CN114824236B - Water-based zinc ion battery anode material with functional protective layer and preparation method thereof - Google Patents
Water-based zinc ion battery anode material with functional protective layer and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of electrode materials of zinc ion batteries, and particularly relates to a water-based zinc ion battery anode material with a functional protective layer and a preparation method thereof. The invention constructs Sn-ZnP functional protective layer on the surface of the metallic zinc anode, inserts P into Zn crystal lattice to form ZnP protective layer by an economic and efficient electrodeposition method, and is beneficial to Zn 2+ And reduces the electrochemical reaction energy barrier during Zn plating/stripping; meanwhile, znSn alloy formed by electrodeposition can effectively inhibit hydrogen evolution reaction of a zinc electrode and generation of irreversible byproducts, so that the cycle life of the battery is prolonged.
Description
Technical Field
The invention belongs to the technical field of preparation of electrode materials of zinc ion batteries, and particularly relates to a water-based zinc ion battery anode material with a functional protective layer and a preparation method thereof.
Background
With the rapid development of technology and industry, the consumption of the society to energy is huge, and the exploitation and use of fossil energy destroys the ecological environment. Therefore, social demands motivate researchers to explore the enthusiasm for low-cost, high-energy density and environmentally friendly renewable energy sources. In recent years, with electric vehicles andthe development of wearable electronic devices is rapid, and lithium ion batteries are widely used. However, due to the limited reserves of lithium resources on earth, uneven distribution, inflammable and explosive organic electrolyte, low environmental friendliness and other problems, the commercial application of lithium ion batteries is further limited, and researchers are promoted to search for low-cost and economical alternative energy storage systems. While zinc metal electrode has high theoretical capacity (820 mAh/g, 5855 mAh/cm) 3 ) The characteristics of low potential (-0.76V vs standard hydrogen electrode), environmental protection, low cost and the like make the zinc ion battery become one of the most potential alternative energy storage ion batteries.
Although there are many advantages of zinc ion batteries, the disadvantages are unavoidable, and solving these problems is of great importance for the design of aqueous zinc ion batteries with high energy density and high power density. Such as dendrite growth, hydrogen evolution reactions, corrosion, etc., of zinc metal anodes. They not only consume a large amount of active material, resulting in a battery with reduced capacity and poor cycle performance, but also severely may puncture the film, thereby causing a short circuit of the battery. In response to these problems, researchers have developed a number of modified strategies to improve the electrochemical performance of batteries. For example, there are researchers to coat hydrogen-substituted graphite diacetines synthesized by cross-coupling and cyclizing 1,3, 5-tri-ethynyl benzene onto zinc sheets, which can selectively transfer Zn due to the ion tunnel structure of the protective layer material 2+ Promoting uniform zinc electrodeposition and inhibiting dendrite growth. There are research teams using atomic layer deposition techniques on zinc foil, such ultra-thin and dense TiO 2 The metal passivation layer prevents the zinc anode from being in direct contact with electrolyte, inhibits zinc corrosion and hydrogen evolution reaction, and reduces Zn (OH) 2 And the formation of byproducts promotes the uniform deposition of zinc ions. Although these modification strategies all inhibit dendrite growth on the zinc anode surface, conventional coating approaches tend to result in non-uniformity of the protective layer, and the equipment required to employ atomic layer deposition methods is relatively complex.
Compared with other methods for preparing the coating, the electrodeposition method has the characteristics of high safety, low cost, simple process, mass production and the like, and is interesting for many researchers. Here, the inventors have desired to provide a simple electrodeposition method of plating a zinc metal anode with a protective layer that not only does not affect the chemical activity of the anode material but also can significantly improve the capacity and cycle stability of the battery.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a water-based zinc ion battery anode material with a functional protective layer and a preparation method thereof, compared with the traditional methods such as a hydrothermal method, a coating method, an ion beam sputtering method and the like, the electrodeposition method adopted by the invention has simple and controllable process and can realize large-scale preparation; by using nontoxic modified zinc sheet negative electrode material and water system Zn 2+ And Mn of 2+ And the safety and the cycling stability of the battery are ensured by mixing the ion electrolyte and the manganese-based positive electrode material.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
a preparation method of a water-based zinc ion battery anode material comprises the following steps:
1) Zinc sheet pretreatment: soaking the cut zinc sheet in dilute hydrochloric acid, removing surface oxides by ultrasonic treatment for a period of time at room temperature, repeatedly cleaning with deionized water and absolute ethyl alcohol after soaking, and finally drying at room temperature for later use;
2) Preparing an electroplating solution: weighing a zinc source, a phosphorus source, a tin source, boric acid, sodium sulfate and disodium ethylenediamine tetraacetate according to a certain molar ratio, adding deionized water, and stirring for dissolution to obtain electroplating solution;
3) Electrochemical deposition: and (3) taking the zinc sheet pretreated in the step (1) as a working electrode, silver chloride as a reference electrode, and a platinum sheet as a counter electrode to assemble a three-electrode electroplating device, adding the electroplating solution prepared in the step (2), and performing constant current deposition by using an electrochemical workstation to obtain the water-based zinc ion battery anode material with the functional protective layer, namely a Zn@Sn-ZnP electrode material.
Further, in the step 1), the concentration of the dilute hydrochloric acid is 0.1 to 0.5mol/L.
Further, in step 2), the zinc source is zinc sulfate, the phosphorus source is sodium hypophosphite, and the tin source is stannous chloride.
Further, in the step 2), the concentration of zinc sulfate in the obtained plating solution is 0.01 to 1mol/L, the concentration of sodium hypophosphite is 0.01 to 0.5mol/L, and the concentration of stannous chloride is 0.005 to 0.05mol/L.
Further, in the step 2), the ratio of the total molar amount of the phosphorus source and the tin source to the molar amount of the zinc source in the obtained plating solution is 0.08 to 2:4.
Further, in the step 2), the molar ratio of sodium hypophosphite to stannous chloride in the obtained electroplating solution is 1:0.005-0.05.
Further, in step 3), the electrochemical deposition process employs a voltage window of 0.8-1.8V.
Further, in the step 3), the deposition current of the chronopotentiometry adopted by the electrochemical deposition process is 10-100 mA, and the deposition time is 30-200 s.
Further, in the step 3), after the Zn@Sn-ZnP electrode material is obtained, deionized water is used for repeated cleaning, and finally, the electrode material is naturally dried at room temperature.
The water-based zinc ion battery anode material with the functional protective layer is prepared by the preparation method.
The beneficial effects of the invention are as follows:
1. the invention has the advantages of abundant raw materials, safety, no pollution and low cost; the reaction condition is mild, the natural environment is enough, the process is simple, the raw material consumption is increased, and the large-scale preparation can be realized; the nano-sheet Zn@Sn-ZnP generated on the surface of the zinc sheet is beneficial to promoting the rapid transmission of ions, realizing uniform zinc electrodeposition, inhibiting dendrite growth and improving the cycle stability and the battery capacity.
2. The Zn@Sn-ZnP coating generated on the surface of the zinc sheet is beneficial to quick transfer of ions and reduction of electrochemical activation energy in the zinc stripping/electroplating process, sn heteroatom doping can reduce the surface free energy of a Zn negative electrode, and Sn is doped under the drive of a local strong electric field 2+ Tends to deposit at the tip of the zinc anode, thereby reducing the surface energy of the zinc at the tip, thereby forming a dendrite-free zinc anode.
3. When the Zn@Sn-ZnP electrode material is used as the negative electrode, the water-based zinc ion full battery can be assembled in a natural environment; the assembled zinc ion battery has positive electrode with manganese base, diaphragm with glass fiber and electrolyte with mixed solution of zinc sulfate and manganese sulfate.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of an electrode material of example 1 at various magnifications Zn@Sn-ZnP;
FIG. 2 is the electrochemical performance of Zn@Sn-ZnP// zinc salt+manganese salt// manganese based full cell of example 1: (a) a charge-discharge cycle curve, (b) an EIS curve of a Zn@Sn-ZnP electrode symmetrical battery, (c) cycle performance;
FIG. 3 is an SEM image of the electrode material of example 2 at various magnifications Zn@Sn-ZnP;
FIG. 4 is the electrochemical performance of Zn@Sn-ZnP// zinc salt+manganese salt// manganese based full cell of example 2: (a) charge-discharge cycle curve, (b) EIS curve of Zn@Sn-ZnP electrode symmetrical battery, (c) cycle performance.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is simple and convenientAnd constructing a Sn-ZnP functional protective layer on the zinc cathode by a controlled electrodeposition method. The preparation method of the modified zinc cathode comprises the following steps: zinc sheet is used as substrate, zinc sulfate heptahydrate, sodium phosphite, stannous chloride dihydrate, boric acid, sodium sulfate, disodium ethylenediamine tetraacetate and deionized water are mixed to form electroplating solution, and zinc phosphide doped with tin is uniformly deposited on the zinc sheet by using an electrodeposition method to form a coating (Zn@Sn-ZnP). The invention constructs Sn-ZnP functional protective layer on the surface of the metallic zinc anode, inserts P into Zn crystal lattice to form ZnP protective layer by an economic and efficient electrodeposition method, and is beneficial to Zn 2+ And reduces the electrochemical reaction energy barrier during Zn plating/stripping; meanwhile, znSn alloy formed by electrodeposition can effectively inhibit hydrogen evolution reaction of a zinc electrode and generation of irreversible byproducts, so that the cycle life of the battery is prolonged.
Specific embodiments of the invention are as follows:
example 1
The preparation method of the water-based zinc ion battery anode material specifically comprises the following steps:
1) Zinc sheet pretreatment: cutting multiple zinc sheets with specification of 2cm×1cm, soaking in 0.3mol/L dilute hydrochloric acid for 3min, removing surface oxide film, repeatedly cleaning the soaked zinc sheets with anhydrous ethanol and deionized water for several times, and naturally drying for use.
2) 100mL of 0.4M zinc sulfate heptahydrate (ZnSO) was formulated 4 ·7H 2 O), 0.1M sodium phosphite (NaH) 2 PO 2 ) 0.08M boric acid (H) 3 BO 3 ) Sodium sulfate (NaSO) 4 ) 0.01M stannous chloride dihydrate (SnCl) 2 ·2H 2 O), 0.006M sodium ethylenediamine tetraacetate (C) 10 H 14 N 2 Na 2 O 8 ) As the plating solution.
3) And (2) taking the zinc sheet pretreated in the step (1) as a working electrode, taking AgCl as a reference electrode, taking Pt as a counter electrode, placing the zinc sheet into the electroplating solution prepared in the step (2) for constant current electroplating, setting a voltage window to be 0.8-1.8V, setting the current to be 20mA, electrodepositing for 120s at room temperature, repeatedly cleaning the obtained product with absolute ethyl alcohol and deionized water after the deposition is finished, and placing the product in a natural environment for drying to obtain the water-based zinc ion battery anode material with the functional protective layer.
The embodiment provides a water-based zinc ion battery, which is assembled by adopting the following method:
assembling a manganese-based anode, a zinc sheet cathode and a diaphragm into a shell, injecting electrolyte, wherein the electrolyte is composed of 2M ZnSO 4 And 0.1M MnSO 4 And the mixed solution is packaged into a Zn@Sn-ZnP// zinc salt+manganese salt// manganese-based positive electrode water-based zinc ion battery.
Example 2
The preparation method of the water-based zinc ion battery anode material specifically comprises the following steps:
1) Zinc sheet pretreatment: cutting multiple zinc sheets with specification of 2cm×1cm, soaking in 0.3mol/L dilute hydrochloric acid for 3min, removing surface oxide film, repeatedly cleaning the soaked zinc sheets with anhydrous ethanol and deionized water for several times, and naturally drying for use.
2) 100mL of 0.4M zinc sulfate heptahydrate (ZnSO) was formulated 4 ·7H 2 O), 0.1M sodium phosphite (NaH) 2 PO 2 ) 0.08M boric acid (H) 3 BO 3 ) Sodium sulfate (NaSO) 4 ) 0.01M stannous chloride dihydrate (SnCl) 2 ·2H 2 O), 0.006M sodium ethylenediamine tetraacetate (C) 10 H 14 N 2 Na 2 O 8 ) As the plating solution.
3) And (2) taking the zinc sheet pretreated in the step (1) as a working electrode, taking AgCl as a reference electrode, taking Pt as a counter electrode, placing the zinc sheet into the electroplating solution prepared in the step (2) for constant current electroplating, controlling the voltage range to be 0.8-1.8V, setting the current to be 60mA, electrodepositing at room temperature for 150s, repeatedly cleaning the obtained product by using absolute ethyl alcohol and deionized water after the deposition is finished, and placing the product in a natural environment for drying to obtain the water-based zinc ion battery anode material with the functional protective layer.
The embodiment provides a water-based zinc ion battery, which is assembled by adopting the following method:
assembling a manganese-based anode, a zinc sheet cathode and a diaphragm into a shell, injecting electrolyte, wherein the electrolyte is composed of 2M ZnSO 4 And 0.1M MnSO 4 And the mixed solution is packaged into a Zn@Sn-ZnP// zinc salt+manganese salt// manganese-based positive electrode water-based zinc ion battery.
The microstructure of the zn@sn-ZnP prepared above in this example 2 was scanned by scanning electron microscopy, and electrochemical tests were performed on the modified negative electrode of this example, including constant current charge/discharge (GCD), electrochemical Impedance Spectroscopy (EIS), and measurements of a symmetric cell.
The high-efficiency and long-life Zn@Sn-ZnP// zinc salt+manganese salt// manganese-based positive electrode water-based zinc ion battery is prepared from a nontoxic electrode material and water-based electrolyte, and has high safety. The nano flake Sn-ZnP coating growing on the zinc flake is uniformly covered on the surface of the electrode, and the structure can accelerate Zn 2+ The zinc is uniformly distributed on the surface of the electrode, and the electrochemical reaction energy barrier in the Zn electroplating/stripping process can be reduced, so that the excessive deposition of zinc and the growth of zinc dendrites are effectively avoided.
The cycle performance test is carried out on the assembled full battery of the cathodes of the two examples, the discharge specific capacity of the example 1 reaches 252.42mAh/g at the maximum after 175 times of test under the current density of 200mA/g, the average coulomb efficiency is close to 100%, and the symmetric battery assembled by Zn@Sn-ZnP electrode material is 0.2mA/cm 2 And a current density of 50mAh/cm 2 After 90 hours of circulation under the limited capacity, the modified electrode has no large voltage fluctuation, and experiments prove that the modified electrode presents a uniform zinc stripping/electroplating process and has better circulation stability.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. The preparation method of the water-based zinc ion battery anode material is characterized by comprising the following steps of:
1) Zinc sheet pretreatment: soaking the cut zinc sheet in dilute hydrochloric acid, removing surface oxides by ultrasonic treatment for a period of time in a room temperature environment, repeatedly cleaning with deionized water and absolute ethyl alcohol after soaking, and finally drying at room temperature for later use;
2) Preparing an electroplating solution: weighing a zinc source, a phosphorus source, a tin source, boric acid, sodium sulfate and disodium ethylenediamine tetraacetate according to a certain molar ratio, adding deionized water, and stirring for dissolution to obtain electroplating solution;
3) Electrochemical deposition: and (3) taking the zinc sheet pretreated in the step (1) as a working electrode, silver chloride as a reference electrode, and assembling a three-electrode electroplating device by taking a platinum sheet as a counter electrode, adding the electroplating solution prepared in the step (2), and performing constant current deposition by using an electrochemical workstation to obtain the water-based zinc ion battery anode material with the functional protection layer on the surface of the zinc sheet, wherein the functional protection layer comprises ZnSn alloy and Sn-doped ZnP.
2. The method for preparing the negative electrode material of the water-based zinc-ion battery according to claim 1, wherein the method comprises the following steps: in the step 1), the concentration of the dilute hydrochloric acid is 0.1-0.5 mol/L.
3. The method for preparing the negative electrode material of the water-based zinc-ion battery according to claim 1, wherein the method comprises the following steps: in the step 2), the zinc source is zinc sulfate, the phosphorus source is sodium hypophosphite, and the tin source is stannous chloride.
4. The method for producing a negative electrode material for an aqueous zinc-ion battery according to claim 3, wherein: in the step 2), the concentration of zinc sulfate in the obtained electroplating solution is 0.01-1 mol/L, the concentration of sodium hypophosphite is 0.01-0.5 mol/L, and the concentration of stannous chloride is 0.005-0.05 mol/L.
5. The method for preparing the negative electrode material of the water-based zinc-ion battery according to claim 4, wherein the method comprises the following steps: in the step 2), the ratio of the total mole amount of the phosphorus source and the tin source to the mole amount of the zinc source in the obtained plating solution is 0.08-2:4.
6. The method for producing a negative electrode material for an aqueous zinc-ion battery according to claim 5, wherein: in the step 2), the molar ratio of sodium hypophosphite to stannous chloride in the obtained electroplating solution is 1:0.005-0.05.
7. The method for preparing the negative electrode material of the water-based zinc-ion battery according to claim 1, wherein the method comprises the following steps: in the step 3), the voltage window adopted by the electrochemical deposition process is 0.8-1.8V.
8. The method for preparing the negative electrode material of the water-based zinc-ion battery according to claim 1, wherein the method comprises the following steps: in the step 3), the deposition current of the chronopotentiometric method adopted by the electrochemical deposition process is 10-100 mA, and the deposition time is 30-200 s.
9. The method for preparing the negative electrode material of the water-based zinc-ion battery according to claim 1, wherein the method comprises the following steps: in the step 3), after the negative electrode material is obtained, deionized water is used for repeated cleaning, and finally, the negative electrode material is naturally dried at room temperature.
10. A water-based zinc ion battery anode material with a functional protective layer, prepared by the preparation method of any one of claims 1-9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752554A (en) * | 2010-01-04 | 2010-06-23 | 北京航空航天大学 | Method for preparing Sn-Zn alloy cathode material of lithium ion battery |
| CN111508728A (en) * | 2020-04-29 | 2020-08-07 | 绍兴博捷智能科技有限公司 | Long-life manganese-based water system mixed zinc ion capacitor and preparation method thereof |
| CN112713268A (en) * | 2019-10-24 | 2021-04-27 | 宁德时代新能源科技股份有限公司 | Lithium metal composite electrode material, preparation method thereof, electrode containing lithium metal composite electrode material, battery module, battery pack and device |
| CN114142013A (en) * | 2021-11-30 | 2022-03-04 | 中南大学 | Lithium-loaded composite framework material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752554A (en) * | 2010-01-04 | 2010-06-23 | 北京航空航天大学 | Method for preparing Sn-Zn alloy cathode material of lithium ion battery |
| CN112713268A (en) * | 2019-10-24 | 2021-04-27 | 宁德时代新能源科技股份有限公司 | Lithium metal composite electrode material, preparation method thereof, electrode containing lithium metal composite electrode material, battery module, battery pack and device |
| CN111508728A (en) * | 2020-04-29 | 2020-08-07 | 绍兴博捷智能科技有限公司 | Long-life manganese-based water system mixed zinc ion capacitor and preparation method thereof |
| CN114142013A (en) * | 2021-11-30 | 2022-03-04 | 中南大学 | Lithium-loaded composite framework material and preparation method and application thereof |
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