CN115261662B - High-entropy alloy CuSnZnAlCD/C carbon-based composite material and preparation method and application thereof - Google Patents
High-entropy alloy CuSnZnAlCD/C carbon-based composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-entropy alloy CuSnZnAlCD/C carbon-based composite material, which comprises the following steps: step one, the copper source, the zinc source, the tin source, the aluminum source and the cadmium source are mixed in the same moleAdding the mixture into a reagent bottle filled with 5-10 mL of absolute ethyl alcohol according to the molar ratio, and isolating air from stirring at room temperature to obtain CuSnZnAlCD precursor solution with the concentration of 1-10 mmol/L; step two, treating the carbon paper in a plasma cleaner for 5 to 30 minutes; step three, taking 10 mu L-100 mu L of the high-entropy precursor solution prepared in the step one, titrating the solution on the carbon paper obtained in the step two, and drying the solution in vacuum; and fourthly, placing the carbon paper obtained in the third step into a tube furnace, and heating to 700-1200 ℃ in an argon-hydrogen mixed gas atmosphere to anneal for 1-5 hours to obtain the high-entropy alloy CuSnZnAlCD/C composite material. The high-entropy alloy CuSnZnAlCD/C composite material regulates lithium ions (Li) through the synergistic effect of high-entropy electronic property cooperative regulation (composite effect) and lithium-philic nucleation (low nucleation barrier) + ) Is uniformly deposited to enable Li to + And the lithium dendrite is uniformly deposited on the surface of the electrode so as to inhibit the growth of lithium dendrite, thereby realizing stable electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of functional materials, relates to a lithium battery electrode material, and in particular relates to a high-entropy alloy CuSnZnAlCD/C carbon-based composite material, and a preparation method and application thereof.
Background
With the global increase of low-carbon economy, ecological environment improvement and energy crisis demand alleviation, the market and application prospect of new energy batteries are rapidly developed. Wherein the lithium metal (3860 mAh.g) -1 ) Lithium metal materials are considered as potential high energy density lithium metal materials due to their high theoretical energy density and lowest electrochemical potential, however, lithium metal as a negative electrode still faces some application problems to be solved. Wherein metallic lithium is combined withThe traditional electrolyte can produce adverse side reactions; lithium dendrite growth at non-uniform nucleation sites during the reaction process may cause short circuit or even explosion of the battery; side reactions and lithium dendrite problems will accelerate electrolyte consumption and result in low coulombic efficiency and poor cycling performance.
Therefore, to achieve the commercial goals of high energy density and safe operation of Lithium Metal Batteries (LMBs), efforts must be made to alleviate or even eradicate the lithium dendrite growth problem. In terms of structural design, structural design or surface treatment of the carbon-based Li negative electrode can alleviate lithium dendrite growth to some extent. At the same time, li is regulated and controlled by utilizing a lithium-philic material through' functional design + Is deposited on the surface Li of the negative electrode + The uniform distribution of (c) can also inhibit the growth of lithium dendrites. However, in practical application, the lithium-philic material has poor electronic/ionic conductivity, high reactivity of binary lithium-containing alloy, large volume change, low energy density and higher cost in structural and functional design, and can be used for solving the problems by more considering ternary/multicomponent lithium alloy and mutually supplementing by multiple components. Then the use of lithium-philic high entropy alloy nanoparticles with high stability to construct "multicomponent complementation" is the best approach to solve this problem.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a high-entropy alloy CuSnZnAlCD/C carbon-based composite material, a preparation method and application thereof, and a high-entropy alloy composite electrode material with excellent and stable electrochemical performance is prepared.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the preparation method of the high-entropy alloy CuSnZnAlCD/C carbon-based composite material comprises the following steps:
firstly, adding a copper source, a zinc source, a tin source, an aluminum source and a cadmium source into a reagent bottle filled with 5-10 mL of absolute ethyl alcohol according to the same molar ratio of copper, zinc, tin, aluminum and cadmium elements, and isolating air from stirring at room temperature to obtain a CuSnZnAlCD precursor solution with the total concentration of copper, zinc, tin, aluminum and cadmium metal ions of 1-10 mmol/L;
step two, treating the carbon paper in a plasma cleaner for 5 to 30 minutes;
step three, taking 10 mu L-100 mu L of the high-entropy precursor solution prepared in the step one and titrating the solution into 0.785cm 2 Drying the carbon paper obtained in the second step in vacuum;
and fourthly, placing the carbon paper obtained in the third step into a tube furnace, and heating to 700-1200 ℃ in an argon-hydrogen mixed gas atmosphere to anneal for 1-5 hours to obtain the high-entropy alloy CuSnZnAlCD/C composite material.
The invention also has the following technical characteristics:
preferably, the copper source in the first step is any one of copper sulfate, copper chloride or copper nitrate and hydrate thereof.
Preferably, the zinc source in the first step is any one of zinc sulfate, zinc chloride or zinc nitrate and hydrate thereof.
Preferably, the tin source in the first step is any one of tin sulfate, tin chloride or tin nitrate and hydrate thereof.
Preferably, the aluminum source in the first step is any one of aluminum sulfate, aluminum chloride or aluminum nitrate and hydrate thereof.
Preferably, the cadmium source in the first step is any one of cadmium sulfate, cadmium chloride and cadmium nitrate.
Preferably, the full stirring in the step one is stirring for 12-24 hours at a rotating speed of 200-400 r/min by using a magnetic stirrer.
Preferably, the vacuum drying in the step three is drying in a vacuum oven at 60-100 ℃ for 8-12 h.
The invention also protects the high-entropy alloy CuSnZnAlCD/C carbon-based composite material prepared by the method and application of the material in the electrode material of the lithium metal battery.
Compared with the prior art, the invention has the following technical effects:
the invention combines the high-entropy alloy CuSnZnAlCD into the carbon-based material by a surface titration method and a high-temperature oxidation-reduction method to form the lithium metal battery electrode material with the high-entropy alloy CuSnZnAlCD/C carbon-based composite material, and the CuSnZnAlCD/C composite material passes through the high entropySynergistic action of electronic property co-modulation (recombination effect) and lithium-philic nucleation (low nucleation barrier) to modulate Li + Is uniformly deposited to enable Li to + Uniformly depositing on the surface of the electrode to inhibit the growth of lithium dendrite; the strategy can be realized at a current density of 20mA cm -2 Under test, the battery also realizes stable electroplating/stripping after 8800h of internal circulation; under the test condition of the full electrode 1C, the cycle of more than 700 circles can be realized, and the average specific capacity is more than 140 mAh.g -1 And coulombic efficiency as high as 99.9%.
Drawings
FIG. 1 is an SEM image (100 μm) of the high entropy alloy CuSnZnAlCD/C carbon-based composite material prepared in example 1;
FIG. 2 is an SEM image (20 μm) of the high entropy alloy CuSnZnAlCD/C carbon-based composite material prepared in example 1;
FIG. 3 is an XRD pattern of the high entropy alloy CuSnZnAlCD/C carbon-based composite material prepared in example 1;
FIGS. 4 to 6 are graphs showing counter electrode performance of the high-entropy alloy CuSnZnAlCD/C carbon-based composite material prepared in example 1;
FIGS. 7 and 8 are full electrode performance graphs of the high-entropy alloy CuSnZnAlCD/C carbon-based composite material prepared in example 1;
FIG. 9 is a graph of the high entropy alloy CuSnZnAlCD/C carbon matrix composite prepared in example 1 versus battery magnification;
fig. 10 is a full cell magnification graph of the high entropy alloy CuSnZnAlCd/C carbon matrix composite prepared in example 1.
Detailed Description
The present invention will be specifically described with reference to the drawings and examples, but the embodiments of the present invention are not limited thereto. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The experimental methods of the specific experimental conditions are not noted in the following examples, and generally follow the conventional experimental conditions. The reagents and starting materials used in the present invention are commercially available unless otherwise specified. The argon-hydrogen mixture in each of the following examples had a hydrogen volume ratio of 10%.
Example 1
The embodiment provides a preparation method of a high-entropy alloy CuSnZnAlCD/C carbon-based composite material for a lithium metal battery electrode, which specifically comprises the following steps:
step one, cuCl 2 ·2H 2 O、SnCl 2 ·2H 2 O、ZnCl 2 、AlCl 3 ·6H 2 O、CdCl 2 Adding the mixture into a reagent bottle filled with 5mL of absolute ethyl alcohol in the same molar ratio, and stirring for 24 hours at room temperature under the condition of isolating air by adopting a magnetic stirrer at 200r/min to obtain the total concentration of metal ions of the precursor of the CuSnZnAlCD solution at 5mmol/L;
step two, the area is 0.785cm 2 Is processed for 30min in a plasma cleaner;
step three, titrating 10 mu L of the high-entropy precursor solution obtained in the step one on the carbon paper obtained in the step two, and putting the carbon paper into a vacuum drying oven to be dried for 10 hours at 80 ℃;
and fourthly, placing the carbon paper obtained in the third step into a tube furnace, and heating to 700 ℃ in an argon-hydrogen mixed gas atmosphere for annealing for 1h to obtain the high-entropy alloy CuSnZnAlCD/C composite material.
Example 2
The embodiment provides a preparation method of a high-entropy alloy CuSnZnAlCD/C carbon-based composite material for a lithium metal battery electrode, which specifically comprises the following steps:
adding copper sulfate, zinc sulfate, tin sulfate, aluminum sulfate and cadmium sulfate into a reagent bottle filled with 10mL of absolute ethyl alcohol according to the same molar ratio, and stirring for 24 hours at room temperature by adopting a magnetic stirrer at 200r/min under the condition of isolating air, wherein the total concentration of metal ions of a precursor of the CuSnZnAlCD solution is 10mmol/L;
step two, the area is 0.785cm 2 Is processed for 30min in a plasma cleaner;
step three, titrating 10 mu L of the high-entropy precursor solution obtained in the step one on the carbon paper obtained in the step two, and putting the carbon paper into a vacuum drying oven to be dried for 24 hours at 70 ℃;
and fourthly, placing the carbon paper obtained in the third step into a tube furnace, and heating to 1100 ℃ in an argon-hydrogen mixed gas atmosphere for annealing for 1h to obtain the high-entropy alloy CuSnZnAlCD/C composite material.
Example 3
The embodiment provides a preparation method of a high-entropy alloy CuSnZnAlCD/C carbon-based composite material for a lithium metal battery electrode, which specifically comprises the following steps:
adding copper nitrate, zinc nitrate, tin nitrate, aluminum nitrate and cadmium nitrate into a reagent bottle filled with 10mL of absolute ethyl alcohol according to the same molar ratio, and stirring for 24 hours at room temperature by adopting a magnetic stirrer at 300r/min under the condition of isolating air to obtain a CuSnZnAlCD solution precursor metal ion total concentration of 5mmol/L;
step two, the area is 0.785cm 2 Is processed for 30min in a plasma cleaner;
step three, titrating 10 mu L of the high-entropy precursor solution obtained in the step one on the carbon paper obtained in the step two, and putting the carbon paper into a vacuum drying oven to be dried for 12 hours at 60 ℃;
and fourthly, placing the carbon paper obtained in the third step into a tube furnace, and heating to 1100 ℃ in an argon-hydrogen mixed gas atmosphere for annealing for 3 hours to obtain the high-entropy alloy CuSnZnAlCD/C composite material.
Example 4
Adding copper chloride, tin chloride, zinc chloride, aluminum chloride and cadmium chloride into a reagent bottle filled with 8mL of absolute ethyl alcohol according to the same molar ratio, and stirring for 12 hours at room temperature by adopting a magnetic stirrer 400r/min under the condition of isolating air, wherein the total concentration of metal ions of a precursor of the CuSnZnAlCD solution is 8mmol/L;
step two, the area is 0.785cm 2 Is processed for 30min in a plasma cleaner;
step three, titrating 10 mu L of the high-entropy precursor solution obtained in the step one on the carbon paper obtained in the step two, and putting the carbon paper into a vacuum drying oven to be dried for 12 hours at 80 ℃;
and fourthly, placing the carbon paper obtained in the third step into a tube furnace, and heating to 1100 ℃ in an argon-hydrogen mixed gas atmosphere for annealing for 2 hours to obtain the high-entropy alloy CuSnZnAlCD/C composite material.
Example 5
Adding copper chloride, tin chloride, zinc chloride, aluminum chloride and cadmium chloride into a reagent bottle filled with 6mL of absolute ethyl alcohol according to the same molar ratio, and stirring for 18 hours at room temperature by adopting a magnetic stirrer at 300r/min under the condition of isolating air to obtain a CuSnZnAlCD solution precursor metal ion total concentration of 1mmol/L;
step two, the area is 0.785cm 2 The carbon paper sheets of (2) are treated in a plasma cleaner for 5min;
step three, titrating 50 mu L of the high-entropy precursor solution obtained in the step one on the carbon paper obtained in the step two, and putting the carbon paper into a vacuum drying oven to be dried for 8 hours at 100 ℃;
and fourthly, placing the carbon paper obtained in the third step into a tube furnace, and heating to 1000 ℃ in an argon-hydrogen mixed gas atmosphere for annealing for 2 hours to obtain the high-entropy alloy CuSnZnAlCD/C composite material.
Example 6
Adding copper chloride, tin chloride, zinc chloride, aluminum chloride and cadmium chloride into a reagent bottle filled with 5mL of absolute ethyl alcohol according to the same molar ratio, and stirring for 24 hours at room temperature under the condition of isolating air by adopting a magnetic stirrer 200r/min to obtain a CuSnZnAlCD solution precursor metal ion total concentration of 10mmol/L;
step two, the area is 0.785cm 2 The carbon paper sheets of (2) are treated in a plasma cleaner for 20min;
step three, titrating 100 mu L of the high-entropy precursor solution obtained in the step one on the carbon paper obtained in the step two, and putting the carbon paper into a vacuum drying oven to be dried for 10 hours at 80 ℃;
and fourthly, placing the carbon paper obtained in the third step into a tube furnace, and heating to 900 ℃ in an argon-hydrogen mixed gas atmosphere for 4 hours of annealing to obtain the high-entropy alloy CuSnZnAlCD/C composite material.
The summary is as follows:
1 morphology
Fig. 1 and fig. 2 are SEM images of the high-entropy alloy cusnzalcd/C carbon-based composite material prepared in example 1 under different magnifications, and it can be seen from fig. 1 and fig. 2 that the microscopic morphology of cusnzalcd is spherical and uniformly grows on the surface of the carbon fiber.
2 composition
FIG. 3 shows XRD diffraction peaks of the high-entropy alloy CuSnZnAlCD/C carbon-based composite material prepared in example 1, and the characteristic peak intensity is high as shown in FIG. 3, which shows that the high-entropy alloy CuSnZnAlCD/C carbon-based composite material has been synthesized.
3 electrochemical Properties
FIG. 4 to FIG. 6 are graphs showing the performance of counter electrodes of the high entropy alloy CuSnZnAlCD/C carbon-based composite material prepared in example 1; as shown in FIG. 4, the example was prepared as a negative electrode at a current density of 20mA cm -2 Specific capacity of 20mAh cm -2 When the electrode stability was tested, stable plating/stripping was also achieved after 8800h of cycling of the cell, and no large overpotential was observed before and after cycling.
As shown in FIGS. 5 and 6, when the current density is further increased, the current density is 40mA cm -2 Specific capacity of 40mAh cm -2 A current density of 60mA cm -2 Specific capacity of 1mAh cm -2 When the stability of the electrode was tested, the battery exhibited excellent long-cycle stability; even at 60 mA.cm -2 The overpotential of the battery is also small at high current densities, and the battery has more excellent electrochemical performance during long-time charge-discharge cycles at such high current densities.
FIGS. 7 to 8 are full electrode performance graphs of the high entropy alloy CuSnZnAlCD/C carbon-based composite material prepared in example 1; as shown in fig. 7, the advantage of cusnzalcd/c@li (HEA/c@li) negative electrode is demonstrated for a carbonate electrolyte system when it is matched to a lithium iron phosphate positive electrode as a full cell; at a current density of 0.1C, 147 mAh.g was provided after 50 cycles -1 Average specific capacity sum of (2)>High coulombic efficiency of 99.9%. Meanwhile, as shown in FIG. 8, under the test condition of 1C, more than 700 cycles can be realized, and the average specific capacity is more than 140 mAh.g -1 And coulombic efficiency as high as 99.9%.
FIG. 9 is a graph of the high entropy alloy CuSnZnAlCD/C carbon matrix composite prepared in example 1 versus battery magnification; as shown in FIG. 9, symmetrical cells were tested at different current densities (1 mA cm -2 /1mAh·cm -2 、2mA·cm -2 /2mAh·cm -2 、5mA·cm -2 /5mAh·cm -2 、10mA·cm -2 /10mAh·cm -2 、20mA·cm -2 /20mAh·cm -2 、40mA·cm -2 /40mAh·cm -2 、60mA·cm -2 /60mAh·cm -2 ) The following rate capability. The results show that the symmetrical cell has stable overpotential, which indicates that the material can have good electrochemical performance under high current density and stripping/deposition.
Fig. 10 is a full cell magnification graph of the high entropy alloy CuSnZnAlCd/C carbon matrix composite prepared in example 1. As shown in fig. 10, the preparation of example 1 as a negative electrode tested the rate performance of the battery at different current densities. The average reversible capacities of the batteries at current densities of 0.1C, 0.2C, 0.5C, 1C, 5C and 0.2C are respectively 148.3 mAh.g -1 、147mAh·g -1 、140.1mAh·g -1 、120.8mAh·g -1 、110.1mAh·g -1 、98.8mAh·g -1 . When the current density is restored to 0.2C, the capacity of the battery may be substantially restored to the initial capacity of 0.2C.
It should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; other combinations of aluminum source, zinc source, tin source, cadmium source, and copper source may be used in the embodiments described above, and deductions or substitutions made by those skilled in the art without departing from the spirit of the present invention are all within the scope of the present invention.
Claims (10)
1. The preparation method of the high-entropy alloy CuSnZnAlCD/C carbon-based composite material is characterized by comprising the following steps of:
firstly, adding a copper source, a zinc source, a tin source, an aluminum source and a cadmium source into a reagent bottle filled with 5-10 mL of absolute ethyl alcohol according to the same molar ratio of copper, zinc, tin, aluminum and cadmium elements, and isolating air from stirring at room temperature to obtain a CuSnZnAlCD precursor solution with the total concentration of copper, zinc, tin, aluminum and cadmium metal ions of 1-10 mmol/L;
step two, treating the carbon paper in a plasma cleaner for 5-30 min;
step three, taking 10-100 mu L of the high-entropy precursor solution prepared in the step one, titrating the solution onto the carbon paper obtained in the step 0.785cm, and drying the carbon paper in vacuum;
and fourthly, placing the carbon paper obtained in the third step into a tube furnace, and heating to 700-1200 ℃ in an argon-hydrogen mixed gas atmosphere to anneal for 1-5 hours to obtain the high-entropy alloy CuSnZnAlCD/C carbon-based composite material.
2. The method for preparing the high-entropy alloy cusnznhalcd/C carbon-based composite material according to claim 1, wherein the copper source in the first step is any one of copper sulfate, copper chloride or copper nitrate and hydrate thereof.
3. The method for preparing the high-entropy alloy CuSnZnAlCD/C carbon-based composite material according to claim 1, wherein the zinc source in the first step is any one of zinc sulfate, zinc chloride or zinc nitrate and hydrate thereof.
4. The method for preparing the high-entropy alloy CuSnZnAlCD/C carbon-based composite material according to claim 1, wherein the tin source in the first step is any one of tin sulfate, tin chloride or tin nitrate and hydrate thereof.
5. The method for preparing the high-entropy alloy cusnznhalcd/C carbon-based composite material according to claim 1, wherein the aluminum source in the first step is any one of aluminum sulfate, aluminum chloride or aluminum nitrate and a hydrate thereof.
6. The method for preparing the high-entropy alloy CuSnZnAlCD/C carbon-based composite material according to claim 1, wherein the cadmium source in the first step is any one of cadmium sulfate, cadmium chloride and cadmium nitrate.
7. The method for preparing the high-entropy alloy CuSnZnAlCD/C carbon-based composite material according to claim 1, wherein the stirring in the step one is stirring for 12-24 hours at a rotating speed of 200-400 r/min by using a magnetic stirrer.
8. The method for preparing the high-entropy alloy CuSnZnAlCD/C carbon-based composite material according to claim 1, wherein the vacuum drying in the third step is performed in a vacuum oven at 60-100 ℃ for 8-12 h.
9. A high entropy alloy cusnzalcd/C carbon matrix composite prepared by the method of any one of claims 1-8.
10. Use of the high-entropy alloy CuSnZnAlCd/C carbon-based composite material according to claim 9 in lithium metal battery electrode materials.
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