air pressure is regulated to 100Pa, so that the surface of the deposition substrate is cleaned for 10min.
(3) Starting a cathode Vtarget, setting the power of the Vtarget to be 200W, setting the working air pressure to be 5Pa, setting the sputtering time to be 5min, and setting the rotating speed of the substrate to be 5r/min.
(4) And (3) placing the sputtered aluminum foil in a tube furnace, and naturally cooling to room temperature under the condition that the temperature rising rate is 5 ℃/min and the reaction temperature is 550 ℃ and the heat preservation is carried out for 2 hours in the argon atmosphere to obtain the Al-V alloy film.
(5) The obtained Al-V alloy film substrate was cut into a wafer with a diameter of 10mm, which was used to assemble a button cell with sodium metal as a counter electrode.
(6) And assembling the Al-V alloy film electrode after electrochemical deposition into a symmetrical battery.
While the invention has been described with respect to certain specific embodiments thereof, it will be understood by those skilled in the art that the present invention is not limited thereto, and that all other embodiments may be made without inventive faculty.
Claims (9)
1. The preparation method of the Al-V alloy film base material for the sodium metal battery is characterized by comprising the following steps of: (1) Fixing a V target at a position corresponding to a target material by adopting a magnetron sputtering method, placing a pretreated aluminum current collector at a position corresponding to a sample, pumping the cavity to high vacuum, applying a sputtering power supply, cleaning a substrate by plasma, and finally performing V deposition to obtain a V film material; (2) And (3) placing the magnetron sputtered sample in a tube furnace, performing heat treatment under a certain condition, and cooling to obtain the Al-V alloy film.
2. The method for preparing the Al-V alloy film base 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 film base 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 collectors 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 film base 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 an Al-V alloy thin film substrate material for sodium metal batteries according to claim 1The method is characterized in that: 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 film base 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 conditions are as follows: the power of the V target is 120-200W, the working air pressure is 5-10 Pa, and the sputtering time is 5-10 min.
7. The method for preparing the Al-V alloy film base 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: argon atmosphere, heating speed of 2-10 ℃/min, reaction temperature of 400-550 ℃ and heat preservation time of 2-4 h.
8. An Al-V alloy thin film base material for sodium metal battery, prepared by the preparation method of any one of claims 1 to 7, characterized in that: the micro-morphology of the Al-V alloy film is in a rod shape, and the length of the micro-morphology is 100-200nm.
9. An application of an Al-V alloy film base material for a sodium metal battery is characterized in that: the Al-V alloy thin film base material application field according to claim 8 is a sodium metal battery.
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