CN116314579B - Preparation method of multifunctional interface layer modified zinc anode - Google Patents
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Abstract
The invention provides a preparation method of a multifunctional interface layer modified zinc negative electrode, which utilizes an in-situ displacement reaction to generate a multifunctional ZnSe-Ag interface layer on the surface of the zinc negative electrode, on one hand, the ZnSe-Ag interface layer can reduce the nucleation overpotential of zinc ions, guide the uniform deposition of the zinc ions, effectively inhibit the growth of dendrites, greatly improve the service life and the cycle performance of a battery, and on the other hand, the ZnSe-Ag interface layer is used as a physical barrier to block the contact of the zinc negative electrode and water molecules, effectively solve the technical problems of side reactions such as hydrogen evolution, corrosion and the like of the zinc negative electrode of a water-based zinc ion battery, avoid the passivation of the surface of the negative electrode and the consumption of active zinc, prolong the service life of the battery, promote the practical process of the water-based zinc ion battery with high specific energy and stable cycle, and have simple operation and simple reaction conditions and can realize large-scale application.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a preparation method of a multifunctional interface layer modified zinc anode.
Background
With the increasing severity of global energy crisis and environmental pollution, there is an urgent need for renewable green clean energy that can be continuously developed. Electrochemical energy storage technology, i.e. batteries, are receiving more and more attention because of the advantages of convenient use, less environmental pollution, high conversion efficiency, etc. At present, lithium ion batteries are dominant in the energy storage market, but the organic electrolyte system used by the lithium ion batteries has potential safety hazards such as toxicity, flammability and the like, and the lithium metal resources are low in abundance and high in cost, so that the large-scale application of the lithium ion batteries is seriously hindered. To cope with this problem, researchers have proposed to replace the organic electrolyte with a safer aqueous electrolyte, and to develop a novel aqueous metal ion battery. Among many metals, zinc is abundant in nature, low in price, and high in energy density (820 mah.g -1 ，5855 mAh·cm -3 ) Has wide application prospect. By combining the angles of the two angles, the angle of the two angles is equal to the angle of the two angles,the water system zinc ion battery is an emerging energy storage system with great development prospect.
However, metallic zinc has thermodynamic instability in aqueous solution, and side reactions such as hydrogen evolution and corrosion inevitably exist when the metallic zinc is directly used as a negative electrode material of an aqueous battery, so that surface passivation and consumption of active zinc are caused. Meanwhile, uneven deposition-stripping of zinc ions is caused by a tip effect in the charge and discharge process, so that zinc dendrite growth is initiated, the battery cycle performance is deteriorated, and serious consequences such as short circuit can be even caused when serious. Various methods for guiding zinc to be uniformly deposited and inhibiting side reactions, such as three-dimensional electrode structure design, electrolyte additives and the like, have been proposed at present, but the problems of complex and complicated preparation process and poor cycle performance of electrode materials under high current density exist in the methods, and the large-scale application of the methods is limited. Therefore, developing a modified zinc anode material which is simple and convenient in preparation process and can be stably recycled under high current density is a problem to be solved in the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of a multifunctional interface layer modified zinc anode, which is simple and convenient in preparation process, suitable for large-scale production and excellent in cycle performance of the prepared multifunctional interface layer modified zinc anode under high current density.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a multifunctional interface layer modified zinc anode, which comprises the following steps:
(1) Mixing silver halide and selenium, and grinding to obtain mixed powder;
(2) Mixing the mixed powder obtained in the step (1) with ethylenediamine, and stirring under a light-shielding and sealing condition to obtain a precipitate;
(3) Washing and vacuum drying the precipitate obtained in the step (2) in sequence to obtain silver selenide;
(4) And (3) covering the silver selenide obtained in the step (3) on the surface of a zinc sheet, and performing hot pressing treatment to form a ZnSe-Ag interface layer on the surface of the zinc sheet to obtain the modified zinc cathode modified by the multifunctional interface layer.
Preferably, the ratio of the amount of silver halide to selenium in the step (1) is (1.8-2.4): 1.
preferably, the ratio of the amount of selenium substance to the volume of organic solvent in step (2) is 1mol: (20-28) mL.
Preferably, the stirring time in the step (2) is 40-54 h.
Preferably, the washing in the step (3) is sequentially performed by absolute ethanol centrifugal washing and deionized water centrifugal washing.
Preferably, the rotation speed of the absolute ethyl alcohol centrifugal cleaning is 4000-5000 r/min, and the time of the absolute ethyl alcohol centrifugal cleaning is 3-10 min.
Preferably, the temperature of the vacuum drying in the step (3) is 75-85 ℃, and the time of the vacuum drying is 22-26 hours.
Preferably, in the step (4), the diameter of the zinc sheet is (1-1.4) cm (180-220) μm.
Preferably, the pressure of the hot pressing treatment in the step (4) is 50-100 MPa, the temperature of the hot pressing treatment is 180-230 ℃, and the time of the hot pressing treatment is 1.5-3 h.
Preferably, the thickness of the ZnSe-Ag interface layer in the step (4) is 0.5-4 μm.
The invention provides a preparation method of a modified zinc cathode modified by a multifunctional interface layer, which comprises the steps of firstly mixing silver halide with selenium, grinding to obtain mixed powder, mixing the mixed powder with ethylenediamine, stirring the mixture under the conditions of light shielding and sealing to obtain a precipitate, and sequentially washing and vacuum drying to obtain silver selenide powder; and covering the silver selenide powder on the surface of a zinc sheet, and performing hot pressing treatment to form a ZnSe-Ag interface layer on the surface of the zinc sheet to obtain the modified zinc cathode modified by the multifunctional interface layer. The method provided by the invention utilizes in-situ substitution reaction (Ag 2 Se+Zn- & gtZnSe+2Ag) generates a multifunctional ZnSe-Ag interface layer on the surface of the zinc cathode, on the one hand, the ZnSe-Ag interface layerThe surface layer can reduce the nucleation overpotential of zinc ions, guide the uniform deposition of zinc ions, effectively inhibit the growth of dendrites, greatly improve the service life and the cycle performance of the battery, and on the other hand, the ZnSe-Ag interface layer is used as a physical barrier to block the contact of a zinc negative electrode and water molecules, so that the technical problems of side reactions such as hydrogen evolution, corrosion and the like existing in the zinc negative electrode of the water-based zinc ion battery are effectively solved, the passivation of the surface of the negative electrode and the consumption of active zinc are avoided, the service life of the battery is prolonged, and the practical process of the water-based zinc ion battery with high specific energy and stable cycle is promoted. The results of the examples show that the contact angle of the electrolyte of ZnSe-Ag@Zn-50 in the example 1 is 18.16 degrees, which is obviously smaller than the contact angle (62.11 degrees) of the unmodified zinc cathode in the comparative example 1, and the electrolyte affinity of the modified zinc cathode modified by the multifunctional interface layer prepared in the example 1 is stronger; znSe-Ag@Zn-50 and ZnSe-Ag@Zn-100 exhibited lower nucleation barriers and better cycling stability than the unmodified zinc anode of comparative example 1; the ZnSe-Ag@Zn-50 assembled symmetrical battery shows better rate performance than an unmodified zinc electrode assembled symmetrical battery; the surface of the unmodified zinc electrode in the comparative example 1 after 200 circles is provided with a large amount of zinc dendrites, and no dendrite is generated on the surface of the ZnSe-Ag@Zn-50 electrode, so that uniform deposition of ions is realized, and zinc dendrites can be effectively inhibited; at 5 mA.cm -2 After zinc is deposited for 1h under the current density, obvious zinc dendrites and bubbles can be seen on the section of the unmodified zinc electrode in the comparative example 1, and ZnSe-Ag@Zn-50 realizes uniform deposition without bubbles, so that dendrite growth and hydrogen evolution reaction can be effectively inhibited.
Drawings
FIG. 1 is an XRD pattern of ZnSe-Ag@Zn-50 prepared in example 1 of the present invention and of Bare Zn, an unmodified zinc anode in comparative example 1;
FIG. 2 is a TEM image of ZnSe-Ag@Zn-50 prepared in example 1 of the present invention;
FIG. 3 is an SEM image of ZnSe-Ag@Zn-50 prepared in example 1 of the present invention and a corresponding element distribution diagram;
FIG. 4 is a SEM image of a cross-section of ZnSe-Ag@Zn-50 prepared in example 1 of the invention;
FIG. 5 is a graph showing the static contact angle of the obtained ZnSe-Ag@Zn-50 prepared in example 1 of the present invention and the unmodified zinc anode of comparative example 1 against an electrolyte;
FIG. 6 is a graph showing the cycle performance of a symmetric battery in which ZnSe-Ag@Zn-50 obtained by the preparation of example 1, znSe-Ag@Zn-100 obtained by the preparation of example 2 and an unmodified zinc anode of comparative example 1 are respectively assembled;
FIG. 7 is a graph showing the ratio performance of the ZnSe-Ag@Zn-50 assembled symmetrical cell prepared in example 1 of the present invention compared to that of the symmetrical cell assembled with the unmodified zinc electrode in comparative example 1;
FIG. 8 is a graph showing a linear scanning curve (LSV) of ZnSe-Ag@Zn-50 prepared in example 1 of the present invention and an unmodified zinc electrode in comparative example 1;
FIG. 9 is an XRD pattern of the ZnSe-Ag@Zn-50 electrode prepared in example 1 and the unmodified zinc electrode in comparative example 1 after 200 cycles of the symmetrical cell of the present invention;
FIG. 10 is an SEM image of the surface morphology of the ZnSe-Ag@Zn-50 electrode prepared in example 1 and the unmodified zinc electrode in comparative example 1 after 200 cycles of the symmetric cell of the present invention;
FIG. 11 is an in-situ photomicrograph of ZnSe-Ag@Zn-50 prepared in example 1 of the present invention and an unmodified zinc electrode in comparative example 1 after zinc deposition.
Detailed Description
The invention provides a preparation method of a multifunctional interface layer modified zinc anode, which comprises the following steps:
(1) Mixing silver halide and selenium, and grinding to obtain mixed powder;
(2) Mixing the mixed powder obtained in the step (1) with ethylenediamine, and stirring under a light-shielding and sealing condition to obtain a precipitate;
(3) Washing and vacuum drying the precipitate obtained in the step (2) in sequence to obtain silver selenide;
(4) And (3) covering the silver selenide obtained in the step (3) on the surface of a zinc sheet, and performing hot pressing treatment to form a ZnSe-Ag interface layer on the surface of the zinc sheet to obtain the modified zinc cathode modified by the multifunctional interface layer.
In the present invention, the raw materials used are all conventional commercial products in the art unless otherwise specified.
The invention mixes silver halide and selenium and then grinds the mixture to obtain mixed powder.
In the present invention, the silver halide is preferably one or more of silver chloride or silver bromide.
In the present invention, the ratio of the amounts of the silver halide and selenium is preferably (1.8 to 2.4): 1, more preferably (1.9 to 2.1): 1, more preferably 2:1.
the manner of grinding is not particularly limited in the present invention, and grinding may be performed by a method well known in the art.
After the mixed powder is obtained, the mixed powder and ethylenediamine are mixed and stirred under the condition of light shielding and sealing to obtain a precipitate.
In the present invention, the ratio of the amount of selenium substance to the volume of the organic solvent is preferably 1mol: (20-28) mL, more preferably 1mol: (23-26) mL. The present invention controls the ratio of the amount of selenium material to the volume of the organic solvent in the above range to promote the full reaction of silver halide and selenium to convert to silver selenide.
In the present invention, the temperature of the stirring is room temperature. In the invention, the stirring time is preferably 40-54 h, more preferably 45-52 h. The invention controls the temperature and time of stirring in the above range to promote the full reaction of silver halide and selenium to convert into silver selenide.
After stirring is completed, the stirred product is preferably filtered to obtain a precipitate.
The filtration mode is not particularly limited in the invention, and solid-liquid separation can be realized by adopting a mode well known in the art.
After a precipitate is obtained, washing and vacuum drying are sequentially carried out on the precipitate to obtain silver selenide;
in the present invention, the washing is preferably sequentially performed by absolute ethanol centrifugal washing and deionized water centrifugal washing. In the invention, the rotation speed of the absolute ethyl alcohol centrifugal cleaning is preferably 4000-5000 r/min, more preferably 4300-4800 r/min. In the invention, the time for centrifugal washing of the absolute ethyl alcohol is preferably 3-10 min, more preferably 4-8 min. In the invention, the times of the centrifugal washing of the absolute ethyl alcohol are preferably 2-6 times, more preferably 4-5 times. The invention controls the rotation speed and time of the centrifugal washing of the absolute ethyl alcohol in the above range so as to remove the organic component impurities in the sediment.
In the invention, the rotation speed of centrifugal cleaning of the deionized water is preferably 4000-5000 r/min, more preferably 4300-4800 r/min. In the invention, the centrifugal cleaning time of the deionized water is preferably 3-10 min, more preferably 4-8 min. The invention controls the rotation speed and time of centrifugal cleaning of deionized water in the above range to remove inorganic component impurities in the precipitate. The invention has no special limit to the times of centrifugal washing of deionized water, and can realize washing until the washing liquid is neutral.
After the washing is completed, the washed product is preferably filtered to obtain a solid.
The filtration mode is not particularly limited in the invention, and solid-liquid separation can be realized by adopting a mode well known in the art.
After the solid is obtained, the silver selenide is obtained by vacuum drying the solid.
In the present invention, the temperature of the vacuum drying is preferably 75 to 85 ℃, more preferably 78 to 83 ℃. In the present invention, the time for vacuum drying is preferably 22 to 26 hours, more preferably 23 to 25 hours.
After silver selenide is obtained, the silver selenide is covered on the surface of a zinc sheet, hot pressing treatment is carried out, a ZnSe-Ag interface layer is formed on the surface of the zinc sheet, and the modified zinc cathode modified by the multifunctional interface layer is obtained.
The mode of covering is preferably uniform covering by using a screen.
In the present invention, the diameter of the zinc sheet is preferably (1 to 1.4) cm (180 to 220) μm, and more preferably 1.2cm 200 μm.
In the present invention, the zinc sheet is preferably pretreated before use.
In the present invention, the pretreatment preferably includes polishing the surface of the zinc sheet, and then sequentially washing the polished zinc sheet with ethanol and vacuum-drying. The invention removes the oxide layer on the surface by pre-treating the zinc sheet, so as to facilitate the subsequent zinc sheet and Ag 2 The Se is in direct contact and fully reacts.
In the present invention, the sandpaper used for polishing is preferably 2300 to 3800 mesh, more preferably 2500 to 3500 mesh, and even more preferably 3000 mesh. The method for cleaning the zinc sheet by the ethanol is not particularly limited, and the impurities on the surface of the zinc sheet can be removed. The invention is not particularly limited to vacuum drying, and the purpose of removing the solvent can be achieved.
In the invention, the pressure of the hot pressing treatment is preferably 50-100 MPa. In the invention, the temperature of the hot pressing treatment is preferably 180-230 ℃, more preferably 190-220 ℃. In the present invention, the time of the hot pressing treatment is preferably 1.5 to 3 hours, more preferably 2 hours. The invention controls the pressure and the temperature of the hot pressing treatment in the above range to ensure the zinc sheet and the Ag 2 Se can be fully contacted and reacted; the control time is in the above range so as to ensure that a complete interface layer can be generated on the surface of the zinc sheet. The complete interface layer can completely prevent water from contacting with the zinc cathode, which is beneficial to inhibiting hydrogen evolution and corrosion reaction; at the same time, provide more active sites to promote Zn 2+ And (5) uniformly depositing.
In the present invention, the thickness of the ZnSe-Ag interface layer is preferably 0.5 to 4. Mu.m, more preferably 1 to 3. Mu.m, and still more preferably 2. Mu.m. The invention controls the thickness of ZnSe-Ag interface layer in the above range to improve the modification effect and obtain the multifunctional interface layer modified zinc anode with excellent cycle performance under high current density.
The preparation method of the multifunctional interface layer modified zinc anode provided by the invention is simple to operate, mild in reaction condition and suitable for large-scale production.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. 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.
Example 1
The preparation method of the multifunctional interface layer modified zinc anode comprises the following steps:
(1) Weighing 2.87g of AgCl and mixing with 0.87g of Se powder, and grinding and mixing uniformly to obtain mixed powder;
(2) Mixing the mixed powder obtained in the step (1) with 25mL of ethylenediamine, transferring to a 30mL brown reagent bottle, sealing by a plug, stirring and reacting on a magnetic stirrer for 48 hours, and filtering to obtain a black precipitate;
(3) Washing the black precipitate obtained in the step (2) with absolute ethyl alcohol ions for 4 times, carrying out centrifugal washing with deionized water for several times until the solution is neutral, filtering to obtain a solid, and vacuum drying the solid at 80 ℃ for 24 hours to obtain silver selenide powder;
(4) Uniformly covering the silver selenide powder obtained in the step (3) on the surface of a zinc sheet by using a screen, placing the zinc sheet in a hot press, and carrying out hot press treatment for 2 hours at 200 ℃ and 50MPa to obtain a multifunctional modified zinc cathode modified by an interface layer, wherein the modified zinc cathode is recorded as ZnSe-Ag@Zn-50;
the zinc sheet is pretreated before use; the pretreatment is that the surface of a zinc sheet is polished by 3000-mesh sand paper, and then is washed by absolute ethyl alcohol and dried in vacuum.
Example 2
A modified zinc anode modified by a multifunctional interface layer, denoted ZnSe-Ag@Zn-100, was prepared as in example 1, differing from example 1 in that: the pressure of the hot pressing treatment in the step (4) is 100MPa.
Comparative example 1
The surface of the zinc sheet was polished with 3000 mesh sand paper, followed by ethanol washing and vacuum drying to obtain an unmodified zinc anode, designated as Bare Zn, except for no treatment.
XRD patterns of ZnSe-Ag@Zn-50 prepared in example 1 and unmodified zinc anode in comparative example 1 were obtained by detection using an X-ray diffractometer as shown in FIG. 1. As can be seen from fig. 1, comparing with the standard PDF card, it is proved that the ZnSe-Ag interface layer is successfully formed on the surface of the modified zinc anode modified by the multifunctional interface layer in example 1.
Observing the modified zinc cathode modified by the multifunctional interface layer prepared in the embodiment 1 by adopting a transmission electron microscope to obtain a TEM image, as shown in figure 2; as can be seen from fig. 2, the respective lattice fringes and distinct grain boundaries of ZnSe and Ag can be clearly seen, confirming the presence of ZnSe-Ag interface layer on the surface of the modified zinc negative electrode modified by the multifunctional interface layer in example 1.
The SEM image of the modified zinc cathode surface modified by the multifunctional interface layer obtained in example 1 and the corresponding element distribution diagram are shown in fig. 3 and the SEM image of the cross section are shown in fig. 4, and it can be seen from fig. 3 and 4 that the uniform distribution of Ag and Se elements and the thickness of ZnSe-Ag interface layer of the modified zinc cathode surface modified by the multifunctional interface layer obtained in example 1 is 2 μm.
The static contact angles of the multifunctional interface layer modified zinc cathode obtained in the example 1 and the unmodified zinc cathode of the comparative example 1 to electrolyte are tested, and a static contact angle test chart is shown in fig. 5; as can be seen from fig. 5, the electrolyte contact angle of the modified zinc negative electrode modified by the multifunctional interface layer prepared in example 1 is 18.16 ° which is significantly smaller than the contact angle (62.11 °) of the unmodified zinc negative electrode in comparative example 1, which indicates that the electrolyte affinity of the modified zinc negative electrode modified by the multifunctional interface layer prepared in example 1 is stronger.
The electrical property detection method comprises the following steps: the ZnSe-Ag@Zn-50 prepared in example 1, znSe-Ag@Zn-100 prepared in example 2 and the unmodified zinc anode in comparative example 1 were each assembled 2032 symmetrical button cell at 5 mAh.cm using a New Wiwe cell test system -2 Constant current charge and discharge is carried out under the current density.
(1) The cycle performance is detected by the electrical performance detection method, so that a cycle performance diagram of 2032 symmetrical batteries respectively assembled by ZnSe-Ag@Zn-50 prepared in example 1, znSe-Ag@Zn-100 prepared in example 2 and an unmodified zinc anode in comparative example 1 is shown in FIG. 6; as can be seen from fig. 6, znSe-ag@zn-50 and ZnSe-ag@zn-100 exhibited lower nucleation barriers and better cycle stability than the unmodified zinc anode of comparative example 1, indicating that the multifunctional interface layer-modified zinc anodes prepared in example 1 and example 2 can effectively improve cycle performance of the battery.
(2) The comparison chart of the multiplying power performance of the ZnSe-Ag@Zn-50 assembled symmetrical battery prepared in example 1 and the multiplying power performance of the symmetrical battery assembled by the unmodified zinc electrode in comparative example 1 is shown in FIG. 7; as can be seen from fig. 7, the ZnSe-ag@zn-50 assembled symmetric cell exhibited better rate performance than the unmodified zinc electrode assembled symmetric cell by varying the current density during cycling.
(3) The linear scanning curve (LSV) diagram of ZnSe-Ag@Zn-50 prepared in example 1 and the unmodified zinc electrode in comparative example 1 is shown in FIG. 8; as can be seen from FIG. 8, the corrosion potential of ZnSe-Ag@Zn-50 is more positive and the corrosion current is smaller than that of the unmodified zinc electrode, indicating that ZnSe-Ag@Zn-50 has excellent corrosion resistance.
(4) By using the electrical property detection method, after the symmetrical battery is circulated for 200 circles, XRD patterns of the ZnSe-Ag@Zn-50 electrode and the unmodified zinc electrode in the comparative example 1 are detected and are shown in figure 9; as can be seen from fig. 9, the surface of the unmodified zinc anode in comparative example 1 showed a significant by-product, which was insulating and electrochemically inactive, severely blocking the transport of zinc ions and electrons, while the ZnSe-ag@zn-50 electrode surface still showed the same diffraction peak as in the original state, indicating that the side reaction was effectively suppressed.
(5) By using the above electrical property detection method, after the symmetric battery is cycled for 200 circles, SEM images of the surface morphology of the ZnSe-Ag@Zn-50 electrode and the unmodified zinc electrode in comparative example 1 are detected, as shown in FIG. 10, as can be seen from FIG. 10, the surface of the unmodified zinc electrode in comparative example 1 after 200 circles is cycled, a large amount of zinc dendrites are formed on the surface of the ZnSe-Ag@Zn-50 electrode, uniform deposition of ions is realized, and the modified zinc cathode modified by the multifunctional interface layer prepared in example 1 can effectively inhibit zinc dendrites.
At 5 mA.cm -2 After zinc is deposited for 1h under the current density, the morphology of the electrode is observed by utilizing a light mirror, and an in-situ light mirror diagram of the modified zinc electrode modified by the multifunctional interface layer prepared in the example 1 and the unmodified zinc electrode in the comparative example 1 after zinc deposition is obtained is shown in fig. 11; as can be seen from fig. 11, the cross section of the unmodified zinc electrode in comparative example 1 can see obvious zinc dendrites and bubbles, while ZnSe-ag@zn-50 realizes uniform deposition without bubbles, indicating that ZnSe-ag@zn-50 electrode can effectively inhibit dendrite growth and hydrogen evolution reaction.
In summary, the surface of the modified zinc anode modified by the multifunctional interface layer in the embodiment 1 successfully generates a ZnSe-Ag interface layer, the contact angle of electrolyte of ZnSe-Ag@Zn-50 is 18.16 degrees, which is obviously smaller than the contact angle (62.11 degrees) of the unmodified zinc anode in the comparative example 1, and the affinity of electrolyte of the modified zinc anode modified by the multifunctional interface layer prepared in the embodiment 1 is stronger; znSe-Ag@Zn-50 and ZnSe-Ag@Zn-100 exhibited lower nucleation barriers and better cycling stability than the unmodified zinc anode of comparative example 1; the ZnSe-Ag@Zn-50 assembled symmetrical battery shows better rate performance than an unmodified zinc electrode assembled symmetrical battery; the surface of the unmodified zinc electrode in the comparative example 1 after 200 circles is provided with a large amount of zinc dendrites, and no dendrite is generated on the surface of the ZnSe-Ag@Zn-50 electrode, so that uniform deposition of ions is realized, and zinc dendrites can be effectively inhibited; at 5 mA.cm -2 After zinc is deposited for 1h under the current density, obvious zinc dendrites and bubbles can be seen on the section of the unmodified zinc electrode in the comparative example 1, and ZnSe-Ag@Zn-50 realizes uniform deposition without bubbles, so that dendrite growth and hydrogen evolution reaction can be effectively inhibited. The modified zinc anode material modified by the multifunctional interface layer can reduce the nucleation barrier in the zinc ion deposition process, and has uniform ion flux, thus realizing dendrite-free deposition; meanwhile, the interface layer is used as a physical barrier to effectively block the contact of the zinc cathode and the water electrolyte and inhibit side reactions such as hydrogen evolution and corrosion.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A preparation method of a multifunctional interface layer modified zinc anode comprises the following steps:
(1) Mixing silver halide and selenium, and grinding to obtain mixed powder;
(2) Mixing the mixed powder obtained in the step (1) with ethylenediamine, and stirring under a light-shielding and sealing condition to obtain a precipitate;
(3) Washing and vacuum drying the precipitate obtained in the step (2) in sequence to obtain silver selenide;
(4) Covering the silver selenide obtained in the step (3) on the surface of a zinc sheet, performing hot pressing treatment, and forming a ZnSe-Ag interface layer on the surface of the zinc sheet to obtain a modified zinc cathode modified by the multifunctional interface layer;
the pressure of the hot pressing treatment in the step (4) is 50-100 MPa, the temperature of the hot pressing treatment is 180-230 ℃, and the time of the hot pressing treatment is 1.5-3 h.
2. The method for preparing a modified zinc anode modified by a multifunctional interface layer according to claim 1, wherein the ratio of the amounts of silver halide and selenium in the step (1) is (1.8-2.4): 1.
3. the method for preparing a modified zinc anode modified by a multifunctional interface layer according to claim 1, wherein the ratio of the amount of selenium in the step (1) to the volume of ethylenediamine in the step (2) is 1mol: (20-28) mL.
4. The method for preparing a modified zinc anode modified by a multifunctional interface layer according to claim 1, wherein the stirring time in the step (2) is 40-54 h.
5. The method for preparing the modified zinc cathode modified by the multifunctional interface layer according to claim 1, wherein the washing in the step (3) is sequentially carried out absolute ethanol centrifugal washing and deionized water centrifugal washing.
6. The method for preparing the modified zinc cathode modified by the multifunctional interface layer according to claim 5, wherein the rotation speed of the absolute ethyl alcohol centrifugal cleaning is 4000-5000 r/min, and the time of the absolute ethyl alcohol centrifugal cleaning is 3-10 min.
7. The method for preparing a modified zinc anode modified by a multifunctional interface layer according to claim 1, wherein the temperature of vacuum drying in the step (3) is 75-85 ℃, and the time of vacuum drying is 22-26 h.
8. The method for preparing a modified zinc anode modified by a multifunctional interface layer according to claim 1, wherein the diameter of the zinc sheet in the step (4) is (1-1.4) cm (180-220) μm.
9. The method for preparing a modified zinc anode modified by a multifunctional interface layer according to claim 1, wherein the thickness of the ZnSe-Ag interface layer in the step (4) is 0.5-4 μm.
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| CN115799512A (en) * | 2022-11-29 | 2023-03-14 | 安徽工业大学 | Preparation and application of cathode material of water-based zinc ion battery capable of inhibiting dendritic crystal growth |
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| JP2014149993A (en) * | 2013-02-01 | 2014-08-21 | Nippon Shokubai Co Ltd | Zinc negative electrode, battery and electrode base layer |
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| CN115799512A (en) * | 2022-11-29 | 2023-03-14 | 安徽工业大学 | Preparation and application of cathode material of water-based zinc ion battery capable of inhibiting dendritic crystal growth |
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